CN107108795A - Fluorine-containing pyrolytic resin, anti-corrosion agent composition, color filter protecting layer composition, etchant resist and color filter protecting layer - Google Patents

Fluorine-containing pyrolytic resin, anti-corrosion agent composition, color filter protecting layer composition, etchant resist and color filter protecting layer Download PDF

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Publication number
CN107108795A
CN107108795A CN201580057850.8A CN201580057850A CN107108795A CN 107108795 A CN107108795 A CN 107108795A CN 201580057850 A CN201580057850 A CN 201580057850A CN 107108795 A CN107108795 A CN 107108795A
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methyl
fluorine
acid
acrylate
foregoing
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CN201580057850.8A
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CN107108795B (en
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笹本慎
高野启
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • C08F20/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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

Abstract

It is an object of the invention to; a kind of resin is provided; it, which can assign high flatness to each pixel of colour filter, the diaphragm of the pixel and can provide in pixel in the case of formation diaphragm and then on diaphragm in the case of coating material coating, is used to form the composition of foregoing diaphragm, can apply the composition of foregoing coating material well; for this purpose; a kind of fluorine-containing pyrolytic resin is provided, it has：The main chain (a) of polymer architecture with polymerizable monomer and following formulas (1) (in formula, R1、R2And R3The respectively organic group of hydrogen atom or carbon number 1~18, R4For fluorinated alkyl or poly- (perfluorinated alkylidene ether) chain.Y1For oxygen atom or sulphur atom.) shown in the side chain (b) with functional group.

Description

Fluorine-containing pyrolytic resin, anti-corrosion agent composition, color filter protecting layer composition, Etchant resist and color filter protecting layer
Technical field
Anti-corrosion agent composition and color filter protecting layer composition the present invention relates to resin, containing the resin and use this Etchant resist and color filter protecting layer obtained from a little compositions, the resin can be to each pixel of colour filter, for protecting colour filter The diaphragm of device assigns high flatness, and can provide in pixel in the case of formation diaphragm and then on diaphragm It is used for composition, the Neng Gouliang for forming foregoing diaphragm in the case of coating coating material, film of the stacking with various functions The composition of foregoing coating material is applied well.
Background technology
The colour filter used in color liquid crystal display arrangement, organic EL display generally has red (R), green (G), indigo plant Etc. (B) each colour element and the purpose such as display contrast for raising therebetween and form the basic structure of black matrix" (BM) Into.For each pixel and black matrix", display quality is improved in order to reduce irregular colour etc., it is desirable to high flatness.
In order to reach the high flatness of colour filter, the combination for forming foregoing each colour element and black matrix" is used as Thing, it is desirable to form uniform thickness and will not occur crawling, repulsion, the composition of color spot will not be formed.Moreover, being Reach the high flatness of colour filter and by the concavo-convex hidden of the surface produced on the border of foregoing each colour element and black matrix" Hide, therefore form color filter protecting layer.For formed the composition of the color filter protecting layer also with for formed each pixel and The composition of black matrix" similarly requires high flatness.
For the combination to the composition for forming each colour element and black matrix", for forming color filter protecting layer Thing assigns flatness, can use fluorine system additive.For example, disclosing containing making the free-radical polymerised list with perfluoroalkyl Composition (the example of the resin containing fluorine atom obtained from body and free radical polymerization monomer copolymerization with polyalkylene glycol chain Such as, with reference to patent document 1.).
But, for the film of the composition containing the resin containing fluorine atom described in patent document 1, in fluorine-contained surface tree Fat can segregation.As a result have and crawling is easily produced when being applied again, repels fully assure the painting through applying again The problem of flatness of film.If directly manufacturing colour filter using the insufficient film of such flatness, display product can be become The colour filter of matter difference.If the region for avoid in order to avoid the problem producing the crawling on film, repelling manufactures colour filter Device, then can cause deterioration, the rising of production cost of the yield rate in colour filter manufacture.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-065865 publications
The content of the invention
Problems to be solved by the invention
Problem to be solved by this invention is that anti-corrosion agent composition, colour filter there is provided resin, containing the resin are protected Film composition and using etchant resist and color filter protecting layer obtained from these compositions, the resin can be to each of colour filter Pixel, for protecting the diaphragm of colour filter to assign high flatness, and the feelings that diaphragm is formed in pixel can be provided It is used to form foregoing guarantor in the case of being coated with the film of coating material, stacking with various functions under condition and then on diaphragm The composition of cuticula, the composition that foregoing coating material can be applied well.
The solution used to solve the problem
The present inventor etc. have made intensive studies to solve the above problems, and as a result find, with through blocked carboxyl, Specifically the resin of the functional group containing fluorine atom shown in following formulas has surface active function, by containing composition The resin, can reach the smoothing of the films such as etchant resist, color filter protecting layer, by the way that the film of smoothedization is placed on into height Under warm environment in the environment of such as 150~300 DEG C, the functional group containing fluorine atom is from through blocked carboxyl disengaging, film coated surface Water repellency and oil repellent can reduce, due to the fluorine-based disappearance that contains of aforementioned resin, the wetability of film coated surface is improved, therefore is held Film (easily applying again) etc. is easily laminated, so as to complete the present invention.
That is, the present invention provides a kind of fluorine-containing pyrolytic resin, it is characterised in that have：It is poly- with polymerizable monomer The side chain (b) with functional group shown in the main chain (a) of compound structure and following formulas (1),
(in formula, R1、R2And R3The respectively organic group of hydrogen atom or carbon number 1~18, R4For fluorinated alkyl or poly- (perfluorinated alkylidene ether) chain.Y1For oxygen atom or sulphur atom.〕.
In addition, the present invention provides a kind of anti-corrosion agent composition, it is characterised in that include foregoing fluorine-containing pyrolytic resin.
In addition, the present invention provides a kind of color filter protecting layer composition, it is characterised in that include foregoing fluorine-containing thermal decomposition Property resin.
And then, the present invention provides a kind of etchant resist, it is characterised in that be using obtained from foregoing anti-corrosion agent composition.
And then, the present invention provides a kind of color filter protecting layer, it is characterised in that be using foregoing color filter protecting layer group Obtained from compound.
The effect of invention
In accordance with the invention it is possible to provide a kind of resin, it can be to each pixel of colour filter, the protection for protecting colour filter Film assign high flatness and also can provide form diaphragm in pixel in the case of so that the coating on diaphragm It is used to form the composition of foregoing diaphragm in the case of the film of material, stacking with various functions, can applies well The composition of foregoing coating material.By using the anti-corrosion agent composition of the fluorine-containing pyrolytic resin containing the present invention, colour filter Device protects film composition, so as to obtain the smooth and easily further etchant resist of stacking film, colour filter protection Film.In addition, by making the fluorine-containing thermal decomposition containing the present invention in semiconductor anti-corrosion agent composition, semiconducting insulation film composition Property resin, smooth and easy further semiconductor etchant resist, semiconducting insulation film, the semiconductor of stacking film can be obtained Antireflection film.
Brief description of the drawings
Fig. 1 is the IR spectrograms of the fluorine-containing pyrolytic resin (1) obtained in embodiment 1.
Fig. 2 is the fluorine-containing pyrolytic resin (1) obtained in embodiment 113C-NMR spectrograms.
Fig. 3 is the GPC figures of the fluorine-containing pyrolytic resin (1) obtained in embodiment 1.
Embodiment
The fluorine-containing pyrolytic resin of the present invention is characterised by having：Polymer architecture with polymerizable monomer The side chain (b) with functional group shown in main chain (a) and aforementioned formula (1).
It is preferred that among the side chain (b) with functional group shown in aforementioned formula (1), R1、R2And R3Respectively hydrogen atom.
From the fluorine-containing pyrolytic resin aspect for obtaining showing excellent flatness, shown in aforementioned formula (1) R in side chain (b) with functional group4Preferably the number of the carbon atom of fluorine atom Direct Bonding for 1~6 fluorinated alkyl, More preferably the number of the carbon atom of fluorine atom Direct Bonding is 4~6 fluorinated alkyl, more preferably fluorine atom direct key The number of the carbon atom of conjunction is 6 fluorinated alkyl.
As foregoing preferred side chain (b), such as may be preferably exemplified out it is following in the side chain that shows.Among these, For the side chain shown in formula (1-1), industrial obtainable raw material can be used and obtains, surface free energy amount is low, therefore easily The fluorine-containing pyrolytic resin of the excellent flatness of synthesis performance, therefore preferably.
The fluorine-containing pyrolytic resin of the present invention can contain except foregoing logical in the range of the effect of the present invention is not damaged Side chain (b') beyond formula (1).As foregoing side chain (b'), for example, following formulas (1') shown side chain can be exemplified.
(in formula, R11、R21And R31The respectively organic group of hydrogen atom or carbon number 1~18, R41For carbon number 1~ 18 organic group, R31And R41It can bond together and be formed with Y11For heteroatomic heterocycle, Y11For oxygen atom or sulphur atom.)
From the difference through blocked carboxyl and the polarity of the carboxyl brought back to life it is big, obtain and can obtain that the smooth of film can be taken into account Set out in terms of the fluorine-containing pyrolytic resins of cured coating film such as etchant resist, the color filter protecting layer of property and recoatability, preferably It is that aforementioned formula is (1') among the shown side chain (b') with functional group, R11、R21And R31Respectively hydrogen atom, R41It is former for carbon The organic group of subnumber 1~18, Y1For oxygen atom or sulphur atom, the more preferably side chain shown in following formula (1'-1).
The fluorine-containing pyrolytic resin of the present invention can for example lead to following methods and effectively manufacture.
Preparation method 1：The polymerizable monomer (α) with carboxyl is set to be reacted with the vinyl ether compound shown in following formulas (2) And obtain having after the polymerizable monomer of blocked carboxyl, the method for polymerizeing the polymerizable monomer,
(in formula, R1、R2And R3The respectively organic group of hydrogen atom or carbon number 1~18, R4For fluorinated alkyl or poly- (perfluorinated alkylidene ether) chain.〕.
Preparation method 2：Make obtained from the polymerizable monomer (α) with carboxyl shown in polymer and aforementioned formula (2) The method of vinyl ether compound reaction.
The fluorine-containing decomposability resin obtained in foregoing preparation method 1 is that will be used as aforementioned polymeric monomer (α) and formula (2) institute The reaction product of the vinyl ether compound shown have the polymerizable monomer through blocked carboxyl as inscape tree Fat.In addition, the fluorine-containing decomposability resin obtained in foregoing preparation method 2 is by with polymerization of the foregoing polymerizable monomer (α) for raw material Vinyl ether compound shown in thing and formula (2) as inscape resin.
As the foregoing polymerizable monomer (α) with carboxyl, for example, it may be preferably exemplified out：(methyl) acrylic acid, clothing health Acid, mesaconic acid, maleic acid, fumaric acid, (methyl) carboxyethyl acrylates, (methyl) acrylic acid carboxyl pentyl ester, 2- (methyl) third Alkene trimethylammonium hexahydrophthalic acid ester, 2- (methyl) acryloxypropyl hexahydrophthalic acid ester, 2- (methyl) Acryloyl-oxyethyl phthalic acid ester, 2- (methyl) acryloyloxyethyl succinate, 2- (methyl) acryloxy Ethyl maleate, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl tetrahydrochysene O-phthalic Acid esters etc..Wherein, from aspect that is cheap and being easily processed, preferably (methyl) acrylic acid, more preferably methacrylic acid.
It should be noted that in the present invention, during " (methyl) acrylate " is methacrylate and acrylate One or both, " (methyl) acryloyl group " refers to one or both of methylacryloyl and acryloyl group, " (methyl) third Olefin(e) acid " is one or both of methacrylic acid and acrylic acid.
As the vinyl ether compound shown in aforementioned formula (2), for example, it can include：3,3,4,4,5,5,6,6,7,7, The fluoro- 1- ethyleneoxies octanes of 8,8,8- 13, the fluoro- 1- ethyleneoxies hexanes of 3,3,4,4,5,5,6,6,6- nine etc..Wherein from The reaction of the polymer obtained using aforementioned polymeric monomer (α) easily carry out and before heating after polarity difference it is big, formed Set out in terms of the flatness of cured coating film and the fluorine-containing pyrolytic resin of recoatability can be taken into account, preferably 3,3,4,4,5,5,6, The fluoro- 1- ethyleneoxies octanes of 6,7,7,8,8,8- 13.
Obtaining having in previous building methods 1 gathers the polymerizable monomer after the polymerizable monomer of blocked carboxyl , can also be not when polymer obtained from using the polymerizable monomer (α) with carboxyl is obtained during conjunction, in manufacture method 2 The polymerizable monomer (γ) in addition to polymerizable monomer (α) is applied in combination to be polymerize in the range of the effect for damaging the present invention Thing.As polymerizable monomer (γ), for example, it can include：Esters of acrylic acid, methyl acrylic ester, acrylic amide, methyl Acrylic amide, allyl compound, vinyl ethers, vinyl ester etc..
As foregoing acrylates class, for example, it can include：Methyl acrylate, ethyl acrylate, propyl acrylate, propylene Sour chloroethene ester, 2-Hydroxy ethyl acrylate, trimethylolpropane mono acrylic ester, benzyl acrylate, methoxyethyl benzyl Ester, acrylic acid furfuryl group ester, acrylic acid tetrahydro furfuryl ester etc..
As foregoing methyl acrylic ester, for example, it can include：Methyl methacrylate, EMA, first Base propyl acrylate, methacrylic acid chloroethene ester, methacrylic acid -2- hydroxy methacrylates, trimethylolpropane monomethacrylate Ester, benzyl methacrylate, methacrylic acid methoxyl group benzyl ester, methacrylic acid furfuryl group ester, methacrylic acid tetrahydro furfuryl ester Deng.
As foregoing acryloyl amine, for example, it can include：Acrylamide, N- alkyl acrylamides (are carbon as alkyl The alkyl of atomicity 1~3, for example, methyl, ethyl, propyl group), N, N- dialkylacrylamides (as alkyl, be carbon number 1~ 3 alkyl), N- hydroxyethyls-N methacrylamide, N-2- acetamide ethyl-N- acetylacrylamides etc..
As foregoing methacryl amine, for example, it can include：Methacrylamide, N- alkyl methacrylamides (being the alkyl of carbon number 1~3 as alkyl, such as methyl, ethyl, propyl group), N, N- dialkyl methacrylamides (are made Be the alkyl of carbon number 1~3 for alkyl), N- hydroxyethyl-N- methyl methacrylamides, N-2- acetamide ethyls-N- Acetylmethacrylamide etc..
As foregoing allylic compound, for example, it can include：Pi-allyl esters are (for example, allyl acetate, caproic acid allyl Ester, allyl octanoate, bay allyl propionate, palm allyl propionate, stearic allyl propionate, allyl benzoate, acetoacetate alkene Propyl ester, allyl lactate etc.), allyloxyethanol etc..
As foregoing vinyl ethers, for example, it can include：Hexyl vinyl ethers, octyl vinyl ether, decyl ethylene base Ether, ethylhexyl vinyl ether, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1- first Base -2,2- dimethylpropyl vinyl ethers, 2- ethylbutyl vinyl ethers, hydroxyethyl vinyl ether, diethylene glycol vinyl Ether, dimethyl aminoethyl vinyl base ether, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ethers, benzyl second Alkene ether, tetrahydrofurfuryl vinyl ethers etc., vinyl ester：Vinyl butyrate, vinyl isobutyrate ester, vinyl trimethylacetate Ester, diethacetic acid vinyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate ester, methoxy Vinyl acetate, butoxy acetic acid vinyl acetate, lactate, beta-phenyl butyric acid vinyl esters, cyclohexane carboxylic acid vinyl acetate Deng.
As foregoing Dialkyl itaconates class, it can include：Dimethyl itaconate, diethyl itaconate, itaconic acid two Butyl ester etc..As the dialkyl esters or monoalkyl esters of fumaric acid, dibutyl fumarate etc. and crotons can also be enumerated Acid, itaconic acid, acrylonitrile, methacrylonitrile, maleoyl nitrile (マ レ イ ロ ニ ト リ Le), styrene etc..
In addition, as polymerizable monomer (γ), the free radical polymerization monomer with oxyalkylene can also be used.As Free radical polymerization monomer with oxyalkylene, for example, can include：Polypropylene glycol list (methyl) acrylate, poly- four methylene Base glycol (methyl) acrylate, poly- (ethylene glycol propane diols) single (methyl) acrylate, polyethylene glycol polypropylene glycol list (methyl) acrylate, poly- (ethylene glycol tetramethylene glycol) single (methyl) acrylate, polyethylene glycol polytetramethylene Glycol list (methyl) acrylate, poly- (propane diols tetramethylene glycol) single (methyl) acrylate, polypropylene glycol poly- four Methylene glycol list (methyl) acrylate, poly- (propane diols butanediol) single (methyl) acrylate, the poly- fourth of polypropylene glycol Glycol list (methyl) acrylate, poly- (ethylene glycol butanediol) single (methyl) acrylate, polyethylene glycol polytetramethylene glycol list (methyl) acrylate, poly- (tetraethylene glycol butanediol) single (methyl) acrylate, poly- tetraethylene glycol polytetramethylene glycol list (first Base) acrylate, polytetramethylene glycol list (methyl) acrylate, poly- (ethylene glycol trimethylene) single (methyl) acrylic acid Ester, polyethylene glycol polytrimethylene glycol list (methyl) acrylate, poly- (propane diols trimethylene) are single (methyl) Acrylate, polypropylene glycol polytrimethylene glycol list (methyl) acrylate, poly- (trimethylene tetramethylene two Alcohol) single (methyl) acrylate, polytrimethylene glycol polytetramethylene glycol list (methyl) acrylate, poly- (fourth two Alcohol trimethylene) single (methyl) acrylate, polytetramethylene glycol polytrimethylene glycol list (methyl) acrylate etc..
It should be noted that foregoing " poly- (ethylene glycol propane diols) " refers to the random copolymer of ethylene glycol and propane diols, " polyethylene glycol polypropylene glycol " refers to the block copolymer of ethylene glycol and propane diols, for other similarly.
As the commercially available product of the foregoing free radical polymerization monomer with oxyalkylene, for example, it can include：Xin Zhong villages Learn " NK ESTER AMP-10G ", " NK ESTER AMP-20G ", " NK ESTER AMP-60G ", the day of Industrial Co., Ltd " Blemmer PME-100 ", " Blemmer PME-200 ", " Blemmer PME-400 ", " Blemmer of oily Co. Ltd. system PME-4000”、“Blemmer PP-1000”、“Blemmer PP-500”、“Blemmer PP-800”、“Blemmer 70PEP- 350B”、“Blemmer 55PET-800”、“Blemmer 50POEP-800B”、“Blemmer 10PPB-500B”、“Blemmer NKH-5050 ", " Blemmer AP-400 ", " SR604 " of SARTOMER company systems etc..Free radical polymerization monomer (γ) can be with It is used alone, two or more can also be applied in combination.
And then, as polymerizable monomer (γ), can also be used in the range of the effect of the present invention is not damaged has fluorine Change alkyl, the free radical polymerization monomer of poly- (perfluorinated alkylidene ether) chain., for example can be with excellent as the free radical polymerization monomer Choosing exemplifies the monomer shown in following formulas (γ 1).
(in above-mentioned formula (γ 1), R represents hydrogen atom or methyl, and L represents wantonly a kind in following formula (L-1)~(L-10) Group, Rf represents wantonly a kind of group in following formula (Rf-1)~(Rf-7).〕
-OCnH2n- (L-1)
-OCH2CH2OCH2- (L-2)
-CnF2n+1 (Rf-1)
-CnF2nH (Rf-2)
-CnF2n-1 (Rf-3)
-CnF2n-3 (Rf-4)
-CmF2mOCnF2nCF3 (Rf-5)
-CH2CmF2m(OCnF2n)lOCpF2pCF3 (Rf-6)
-CF2OC2F4OC2F4OCF3 (Rf-7)
N in above-mentioned formula (Rf-1)~(Rf-4) is, for example, 1~6 integer, preferably 4~6 integer.Above-mentioned formula (Rf- 5) m in is, for example, 1~18 integer, and n is 0~5 integer, and m and n summation is 1~23.Preferably, m is 1~5 Integer, n is 0~4 integer, and m and n adds up to 4~5.M in above-mentioned formula (Rf-6) is, for example, 1~6 integer, n It is 1~20 integer for 1~3 integer, 1, p is 0~5 integer, also, the summation of m, p and n and l product is 2~71. Preferably, m is 1~3 integer, and n is 1~3 integer, and l is 1~6 integer, and p is 0~2 integer, also, m, p and n Summation with 1 product is 2~23.
It is used as the foregoing specific example with fluorinated alkyl, the free radical polymerization monomer of poly- (perfluorinated alkylidene ether) chain Son, such as may be preferably exemplified out following polymerizable monomers (γ 1-1)~(γ 1-15).
N in formula (γ 1-1)~formula (γ 1-11) is, for example, 0~5.In addition, the n in (γ 1-12)~(γ 1-15) is for example For 0~20.
In addition, when obtaining the fluorine-containing pyrolytic resin of the present invention, the model of effect of the invention can also do not damaged The ethene shown in the vinyl ether compound and formula (2) in addition to the compound shown in aforementioned formula (2) is applied in combination in enclosing Base ether compound.As such vinyl ether compound, for example, it can include：It is methyl vinyl ether, ethyl vinyl ether, different Propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, IVE, 2- ethylhexyl vinyl ethers, The aliphatic ethylene base ether compound such as cyclohexyl vinyl ether；The aliphatic ethylene base sulfide compound corresponding with them；2, 3- dihydrofuran, 3,4- dihydrofuran, 2,3- dihydro -2H- pyrans, 3,4- dihydro -2H- pyrans, 3,4- dihydro -2- methoxyl groups - 2H- pyrans, 3,4- dihydro -4,4- dimethyl -2H- pyran-2-ones, 3,4- dihydro -2- ethyoxyl -2H- pyrans, 3,4- dihydros - The cyclic vinyl ether compounds such as 2H- pyrans -2- carboxylic acid sodiums；Cyclic vinyl sulfide compound corresponding with them etc..
In foregoing preparation method 1, the polymerizable monomer (α) with carboxyl is set to be etherified with the vinyl shown in aforementioned formula (2) Compound reacts.Thus obtain that there is the polymerizable monomer through blocked carboxyl.Reaction condition can be for example included in acid catalysis In the presence of agent, in 20~100 DEG C or so the conditions heated.Moreover, making that there is the polymerism list through blocked carboxyl When body polymerize, it can make to carry out under conditions of polymerizable monomer (α) polymerization aftermentioned.
In foregoing preparation method 2, as the method that polymer is obtained using polymerizable monomer (α), it is not particularly limited, for example It can include using radical polymerization initiator, make polymerizable monomer (α) and the free radical polymerization monomer used as needed Method that (γ) polymerize in organic solvent etc..It is used as organic solvent used herein, preferably ketone, esters, amide-type, sulfoxide Class, ethers, hydro carbons, specifically, can be included：Acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl acetate, acetic acid Butyl ester, propylene glycol methyl ether acetate, dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), Anaesthetie Ether, Di Iso Propyl Ether, tetrahydrofuran, dioxanes, toluene, dimethylbenzene etc..They can contemplate boiling point, compatibility, gather Conjunction property is suitably selected.As radical polymerization initiator, peroxide, idol such as can exemplify benzoyl peroxide Azo-compounds such as the double isobutyronitriles of nitrogen etc..And then can use as needed lauryl mercaptan, 2 mercapto ethanol, thioglycerol, The chain-transferring agents such as ethyl thioglycolate, TGA monooctyl ester.
In foregoing preparation method 2, vinyl ether compound shown in aforementioned polymer and aforementioned formula (2) can be for example, by In the presence of acid catalyst, heated to react at 20~100 DEG C or so.By the reaction, the carboxylic that polymer has Base progress is blocked, obtains the polymer with the structure shown in aforementioned formula (1).For foregoing through blocked carboxyl, Under hot environment in the environment of such as 150~300 DEG C, it can depart from through blocked vinyl ethers, then produce carboxyl.
Due to containing fluorine atom, therefore in film coated surface segregation occurs for the fluorine-containing pyrolytic resin of the present invention.In the table Occur on face in the state of segregation, fluorinated alkyl, poly- (perfluorinated alkylidene ether) chain depart from and volatilized from fluorine-containing pyrolytic resin, So as to water repellency and the oil repellent reduction of film coated surface.As the result of such phenomenon, inventor etc. thinks to can obtain easily The film applied again.
For the number-average molecular weight (Mn) of the fluorine-containing pyrolytic resin of the present invention, protected from forming etchant resist, colour filter The aspect that the compatibility of other resins of the cured coating films such as cuticula is good is set out, preferably 1000~50000 scope, more preferably 1500~20000 scope, further preferred 2000~8000 scope.In addition, from formed cured coating film other resins The good aspect of compatibility set out, the scope of weight average molecular weight (Mw) preferably 1000~100000, more preferably 5000~70000 Scope.
In present invention, it is desirable to explanation, number-average molecular weight (Mn) and weight average molecular weight (Mw) are to be impregnated with color based on gel Spectrometry (it is following, it is abbreviated as " GPC ".) determine the value for having carried out polystyrene conversion.It should be noted that GPC condition determination It is as follows.
[GPC condition determinations]
Determine device：TOSOH CORPORATION systems " HLC-8220GPC ",
Post：TOSOH CORPORATION guard columns " HHR-H " (6.0mmI.D. × 4cm)+TOSOH CORPORATION " TSK-GELGMHHR-N " (7.8mmI.D. × 30cm)+TOSOH CORPORATION systems " TSK-GELGMHHR-N " of system (7.8mmI.D. × 30cm)+TOSOH CORPORATION systems " TSK-GELGMHHR-N " (7.8mmI.D. × 30cm)+TOSOH CORPORATION systems " TSK-GELGMHHR-N " (7.8mmI.D. × 30cm)
Detector：ELSD (Alltech company systems " ELSD2000 ")
Data processing：TOSOH CORPORATION systems " GPC-8020model II data analysis edition 4s .30 "
Condition determination：40 DEG C of column temperature
Developing solvent tetrahydrofuran (THF)
Flow velocity 1.0ml/ minutes
Sample：The tetrahydrofuran solution that 1.0 mass % are scaled with resin solid content was carried out with millipore filter Material (5 μ l) obtained by filter.
Standard specimen：According to it is foregoing " GPC-8020model II data analysis edition 4s .30 " measure handbook, using point The known following monodisperse polystyrene of son amount.
(monodisperse polystyrene)
TOSOH CORPORATION systems " A-500 "
TOSOH CORPORATION systems " A-1000 "
TOSOH CORPORATION systems " A-2500 "
TOSOH CORPORATION systems " A-5000 "
TOSOH CORPORATION systems " F-1 "
TOSOH CORPORATION systems " F-2 "
TOSOH CORPORATION systems " F-4 "
TOSOH CORPORATION systems " F-10 "
TOSOH CORPORATION systems " F-20 "
TOSOH CORPORATION systems " F-40 "
TOSOH CORPORATION systems " F-80 "
TOSOH CORPORATION systems " F-128 "
TOSOH CORPORATION systems " F-288 "
TOSOH CORPORATION systems " F-550 "
For the present invention fluorine-containing pyrolytic resin in fluorine atom containing ratio, from for forming cured coating film The compatibility of other resins is good and obtains setting out in terms of the excellent cured coating film of flatness, with the fluorine-containing pyrolytic On the basis of the quality of resin, preferably 1~35 mass % scope, more preferably 5~30 mass % scope, further preferred 10~ 25 mass % scope.It should be noted that the containing ratio of foregoing fluorine atom being contained by the quality of fluorine atom relative to of the invention The ratio of the total amount of the raw material used in the preparation of fluorine pyrolytic resin is calculated.
The anti-corrosion agent composition of the present invention is characterised by, includes the fluorine-containing pyrolytic resin of the present invention.Specifically, As the anti-corrosion agent composition of the present invention, for example, it can include：Photo-corrosion-resisting agent composition, colour resist composition etc..Before State fluorine-containing pyrolytic resin and photoresist that photo-corrosion-resisting agent composition for example includes the present invention, photoresist example Such as comprising (1) alkali soluble resin, (2) radiation irritability material (photosensitive material), (3) solvent.
As foregoing (1) alkali soluble resin, for example, it can include：For as using in the patterning of resist The resin of the alkaline solution-soluble of developer solution.As the example of foregoing alkali soluble resin, can for example include by selected from phenol, The aromatic hydroxy compounds such as cresols, xylenols, resorcinol, phloroglucin, quinhydrones and their alkyl substitution or halogen Novolaks tree obtained from the condensation of the aldehyde compounds such as at least one kind of and formaldehyde, acetaldehyde, benzaldehyde in substituted aromatic compound The vinyl benzene phenolic compounds such as fat, adjacent vinylphenol, a vinylphenol, 4-Vinyl phenol, Alpha-Methyl vinylphenol And the polymer or copolymer of their halogen-substituted compounds, acrylic acid, methacrylic acid, (methyl) Hydroxyethyl Acrylate Deng acrylic acid series or metha crylic polymer or copolymer, polyvinyl alcohol and then by one of above-mentioned various resins Hydroxyl is divided to import quinone diazido, naphthoquinones azido, aromatic series azido, aromatic series cinnamoyl israds irritability group Obtained from modified resin etc..These alkali soluble resins may be used singly or in combination of two or more.
And then, as foregoing alkali soluble resin, acidic-group in the molecule comprising carboxylic acid, sulfonic acid etc. can be used Carbamate resins, alternatively, it is also possible to which the carbamate resins are applied in combination with above-mentioned alkali soluble resin.
(2) the radiation irritability material (photosensitive material) used in anti-corrosion agent composition as the present invention, as long as Be by mixed with above-mentioned alkali soluble resin and irradiation ultraviolet radiation, far ultraviolet, PRK, X-ray, electron ray, Ion irradiation, molecular ray, gamma-rays etc. and make the material that dissolubility of the alkali soluble resin in developer solution changes just It can use.
As aforementioned radiation line irritability material, for example, it can include：The nitrine based compound of quinone two, diazonium based compound, Two nitrine based compounds, salt compound, halogenated organic compounds, the mixing of halogenated organic compounds and organo-metallic compound Thing, organic acid esters compound, organic acid amide compound, organic acid imide compound and Japanese Unexamined Patent Application 59-152 Poly- (olefin sulfone) compound described in publication etc..
As the foregoing nitrine based compound of quinone two, for example, it can include：1,2- benzoquinones nitrine -4- sulphonic acid esters, 1,2- naphthoquinones Two nitrine -4- sulphonic acid esters, the nitrine -5- sulphonic acid esters of 1,2- naphthoquinones two, the nitrine -4- sulphonic acid esters of 2,1- naphthoquinones two, 2,1- naphthoquinones two are folded Nitrogen -5- sulphonic acid esters and 1,2- benzoquinones nitrine -4- sulfonic acid chlorides, the nitrine -4- sulfonic acid chlorides of 1,2- naphthoquinones two, the nitrine of 1,2- naphthoquinones two - The sulphur of the azido derivants of quinone two such as 5- sulfonic acid chlorides, the nitrine -4- sulfonic acid chlorides of 2,1- naphthoquinones two, the nitrine -5- sulfonic acid chlorides of 2,1- naphthoquinones two Acyl chlorides etc..
As foregoing diazonium compound, for example, it can include：To diazonium diphenylamines and the salt of the condensation product of formaldehyde or acetaldehyde, For such as hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the diazonium of the reaction product of above-mentioned condensation product The weight of reaction products such described in resin inorganic salts, USP3300309 specifications, for above-mentioned condensation product and sulphonic acids Nitrogen resin organic salt etc..
As foregoing azido compound and two azido compounds, for example, it can include：Japanese Unexamined Patent Application 58-203438 public affairs Nitrine chalcone acid, two nitrine benzal methyl cyclohexane ketones and the sub- acetophenones of nitrine cinnamyl, Japanization described in report Aromatic series azido compound or the azido compound of aromatic series two described in association periodical No.12, p1708-1714 (nineteen eighty-three) etc..
As foregoing halogenated organic compounds, as long as example, the halides of organic compound can be used as tool to use Style, can also enumerate containing the plain oxadiazole based compound of halogen, the based compound of triazine containing halogen, the based compound of acetophenone containing halogen, The compound of benzophenone series containing halogen, the based compound of sulfoxide containing halogen, the based compound of sulfone containing halogen, the chemical combination of thiazole system containing halogen Thing, containing the plain oxazole based compound of halogen, the based compound of triazole containing halogen, the pyranone of 2- containing halogen based compound, aliphatic containing halogen Hydrocarbon system compound, halogen-containing fragrant race hydrocarbon system compound, other compounds of shape containing halo heterocycle, the sub- sulfenyl halides of oxygen The various compounds such as (Sulfenyl halide) based compound and then such as three (2,3- dibromopropyls) phosphates, three (2,3- Two bromo- 3- chloropropyls) phosphate, chlorine tetrabromomethane, hexachloro-benzene, HBB, HBCD, hexabromobiphenyl, tribromo phenyl Allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, double (bromoethyl ether) tetrabromobisphenol As, double (chloroethyl ether) tetrachlorobisphenol As, three Double (4- hydroxyl -3,5- dibromo phenyls) propane of (2,3- dibromopropyls) isocyanuric acid ester, 2,2-, 2,2- it is double (4- hydroxyl-oxethyls - 3,5- dibromo phenyls) compound, the dichlorophenyl trichloroethanes that are used as halogen-system fire retardant such as propane etc. be as organochlorine It is compound of Pesticide use etc..
As foregoing organic acid esters, such as can include carboxylate, sulphonic acid ester.In addition, as foregoing organic acid amide, Carboxylic acid amide, sulfonic acid amides etc. can be included.And then, as organic acid imide, carboxylic acid imide, sulfonic acid acyl Asia can be included Amine etc..These radiation irritability materials may be used singly or in combination of two or more.
It is solvable relative to alkali for the compounding ratio of radiation irritability material in foregoing photo-corrosion-resisting agent composition The property mass parts of resin 100, the preferably scope of 10~200 mass parts, the scope of more preferably 50~150 mass parts.
(3) solvent used in anti-corrosion agent composition as the present invention, for example, can include：Acetone, MEK, hexamethylene The ketones such as ketone, cyclopentanone, cycloheptanone, 2-HEPTANONE, methyl iso-butyl ketone (MIBK), butyrolactone；Methanol, ethanol, normal propyl alcohol, isopropanol, just The alcohols such as butanol, isobutanol, the tert-butyl alcohol, amylalcohol, enanthol, octanol, nonyl alcohol, decyl alcohol；Glycol dimethyl ether, ethylene glycol diethyl ether, The ethers such as dioxane；
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, the third two The alcohol ethers such as alcohol list propyl ether；Ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, acetic acid third Ester, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, breast The esters such as acetoacetic ester, butyl lactate, 2- oxygen methyl propionate, 2- oxygen ethyl propionate, 2- oxygen propyl propionate, 2- oxygen butyl propionate, 2- The monocarboxylates such as methoxy methyl propionate, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- methoxy propyl acid butyl esters Class；
Cellosolve acetate, methylcellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetic acid esters, butyl The cellosolve esters such as cellosolve acetate；Propane diols, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dihydroxypropane single-ether The propandiolses such as acetic acid esters, glycol monobutyl ether acetic acid esters；Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol The diethylene glycol class such as dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether；Trichloro ethylene, Freon solvent, The halogenated hydrocarbons such as HCFC, HFC；The fragrance such as fully fluorinated solvent, toluene, dimethylbenzene same clan as PFO；Dimethyl Acetamide, dimethylformamide, N- methylacetamides, 1-METHYLPYRROLIDONE polar solvent etc., published book《Solvent is pocket Handbook》Solvent described in (Synthetic Organic Chemistry association volume, Ohmsha, Ltd.).These solvents can be used alone, can also Two or more is applied in combination.
As the present invention anti-corrosion agent composition another specific form colour resist composition, for example comprising The fluorine-containing pyrolytic resin and colour resist of the present invention, the colour resist is for example comprising (1) alkali soluble resin, (4) Polymerizable compound, (5) colouring agent.
As (1) alkali soluble resin used in colour resist composition, for example, it can use foregoing photoresist Alkali soluble resin used in agent composition etc..
Foregoing (4) as long as polymerizable compound have by ultraviolet isoreactivity energy-ray irradiation can polymerize or be crosslinked The compound of the optical polymerism functional group of reaction can just be not particularly limited to use.It is used as such (4) polymerism chemical combination Thing, for example, can include：The unsaturated carboxylic acids such as (methyl) acrylic acid, the ester of monohydroxy compound and unsaturated carboxylic acid, aliphatic The ester of polyol and unsaturated carboxylic acid, the ester of aromatic polyhydroxy compounds and unsaturated carboxylic acid, pass through unsaturated carboxylic The esterification of acid and the polyol such as polybasic carboxylic acid and foregoing aliphatic polyhydroxy compound, aromatic polyhydroxy compounds React obtained ester, make polyisocyanate compound that there is ammonia with containing obtained from (methyl) acryloyl group hydroxy compounds reacts Polymerizable compound of carbamate skeleton etc..
As foregoing aliphatic polyhydroxy compound and the ester of unsaturated carboxylic acid, for example, it can include：(the first of ethylene glycol two Base) acrylate, triethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trihydroxy methyl second Alkane three (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite Four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta (methyl) acrylate such as tetrol six (methyl) acrylate, (methyl) glycerol acrylate.Alternatively, it is also possible to enumerate these The partial replacement of (methyl) acrylic acid of acrylate for itaconic acid itaconate, replace with crotonic acid crotonates or Replace with maleate of maleic acid etc..
As aforementioned fragrance race polyol and the ester of unsaturated carboxylic acid, for example, it can include：Quinhydrones two (methyl) Acrylate, resorcinol two (methyl) acrylate, pyrogallol three (methyl) acrylate etc..In addition, passing through unsaturation The ester that the esterification of carboxylic acid, polybasic carboxylic acid and polyol is obtained can be single substance, or mixture.Make For such ester, for example, it can include：The ester that is obtained by (methyl) acrylic acid, phthalic acid and ethylene glycol, by (methyl) third Ester that olefin(e) acid, maleic acid and diethylene glycol are obtained, the ester obtained by (methyl) acrylic acid, terephthalic acid (TPA) and pentaerythrite, by Ester that (methyl) acrylic acid, adipic acid, butanediol and glycerine are obtained etc..
It is used as tool obtained from making aforementioned polyisocyanates compound and being reacted containing (methyl) acryloyl group hydroxy compounds There is the polymerizable compound of carbamate skeleton, can include：Hexamethylene diisocyanate, tri-methyl hexamethylene two are different The aliphatic diisocyanates such as cyanate；The isocyanic acid of the ester ring types such as cyclohexane diisocyanate, IPDI two Ester；The aromatic diisocyanates such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and (methyl) acrylic acid -2- hydroxyls Ethyl ester, 3- hydroxyls (1,1,1- tri- (methyl) acryloyloxymethyl) propane etc. have the hydroxy compounds of (methyl) acryloyl group Reaction product.
As (4) polymerizable compound used in the present invention than that described above, for example, it can include：Double (the first of ethene Base) (methyl) acrylamide such as acrylamide；The allyl esters such as diallyl phthalate；Divinyl phthalic acid ester Deng compound with vinyl etc..
In addition, as foregoing (4) polymerizable compound, the polymerizable compound with acidic group can be used.It is used as the tool There is the ester of the polymerizable compound of acidic group, for example, aliphatic polyhydroxy compound and unsaturated carboxylic acid, preferably make aliphatic many The unreacted hydroxyl of hydroxy compounds polyfunctional monomer with acidic group with non-aromatic carboxylic acid anhydride reactant.In addition, especially The foregoing aliphatic polyhydroxy compound of preferred pair person of obtaining using pentaerythrite, dipentaerythritol.These monomers can only make With a kind, two or more can also be applied in combination.Alternatively, it is also possible to which the monomer with acidic group and the list without acidic group is applied in combination Body.
And then, as the preferred concrete example of the multifunctional polymerizable compound with acidic group, for example, it can include：From east Asia synthesis Co., Ltd. as " ARONIX TO-1382 " and it is commercially available with dipentaerythritol acrylate, dipentaerythritol five The succinate of acrylate and Dipentaerythritol Pentaacrylate is the mixture of principal component.The multifunctional polymerizable compound It can also be applied in combination with other multifunctional polymerizable compounds.
For the acid number of the foregoing multifunctional polymerizable compound with acidic group, from the good side such as developability, curability Face is set out, preferably 0.1~40 scope, more preferably 5~30 scope.It is further preferred, that two or more is being applied in combination not The situation of the multifunctional polymerizable compound of same acid number, the feelings that the multifunctional polymerizable compound without acidic group is applied in combination Under condition, the acid number of all multifunctional mixed mixtures of polymerizable compound is changed into above-mentioned scope.
In foregoing colour resist composition, in all solids composition, foregoing (4) polymerizable compound contain than Rate is preferably 5~80 mass % scope, is more preferably 10~70 mass % scope, more preferably 20~50 mass % Scope.In addition, foregoing (4) polymerizable compound is preferably 5~200 mass %, more relative to the ratio of aftermentioned (5) colouring agent Preferably 10~100 mass % scope, more preferably 20~80 mass % scope.
As foregoing (5) colouring agent, as long as can colour, either pigment or dyestuff can make without particular limitation With.In addition, pigment can also use any one in organic pigment, inorganic pigment.As foregoing organic pigment, red can be used The pigment of each form and aspect such as pigment, viridine green, blue pigment, yellow uitramarine, violet pigment, orange pigment, brown.Separately Outside, as the chemical constitution of organic pigment, for example, it can include：Azo system, phthalocyanine system, quinacridone, benzimidazolone system, Isoindolinone system, dioxazines system, indanthrene (indanthrene) Xi, perylenes system etc..It should be noted that following " C.I. " refers to color index (colour index).
As foregoing red pigment, for example, it can include：C.I. paratonere (Pigment red) 1,2,3,4,5,6,7,8, 9、12、14、15、16、17、21、22、23、31、32、37、38、41、47、48、48：1、48：2、48：3、48：4、49、49：1、 49：2、50：1、52：1、52：2、53、53：1、53：2、53：3、57、57：1、57：2、58：4、60、63、63：1、63：2、64、 64：1、68、69、81、81：1、81：2、81：3、81：4、83、88、90：1、1 01、101：1、104、108、108：1、109、 112、113、114、122、123、144、146、147、149、151、166、168、169、170、172、173、174、175、176、 177、178、179、181、184、185、187、188、190、193、194、200、202、206、207、208、209、210、214、 216、220、221、224、230、231、232、233、235、236、237、238、239、242、243、245、247、249、250、 251、253、254、255、256、257、258、259、260、262、263、264、265、266、267、268、269、270、271、 272nd, 273,274,275,276 etc..Among these, preferred C.I. pigment red 4s 8：1、122、168、177、202、206、207、 209th, 224,242 or 254, more preferably C.I. paratoneres 177,209,224 or 254.
As foregoing viridine green, for example, can include：C.I. naphthol green (Pigment Green) 1,2,4,7,8,10, 13rd, 14,15,17,18,19,26,36,45,48,50,51,54,55,58 etc..Among these, preferably C.I. pigment Green 7s, 36 or 58。
As aforementioned blue pigment, for example, it can include：C.I. alizarol saphirol (Pigment Blue) 1,1：2、9、14、15、 15：1、15：2、15：3、15：4、15：6、16、17、19、25、27、28、29、33、35、36、56、56：1、60、61、61：1、62、 63rd, 66,67,68,71,72,73,74,75,76,78,79 etc..Among these, preferably C.I. pigment blue 15s, 15：1、15：2、15： 3、15：4 or 15：6, more preferably C.I. pigment blue 15s：6.
As foregoing yellow uitramarine, for example, it can include：C.I. pigment yellow (Pigment yellow) 1,1：1、2、3、4、 5、6、9、10、12、13、14、16、17、24、31、32、34、35、35：1、36、36：1、37、37：1、40、41、42、43、48、 53、55、61、62、62：1、63、65、73、74、75,81、83、87、93、94、95、97、100、101、104、105、108、109、 110、111、116、117、119、120、126、127、127：1、128、129、133、134、136、138、139、142、147、 148、150、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、 170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191：1、192、 193rd, 194,195,196,197,198,199,200,202,203,204,205,206,207,208 etc..Among these, preferably C.I. pigment yellow 83,117,129,138,139,150,154,155,180 or 185, more preferably C.I. pigment yellow 83s, 138,139, 150 or 180.
As foregoing violet pigment, for example, it can include：C.I. pigment violet (Pigment Violet) 1,1：1、2、2：2、 3、3：1、3：3、5、5：1st, 14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49,50 etc..These it In, preferably C.I. pigment violet 1s 9 or 23, more preferably C.I. pigment Violet 23s.
As foregoing orange pigment, for example, it can include：C.I. pigment orange (Pigment Orange) 1,2,5,13,16, 17、19、20、21、22、23、24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、 73rd, 74,75,77,78,79 etc..Among these, preferred C.I. pigment oranges 38 or 71.
Because trichromatic each pixel of the colour filter used in liquid crystal display device and organic EL display is red (R), green (G), blue (B), therefore can be using foregoing red pigment, viridine green and blue pigment as principal component, for raising The purpose of colorrendering quality and use the organic pigment of the color such as yellow, purple, orange as adjustment of color.
In addition, as foregoing inorganic pigments, such as can include：Barium sulfate, Liu Suan qian, titanium oxide, chrome yellow, Indian red (bengala), chromium oxide etc..
It should be noted that the brightness in order to improve color liquid crystal display arrangement and organic EL display, foregoing organic Preferably less than 1 μm, more preferably less than 0.5 μm, further preferred less than 0.3 μm of the average grain diameter of pigment.Preferred pair organic pigment Decentralized processing is carried out to use to become these average grain diameters.In addition, the preferred 100nm of the average primary particle diameter of foregoing organic pigment Below, more preferably below 50nm, further preferred below 40nm, particularly preferred 10~30nm scope.It should be noted that having The average grain diameter of machine pigment is determined using dynamic light scattering formula particle size distribution meter, it is possible to use such as Nikkiso Company Limited The Nanotrac particle size distribution devices " UPA-EX150 " of system, " UPA-EX250 " etc. are measured.
It is used as (5) used in the case where using foregoing colour resist composition to form black matrix" (BM) Colouring agent, as long as black is just not particularly limited, can be included：Carbon black, lampblack, acetylene black, boneblack, thermal black, channel process Carbon black, furnace black, graphite, iron oxide black, titanium are black etc..Furthermore it is possible to mix two or more organic pigment, be combined as black by colour mixture. Among these, from the viewpoint of shading rate, picture characteristics, preferably carbon black, titanium are black.
As the commercially available product of foregoing carbon black, for example, it can include：The MA7 of Mitsubishi chemical Co., Ltd, MA8, MA11, MA100、MA100R、MA220、MA230、MA600、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、# 50、#52、#55、#650、#750、#850、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、# 2400、#2600、#3050、#3150、#3250、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、 OIL11B, OIL30B, OIL31B etc., can be included：Evonik Japan Co., Ltd. Printex3, Printex3OP, Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、 Printex80、Printex85、Printex90、PrintexA、PrintexL、PrintexG、PrintexP、PrintexU、 PrintexV、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、 SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、ColorBlackFW1、 ColorBlackFW2、ColorBlackFW2V、ColorBlackFW18、ColorBlackFW18、ColorBlackFW200、 ColorBlackS160, ColorBlackS170 etc., can be included：Cabot Japan K.K. Monarch120, Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、 Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL99、REGAL99R、REGAL415、 REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、 BLACKPEARLS480, PEARLS130, VULCANXC72R, ELFTEX-8 etc., can be included：コロンビヤンカーボン The RAVEN11 of society, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、 RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、 RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、 RAVEN7000 etc..
Among above-mentioned carbon black, the high optical concentration required by the black matrix" with colour filter and high surface electricity are used as The carbon black of resistance rate, preferably uses the carbon black covered by resin.It should be noted that the carbon black covered by resin can for example pass through Japanese Unexamined Patent Publication 9-26571 publications, Japanese Unexamined Patent Publication 9-71733 publications, Japanese Unexamined Patent Publication 9-95625 publications, Japan Method described in Unexamined Patent 9-238863 publications or Japanese Unexamined Patent Publication 11-60989 publications to known carbon black at Manage to obtain.
In addition, as the black preparation method of foregoing titanium, can include：Described in Japanese Unexamined Patent Application 49-5432 publications The mixture of titanium dioxide and Titanium is heated to the method for reducing it, Japanese Unexamined Patent Application 57-205322 under reducing atmosphere The ultra rme titanium dioxide for obtaining the pyrohydrolysis by titanium tetrachloride described in number publication is in the reducing atmosphere containing hydrogen Described in method, Japanese Unexamined Patent Application 60-65069 publications and the Japanese Unexamined Patent Application 61-201610 publications of middle reduction by two Titanium oxide or titanium hydroxide carry out the method for high temperature reduction, described in Japanese Unexamined Patent Application 61-201610 publications in the presence of ammonia Make to adhere to vfanadium compound on titanium dioxide or titanium hydroxide, carry out method etc. of high temperature reduction in the presence of ammonia.It is black as titanium Commercially available product, can for example include the Mitsubishi Materials Corporation black 10S of titanium, 12S, 13R, 13M, 13M-C etc..
As mixing two or more organic pigment, the combination of black being made up of colour mixture, it can include red, green, indigo plant The black pigment that the pigment of these three colors of color is obtained by mixing.As for the color for preparing black pigment and can be used in mixed way Material, can be included：Victoria pure blue (Victoria Pure Blue) (C.I.42595), auramine O (C.I.41000), sun from Sub- lucidin (Cathilon Brilliant Flavin, Basic13), rhodamine (Rhodamine) 6GCP (C.I.45160), Rhodamine B (C.I.45170), safranin O K70：100 (C.I.50240), the red X of small-mouthed jar (C.I.42080), No.120/ thunders Nore difficult to understand are yellow (Lionol Yellow) (C.I.21090), thunder Austria Nore Huang (Lionol Yellow) GRO (C.I.21090), SYMULER Fast Yellow) 8GF (C.I.21105), benzidine yellow 4T-564D (C.I.21095), SYMULER Fast red 4015 (C.I.12355), thunder Nore difficult to understand red (Lionol red 7B4401 (C.I.15850), FASTOGEN Blue TGR-L (C.I.74160), thunder Nore indigo plant (Lionol Blue) SM (C.I.26150) difficult to understand, thunder Nore indigo plant (Lionol Blue) ES difficult to understand (C.I. pigment blue 15s：6), green (Lionol Green) 2YS of LIONOGEN Red GD (C.I. paratoneres 168), thunder Nore difficult to understand (C.I. pigment green 36s) etc..
As other colorants that can be used in mixed way to prepare black pigment, for example, it can include：C.I. yellow uitramarine 20th, 24,86,93,109,110,117,125,137,138,147,148,153,154,166, C.I. orange pigments 36,43,51, 55th, 59,61, C.I. red pigments 9,97,122,123,149,168,177,180,192,215,216,217,220,223, 224th, 226,227,228,240, C.I. violet pigments 19,23,29,30,37,40,50, C.I. blue pigments 15,15：1、15： 4th, 22,60,64, C.I. viridine greens 7, C.I. browns 23,25,26 etc..
On the other hand, in the case of using carbon black as black pigment, preferably 0.01~0.08 μm of average primary particle diameter Scope, from the good aspect of developability, more preferably 0.02~0.05 μm of scope.In addition, the adjacent benzene two of the carbon black used Formic acid dibutyl ester (it is following, it is abbreviated as " DBP ".) uptake preferably 40~100cm3/ 100g scope, from dispersed developability Good aspect is set out, more preferably 50~80cm3/ 100g scope.And then, the ratio that the utilization BET method of the carbon black used is obtained Surface area preferably 50~120m2/ g scope, from the good aspect of dispersion stabilization, more preferably 60~95m2/ g scope.
In addition, for carbon black, the difference such as grain shape and organic pigment, with the structure referred to as 1 grain fusing State exist, in addition sometimes through post processing fine pore is formed in particle surface.Therefore, in order to represent the particle of carbon black Shape, it is usually preferred to also right in addition to the average grain diameter of 1 particle by being obtained with foregoing organic pigment identical method DBP uptakes (JISK6221) and the specific surface area (JISK6217) obtained using BET method are measured, and are used as structure, pore The index of amount.
In addition, as the colouring agent used in the present invention, dyestuff can also be used.As such dyestuff, for example, it can arrange Enumerate：Azo based dye, anthraquinone based dye, phthalocyanine based dye, quinone imines based dye, quinoline based dye, nitro based dye, carbonyl Based dye, methine based dye, xanthene based dye etc..
As foregoing azo based dye, for example, it can include：C.I. acid yellow 11, C.I. acid orange 7s, C.I. acid reds 37th, C.I. acid red 18s 0, C.I. acid blues 29, C.I. directly red 28, C.I. directly red 83, C.I. directly Huang 12, C.I. are direct Orange 26, C.I. direct greens 28, C.I. direct greens 59, C.I. active yellows 2, C.I. active reds 17, C.I. active reds 120, C.I. live Property black 5, C.I. disperse oranges 5, C.I. disperse reds 58, C.I. disperse blues 165, C.I. alkali blues 41, C.I. Basic Red 18s, C.I. matchmaker Incarnadine 7, C.I. mordant yellows 5, C.I. mordant dyeings black 7 etc..
As foregoing anthraquinone based dye, for example, it can include：C.I. Vat blue 4, C.I. Acid Blue 40s, C.I. acid greens 25th, C.I. active blue 19s, C.I. reactive blue 4s 9, C.I. disperse red 60s, C.I. Disperse Blue-56s, C.I. disperse blue 60s etc..
As foregoing phthalocyanine based dye, such as can include C.I. vat blues 5, foregoing quinone imines based dye, example are used as C.I. alkali blue 3s, C.I. alkali blues 9 can be such as included, as foregoing quinoline based dye, for example, can be included：C.I. solvent Huang 33, C.I. quinoline yellows, C.I. dispersion yellow 64s etc., as foregoing nitro based dye, for example, can be included：C.I. Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42s etc..As foregoing methine based dye, such as can include C.I. disperse yellows 201. As foregoing xanthene based dye, such as can include C.I. acid reds 289.
In above-mentioned (5) colouring agent enumerated, from the side that the light resistance, weatherability and fastness of the film finally given are excellent Face is set out, and preferably uses pigment, but in order to carry out the adjustment of form and aspect, dyestuff can also be applied in combination in pigment as needed.
Containing ratio of foregoing (5) colouring agent in all solids composition in foregoing colour resist composition be preferably More than 1 mass %, more preferably 5~80 mass % scope, more preferably 5~70 mass % scope.
In addition, foregoing colour resist composition to be used for red (R), green (G) of colour filter, each pixel of blue (B) In the case of formation, foregoing (5) colouring agent the containing in all solids composition in colour resist composition of the invention Ratio is preferably 5~60 mass % scope, is more preferably 10~50 mass % scope.
And then, it is colored in the case where foregoing colour resist composition to be used for the formation of black matrix" of colour filter The containing ratio of (5) colouring agent in anti-corrosion agent composition in all solids composition be preferably 20~80 mass % scope, More preferably 30~70 mass % scope.
It is preferably previously prepared by making in the case where (5) colouring agent is pigment for foregoing colour resist composition With dispersant and make it disperse the dispersible pigment dispersion that is prepared from organic solvent to use.As foregoing dispersant, It can include：Surfactant；The intermediate or derivative of pigment；The intermediate or derivative of dyestuff；Polyamide-based tree Resin type dispersant such as fat, polyurethane series resin, polyester based resin, acrylic resin etc..It is preferably former with nitrogen among these Graft copolymer, the acrylic block copolymer with nitrogen-atoms, carbamate resins dispersant of son etc..Due to these Dispersant has nitrogen-atoms, therefore by making nitrogen-atoms that there is the part of compatibility, raising in addition to nitrogen-atoms to surface of pigments To the compatibility of medium, so that dispersion stabilization is improved.It should be noted that these dispersants can be used alone, can also Two or more is applied in combination.
As the commercially available product of foregoing dispersant, it can include：Efka CHEMICALS Co., Ltd. " EFKA " series (" EFKA 46 " etc.)；BYK Japan K.K. " Disperbyk " series, " BYK " series (" BYK-160 ", " BYK- 161 ", " BYK-2001 " etc.)；Lubrizol Japan Ltd. " Solsperse " series；SHIN-ETSU HANTOTAI's chemical industry strain formula meeting " KP " series of society, " Polyflow " series of Kyoeisha Chemical Co., Ltd.；Nanmu this chemical conversion Co. Ltd. system " DISPARLON " series；Ajinomoto Fine-Techno Co., Inc. " AJISPER " series (" AJISPER PB- 814 " etc.) etc..
In addition, as aforesaid pigments dispersion liquid preparation when the organic solvent that uses, can for example include：Propane diols list first The acetic acid ester series solvent such as ether acetic acid ester, propylene glycol monoethyl ether acetate；The propionic acid ester series solvent such as ethoxy-c acid esters；Toluene, two The fragrant family solvent such as toluene, methyl phenyl ethers anisole；Butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol diformazan The ether series solvents such as ether；The ketone series solvents such as MEK, methyl iso-butyl ketone (MIBK), cyclohexanone；The aliphatic hydrocarbon series solvent such as hexane；N, N- bis- The nitrogen compound series solvent such as NMF, butyrolactam, METHYLPYRROLIDONE；The lactone such as gamma-butyrolacton system is molten Agent；Carbamate etc..These solvents may be used singly or in combination of two or more.
As the preparation method of aforesaid pigments dispersion liquid, it can include：Mixing dispersion step and differential through (5) colouring agent The method of day labor sequence, the method only carried out by micro- dispersion step etc..In foregoing mixing dispersion step, by (5) colouring agent, (1) A part for alkali soluble resin and the foregoing dispersant used as needed are mixed and kneaded.What is used in mixing sets It is standby to include：Two roller mills, triple-roller mill, ball mill, rotary screen (trommel), dispersion machine, kneader, co-kneader, homogeneous Device, blender, extruder of single shaft or twin shaft etc., by using these kneading machines, are disperseed when applying Strong shear power, So as to which colouring agent is disperseed.It is further preferred, that (5) colouring agent is before above-mentioned mixing is carried out, beforehand through salt mill method etc. By particle size miniaturization.
On the other hand, in foregoing micro- dispersion step, by using dispersion machine, it will be obtained into foregoing mixing dispersion step The composition comprising (5) colouring agent in add solvent material or mixing (5) colouring agent, (1) alkali-soluble tree The material and glass of fat, solvent and the foregoing dispersant used as needed, zirconium oxide, scattered use of the particulate of ceramics are situated between Matter is mixed together scattered, and the particle of (5) colouring agent can be dispersed to the small state reached close to primary particle.
In addition, from the viewpoint such as transmitance, contrast for improving colour filter, the primary particle of (5) colouring agent is averaged Particle diameter is preferably 10~100nm, more preferably 10~60nm.It should be noted that the average grain diameter for being somebody's turn to do (5) colouring agent is to utilize Dynamic light scattering formula particle size distribution meter is determined, it is possible to use the Nanotrac particle size distributions of such as Nikkiso Company Limited Device " UPA-EX150 ", " UPA-EX250 " etc. are measured.
The present invention anti-corrosion agent composition fluorine-containing pyrolytic resin content because anti-corrosion agent composition species, coating Method, target film thickness etc. and it is different, but because a small amount of addition can show the effect above of the present invention, therefore relative to resist The mass parts of solid constituent 100 in composition, preferably 0.0001~10 mass parts, more preferably 0.00001~5 mass parts, enter one Walk preferably 0.01~2 mass parts.
The color filter protecting layer composition of the present invention is characterised by, includes the fluorine-containing pyrolytic resin of the present invention. Color filter protecting layer composition can use active energy ray curable resin or active energy ray-curable monomer to make For its principal component.It should be noted that foregoing active energy ray-curable resin and active energy ray-curable monomer can To be each used alone, it can also be applied in combination.
Foregoing active energy ray-curable resin can for example be included：Carbamate (methyl) acrylate, Unsaturated polyester resin, epoxy (methyl) acrylate, polyester (methyl) acrylate, acrylic compounds (methyl) third Alkene acid ester resin, resin containing dimaleoyl imino etc..
Carbamate (methyl) acrylate wherein used can be included：Make aliphatic polyisocyante chemical combination Thing or aromatic polyisocyanate compound obtained from the reaction of hydroxyl (methyl) acrylate compounds with having amino first Resin of acid esters key and (methyl) acryloyl group etc..
As foregoing aliphatic polyisocyanate compound, for example, it can include：Tetramethylene diisocyanate, five methylenes Group diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, eight methylene diisocyanates, ten methylenes Group diisocyanate, 2- methyl isophthalic acids, 5- pentane diisocyanates, 3- methyl isophthalic acids, 5- pentane diisocyanates, ten dimethylenes two Isocyanates, 2- methyl pentamethylene diisocyanate, 2,2,4- trimethyl hexamethylene diisocyanates, 2,4,4- trimethyls Hexamethylene diisocyanate, IPDI, norbornene alkyl diisocyanate, the isocyanide of hydrogenated diphenyl methane two Acid esters, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenation tetramethyl xylylene diisocyanate, Cyclohexyl diisocyanate etc., in addition, as aromatic polyisocyanate compound, can include：Toluene di-isocyanate(TDI), 4, 4 '-methyl diphenylene diisocyanate, xylylene diisocyanate, 1,5- naphthalene diisocyanates, the isocyanic acid of tolidine two Ester, PPDI etc..
As foregoing hydroxyl (methyl) acrylate compounds, for example, it can include：(methyl) acrylic acid -2- hydroxyl second Ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -2- hydroxybutyls, (methyl) acrylic acid -4- hydroxybutyls, 1, 5- pentanediols list (methyl) acrylate, 1,6-HD list (methyl) acrylate, neopentyl glycol single (methyl) acrylate, List (methyl) acrylate of 2 yuan of alcohol such as 3-hydroxypivalic acid neopentyl glycol single (methyl) acrylate；(the first of trimethylolpropane two Base) acrylate, ethoxylated trimethylolpropane (methyl) acrylate, propoxylation trimethylolpropane two (methyl) third 3 yuan of olefin(e) acid ester, glycerine two (methyl) acrylate, double (2- (methyl) acryloyl-oxyethyl) hydroxyethyl isocyanuric acid esters etc. The list of alcohol or two (methyl) acrylate contain obtained from a part for these alcoholic extract hydroxyl groups is modified with 6-caprolactone Hydroxyl list and two (methyl) acrylate；Pentaerythrite three (methyl) acrylate, two (trimethylolpropane) three (methyl) third Olefin(e) acid ester, dipentaerythritol five (methyl) acrylate etc. have (methyl) acryloyl more than hydroxyl and 3 functions of simple function The compound of base or multifunctional (methyl) propylene of hydroxyl obtained from being modified by the compound and then with 6-caprolactone Acid esters；DPG list (methyl) acrylate, diethylene glycol list (methyl) acrylate, polypropylene glycol list (methyl) acrylic acid Ester, polyethyleneglycol (methyl) acrylate etc. have (methyl) acrylate compounds of oxyalkylene chain；Polyethylene glycol Propane diols list (methyl) acrylate, polyoxy butylidene-polyoxypropylene list (methyl) acrylate etc. has block structure (methyl) acrylate compounds of oxyalkylene chain；It is poly- (ethylene glycol-tetramethylene glycol) single (methyl) acrylate, poly- (propane diols-tetramethylene glycol) single (methyl) acrylate etc. has (methyl) acrylic acid of the oxyalkylene chain of disordered structure Ester compounds etc..
Above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and hydroxyl (methyl) propylene The reaction of ester compound can for example be carried out in the presence of urethanation catalyst, by conventional method.Herein may be used The urethanation catalyst used can specifically be included：The amine such as pyridine, pyrroles, triethylamine, diethylamine, dibutyl amine Class；The phosphines such as triphenylphosphine, triethyl phosphine；Dibutyltin dilaurate, tin octylate trilaurin, tin octylate oxalic acid The organo-tin compounds such as ester, dibutyltin bisacetate, tin octoate；The organo-metallic compounds such as zinc octoate.
In these carbamate (methyl) acrylates, from the transparent excellent of cured coating film and to activity The aspect that sensitivity is good, curability is excellent of energy-ray is set out, and makes aliphatic polyisocyanate compound and hydroxyl (first Base) acrylate compounds reaction obtained from material be particularly preferred.
Then, unsaturated polyester resin can be for example included by α, β-unsaturated dibasic acid or its acid anhydrides, except the binary Binary acid beyond acid or its acid anhydrides and curable resin obtained from the polycondensation of glycols etc..It is used as α, β-unsaturated dibasic acid Or its acid anhydrides, for example, can include：Maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlorine maleic acid and they Ester etc..
As except α, binary acid, its acid anhydrides beyond β-unsaturated dibasic acid or its acid anhydrides can for example be included：Aromatic series Monounsaturated dicarboxylic acid, aliphatic dibasic acid, alicyclic monounsaturated dicarboxylic acid and their acid anhydrides etc..As aromatic series monounsaturated dicarboxylic acid or Its acid anhydrides, for example, can include：The adjacent benzene two of phthalic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), nitro Formic acid, tetrabydrophthalic anhydride, Nadic anhydride, halophthalic acid acid anhydride and their ester etc.. As aliphatic dibasic acid, alicyclic monounsaturated dicarboxylic acid and their acid anhydrides, for example, it can include：Oxalic acid, malonic acid, amber Acid, adipic acid, decanedioic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and their ester etc..As glycols, it can enumerate Go out：Ethylene glycol, propane diols, diethylene glycol, DPG, 1,3 butylene glycol, 1,4- butanediols, 2- methylpropane -1,3- glycol, Neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5- pentanediols, 1,6-HD, bisphenol-A, hydrogenated bisphenol A, diglycol carbonate Ester, 2,2- bis- (4- hydroxy propyloxy groups diphenyl) propane etc., in addition, the oxide such as oxirane, expoxy propane similarly can be with Use.
Then, as epoxy vinyl ester resin, for example, it can include：Bisphenol A type epoxy resin, bisphenol F type epoxy tree Fat, phenol novolak type epoxy resin, cresol novolak type epoxy resin etc. make the epoxy radicals and (methyl) of epoxy resin Epoxy vinyl ester resin etc. obtained from propylene acid reaction.
As resin containing dimaleoyl imino, for example, it can include：By N- hydroxyethyls maleimide and isophorone 2 function maleimide carbamate compounds obtained from diisocyanate carries out urethane, by maleimide 2 function maleimide ester compounds obtained from amine acetic acid and polytetramethylene glycol esterification, by maleimidohexanoic acid and 4 function maleimide ester compounds obtained from the tetraoxane addition product esterification of pentaerythrite, by maleimide second Multifunctional maleimide ester compounds etc. obtained from acid and polyol compound esterification.These active energy ray curables Resin may be used singly or in combination of two or more.
As foregoing active energy ray-curable monomer, for example, it can include：Ethylene glycol two (methyl) acrylate, two Ethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, number-average molecular weight are in 150~1000 scope Polyethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, DPG two (methyl) acrylate, three Propane diols two (methyl) acrylate, number-average molecular weight are in polypropylene glycol two (methyl) acrylic acid of 150~1000 scope Ester, neopentyl glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) propylene Acid esters, 1,6-HD two (methyl) acrylate, 3-hydroxypivalic acid ester neopentyl glycol two (methyl) acrylate, bisphenol-A two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, two seasons penta 4 Alcohol six (methyl) acrylate, 6-caprolactone are modified six (methyl) acrylate, the pentaerythrite four (methyl) of dipentaerythritol Acrylate, trimethylolpropane two (methyl) acrylate, dipentaerythritol five (methyl) acrylate, 6-caprolactone are modified Five (methyl) acrylate, (methyl) acrylic acid dicyclopentenyl ester, (methyl) methyl acrylate, (methyl) third of dipentaerythritol Olefin(e) acid propyl ester, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) third Olefin(e) acid monooctyl ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid (methyl) acrylic acid aliphatic Arrcostabs such as stearyl, (methyl) acrylic acid iso stearyl ester, (methyl) glycerol acrylate, (methyl) 2-Hydroxy ethyl acrylate, 3- chlorine-2-hydroxyls propyl group (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) allyl acrylate, (methyl) acrylic acid -2- butoxyethyls, 2- (diethylamino) ethyl (methyl) acrylic acid Ester, 2- (dimethylamino) ethyl (methyl) acrylate, γ-(methyl) acryloxypropyl trimethoxy silane, 2- first Epoxide ethyl (methyl) acrylate, methoxyl group diethylene glycol (methyl) acrylate, methoxyl group DPG (methyl) propylene Acid esters, Nonylphenoxy polyethylene glycol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) It is acrylate, phenoxy group DPG (methyl) acrylate, phenoxy group polypropylene glycol (methyl) acrylate, poly- Butadiene (methyl) acrylate, polyethylene glycol propane diols (methyl) acrylate, polyethylene glycol butanediol (methyl) Acrylate, polystyrene-based ethyl (methyl) acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (first Base) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) isobornyl acrylate, the methoxylation ring last of the ten Heavenly stems Triolefin (methyl) acrylate, (methyl) phenyl acrylate；Maleimide, N- methylmaleimidos, N- ethyls Malaysia acyl Imines, N- propylmaleimides, N- butyl maleimides, N- hexyls maleimide, N- octyl groups maleimide, N- ten Dialkyl group maleimide, N- stearyls maleimide, N-phenylmaleimide, N- N-cyclohexylmaleimides, 2- horses Come acid imide ethyl-ethyl carbonate ester, 2- Mailed Ethyls-propyl carbonate, N- ethyls-(2- Mailed Ethyls) Carbamate, N, N- hexa-methylenes BMI, polypropylene glycol-bis- (3- maleimides propyl group) ether, double (2- Malaysias Acid imide ethyl) maleimide such as carbonic ester, 1,4- dimaleimide hexamethylenes etc..
Among these, particularly from the excellent aspect of the hardness of cured coating film, preferably trimethylolpropane tris (first Base) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, (the first of pentaerythrite four Base) more than 3 functions such as acrylate multifunctional (methyl) acrylate.These active energy ray-curable monomers can be single Solely use, two or more can also be applied in combination.
The color filter protecting layer composition of the present invention can be after being applied on base material by irradiating active energy beam To form cured coating film.The active energy beam refers to the such ionization of ultraviolet, electron ray, alpha ray, β rays, gamma-rays Radiation.In the case where irradiation ultraviolet radiation forms cured coating film as active energy beam, preferably in active energy beam Photoepolymerizationinitiater initiater is added in curing composition to improve curability.In addition, if need can with so that add sensitising agent To improve curability.On the other hand, in the situation using ionization radial line as electron ray, alpha ray, β rays, gamma-rays Under, also can promptly it solidify even if without using Photoepolymerizationinitiater initiater, sensitising agent, therefore photopolymerization initiation need not be especially added with Agent, sensitising agent.
As foregoing photo-polymerization initiator, intramolecular cracking type Photoepolymerizationinitiater initiater can be included and hydrogen-abstraction photopolymerization is drawn Send out agent.As intramolecular cracking type Photoepolymerizationinitiater initiater, for example, it can include：Diethoxy acetophenone, 2- hydroxy-2-methyls- 1- phenyl-propane -1- ketone, benzil dimethyl ketal, 1- (4- isopropyl phenyls) -2- hydroxy-2-methyl propane -1- ketone, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone, 1- hydroxycyclohexylphenylketones, 2- methyl -2- morpholinyl (4- sulphur For aminomethyl phenyl) the acetophenone system chemical combination such as propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone Thing；
The benzoin class such as benzoin, benzoin methyl ether, benzoin isopropyl ether；2,4,6- trimethylbenzene acyloin diphenyl The acylphosphine oxide based compounds such as phosphine oxide, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides；Benzil, benzoyl first Sour methyl esters etc..
As foregoing hydrogen-abstraction Photoepolymerizationinitiater initiater, for example, it can include：Benzophenone, methyl o-benzoylbenzoate, 4- phenyl benzophenones, 4,4' dichloro benzophenones, dihydroxy benaophenonel, 4- benzoyls -4'- methyl-diphenylsulfide, propylene Acylated benzophenone, 3,3', 4,4'- tetra- (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3'- dimethyl -4- methoxyl group hexichol The benzophenone based compound such as ketone；ITX, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, 2,4 2 The thioxanthones based compound such as clopenthixal ketone；The aminobenzophenone system chemical combination such as michaelis ketone, 4,4'- diethylamino benzophenone Thing；10- butyl -2- chloro-acridines ketone, 2- EAQs, 9,10- phenanthrenequione, camphorquinone etc..
In above-mentioned Photoepolymerizationinitiater initiater, the foregoing active energy ray-curable from color filter protecting layer composition Set out in terms of the excellent compatibility of resin and active energy ray-curable monomer, preferably 1- hydroxycyclohexylphenylketones and Benzophenone, particularly preferred 1- hydroxycyclohexylphenylketones.These Photoepolymerizationinitiater initiaters can be used alone, and can also combine makes Use two or more.
In addition, as foregoing photo sensitizers, such as can include：The amines such as aliphatic amine, aromatic amine, o-tolyl thiocarbamide Deng sulphur compounds such as ureas, diethyldithioposphoric acid sodium, s- benzylisothioureas-tosilate etc..
For these Photoepolymerizationinitiater initiaters and the consumption of sensitising agent, relative to color filter protecting layer with not waving in composition The mass parts of composition 100 are sent out, respectively preferably 0.01~20 mass parts, more preferably 0.1~15 mass %, further preferred 0.3~7 matter Measure part.
In addition, above-mentioned color filter protecting layer with can suitably add organic solvent as needed in composition；Pigment, dye The colouring agents such as material, carbon；The inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, calcium carbonate；It is high Level aliphatic acid, acrylic resin, phenolic resin, polyester resin, polystyrene resin, carbamate resins, urea resin, Melmac, alkyd resin, epoxy resin, polyamide, polycarbonate resin, Petropols, fluororesin (PTFE (polytetrafluoroethylene (PTFE)) etc.), polyethylene, the various resin micropowders ends such as polypropylene；It is antistatic additive, defoamer, viscosity modifier, fast light Stabilizer, weathering stabilizers, heat-resisting stabilizing agent, antioxidant, antirust agent, slip agent, wax, gloss modifiers, releasing agent, increase-volume Agent, conductive conditioning agent, dispersant, dispersion stabilizer, thickener, anti-settling agent, silicon-type or hydrocarbon system surfactant etc. are various Additive.
Aforementioned organic solvents suitably regulation aforementioned coating composition solution viscosity in terms of be it is useful, especially for Film coated is carried out, adjustment thickness becomes easy.As the organic solvent that can be used herein, for example, it can include：Toluene, two The aromatic hydrocarbons such as toluene；The alcohols such as methanol, ethanol, isopropanol, the tert-butyl alcohol；The esters such as ethyl acetate, propylene glycol methyl ether acetate Class；Ketones such as MEK, methyl iso-butyl ketone (MIBK), cyclohexanone etc..These solvents may be used alone, can also be used in combination 2 kinds More than.
Foregoing anti-corrosion agent composition of the invention, color filter protecting layer composition coating method according to purposes without Together, it can for example include and be applied using gravure coater, roll coater, comma coater, knife type coater, Kohler coater, curtain Cloth machine, lip type coating machine, spray coating machine, wheeled coating machine (wheeler coater), spinner, dipping, silk-screen printing, spray The coating method of painting, applicator, bar coater, electrostatic spraying etc. uses manufacturing process of various moulds etc..
Above-mentioned anti-corrosion agent composition, color filter protecting layer composition by irradiate the light such as visible ray, ultraviolet light and resin The physical property such as dissolubility, viscosity, transparency, refractive index, conductivity, ion permeability can change.The active energy ray-curable Among type composition, anti-corrosion agent composition (photo-corrosion-resisting agent composition, colour resist composition of colour filter etc.) requirement The levelability of height.Generally, in semiconductor or the related photoetching process of liquid crystal, it will generally be resisted by rotary coating, slot coated Erosion agent composition is coated in the way of thickness turns into 0.01~5 μm or so on Silicon Wafer or evaporation has the glass base of various metals On plate.Now, the deviation of coating film thickness may cause semiconductor, the reduction of the quality of liquid crystal cell, defect, but by using this The fluorine system surfactant of invention can be formed uniformly as the additive of the photosensitive polymer combination with its high-leveling Film, therefore productivity ratio raising, the multifunction of semiconductor, liquid crystal cell can be realized etc..
The present inventor etc. thinks, uses the anti-corrosion agent composition of the present invention, color filter protecting layer composition formation film After layer, film layer is heated in the environment of 150~300 DEG C, thus the functional group containing fluorine atom is from through blocked carboxylic Base departs from, and water repellent, oil repellent can be reduced.As a result the wetability of film layer is improved, and can form the excellent film layer of recoatability.
[embodiment]
Hereinafter, embodiments of the invention are enumerated, the present invention is described in detail while being compared with comparative example. In example, " part ", " % " are exactly quality criteria unless otherwise specified.
Embodiment 1 (fluorine-containing pyrolytic resin of the invention)
In the glass flask for possessing agitating device, thermometer, cooling tube, Dropping feeder, acrylic acid 26.8g and 3 is put into, 3,4,4,5,5,6,6,7,7,8,8,8- ten three fluoro- 1- ethyleneoxies octane 30.0g, under dry air air-flow, are at room temperature stirred Mix 21 hours.Then, MEHQ 0.003g and Di Iso Propyl Ether 107.6g is added, saturated aqueous sodium carbonate is added 161.4g, ion exchange water 161.4g simultaneously carry out a point liquid.Then, take out behind upper strata, add ion exchange water 161.4g and carry out Divide liquid.And then, take out behind upper strata, solvent is removed in progress, is obtained with the polymerization through blocked carboxyl shown in aforementioned formula (1) Property monomer.
In the glass flask for possessing agitating device, thermometer, cooling tube, Dropping feeder, the third two as solvent are put into Alcohol methyl ether acetate 50g, warming while stirring is to 80 DEG C under nitrogen flowing.Then, it will make foregoing with through blocked carboxylic Polymerizable monomer 17.5g, the propane diols polytetramethylene glycol monomethacrylates 32.5g of base are dissolved in propylene glycol methyl ether acetate 40g monomer solution and it is dissolved in double (methyl isobutyrate) 0.5g of 2,2 '-azo as radical polymerization initiator This 2 kinds of dropping liquids of propylene glycol methyl ether acetate 17g polymerization initiator solution are respectively placed in respective Dropping feeder, 80 DEG C will be remained in flask, start simultaneously at dropwise addition, monomer solution was added dropwise with 3 hours, initiator solution was added dropwise with 4 hours.Drop Plus after terminating, after being stirred 10 hours at 80 DEG C, and then add propylene glycol methyl ether acetate, obtain containing the fluorine-containing of the present invention The mass % of pyrolytic resin (1) 20 propylene glycol methyl ether acetate solution.It is right by GPC (polystyrene conversion molecular weight) The molecular weight of obtained fluorine-containing pyrolytic resin (1) is measured, and as a result number-average molecular weight is that 2900, weight average molecular weight is 28000th, maximum molecular weight is 300000.The IR spectrograms of fluorine-containing pyrolytic resin (1) are shown in Fig. 1, will13C-NMR spectrograms show In Fig. 2, GPC is illustrated in Fig. 3.
Embodiment 2 (ibid)
In the glass flask for possessing agitating device, thermometer, cooling tube, Dropping feeder, methacrylic acid 32.0g is put into With 3,3,4,4,5,5,6,6,7,7,8,8,8- ten three fluoro- 1- ethyleneoxies octane 30.0g, under dry air air-flow, 60 DEG C stirring 20 hours.Then, MEHQ 0.003g and Di Iso Propyl Ether 97.8g is added, saturated sodium carbonate is added water-soluble Liquid 146.7g, ion exchange water 146.7g simultaneously carry out a point liquid.Then, take out behind upper strata, add ion exchange water 146.7g and go forward side by side Row point liquid.And then, take out behind upper strata, solvent is removed in progress, obtain with poly- through blocked carboxyl shown in aforementioned formula (1) Conjunction property monomer.
In the glass flask for possessing agitating device, thermometer, cooling tube, Dropping feeder, the third two as solvent are put into Alcohol methyl ether acetate 50g, warming while stirring is to 80 DEG C under nitrogen flowing.Then, it will make foregoing with through blocked carboxylic Polymerizable monomer 18.0g, the propane diols polytetramethylene glycol monomethacrylates 32.0g of base are dissolved in propylene glycol methyl ether acetate 40g monomer solution and it is dissolved in double (methyl isobutyrate) 0.5g of 2,2 '-azo as radical polymerization initiator This 2 kinds of dropping liquids of propylene glycol methyl ether acetate 16.3g polymerization initiator solution are respectively placed in respective Dropping feeder In, while 80 DEG C will be remained in flask, dropwise addition is started simultaneously at, monomer solution was added dropwise with 3 hours, it is molten that initiator was added dropwise with 4 hours Liquid.After completion of dropwise addition, after being stirred 10 hours at 80 DEG C, and then propylene glycol methyl ether acetate is added, obtained containing the present invention The mass % of fluorine-containing pyrolytic resin (2) 20 propylene glycol methyl ether acetate solution.Pass through GPC (polystyrene conversions point Son amount) molecular weight of fluorine-containing pyrolytic resin (2) to obtaining is measured, and as a result number-average molecular weight is 2800, divided equally again Son amount is that 51000, maximum molecular weight is 1200000.
Embodiment 3 (anti-corrosion agent composition)
Using 3 parts as ultraviolet curing resin Dainippon Ink Chemicals UNIDIC RS20-160,1.2 parts gather as light Toagosei Co., Ltd ARONIX M-402, the 0.1 part of BASF JAPAN as Photoepolymerizationinitiater initiater of conjunction property monomer LTD. Irgacure#369 processed, be scaled in solid constituent form 0.0024 part of fluorine-containing pyrolytic resin (1) and propane diols 8 parts of mixing of methyl ether acetate, prepare the anti-corrosion agent composition (1) of the present invention.Obtained using obtained anti-corrosion agent composition (1) Cured coating film.Outward appearance to cured coating film and the recoatability of cured coating film is evaluated.The making of cured coating film is illustrated below Method and evaluation method.Evaluation result is shown in the 1st table.
<The preparation method of cured coating film>
After anti-corrosion agent composition is rotated into 10 seconds rotary coatings on 7cm × 7cm glass plate with rotating speed 1000rpm, With high-pressure sodium lamp in 50mJ/cm2Condition be exposed and form film.
<The evaluation method of the outward appearance of cured coating film>
To cured coating film irradiate sodium vapor lamp, visually observation film coated surface bumps (crawling) a situation arises, according to Under judgment standard the flatness of film coated surface is evaluated.
◎：Almost do not observe that film is uneven.
○：It was observed that a part of crawling.
×：It was observed that many crawlings.
<To the evaluation method of the recoatability of cured coating film>
The change of the polarity on cured coating film surface is determined, the evaluation of recoatability is used as.Specifically, it is dry using 230 DEG C Dry machine heats cured coating film 20 minutes, and the water and the contact angle of propylene glycol methyl ether acetate before and after it are measured. Contact angle after heating is smaller, and judgement obtains the more excellent cured coating film of recoatability.
Embodiment 4 (ibid)
Using being scaled 0.0024 part of fluorine-containing pyrolytic resin (2) in solid constituent form come instead of using with solid Ingredient form is scaled 0.0024 part of fluorine-containing pyrolytic resin (1), in addition, operates similarly to Example 3, prepares The anti-corrosion agent composition (2) of the present invention.Cured coating film is obtained using obtained anti-corrosion agent composition (2).Similarly to Example 1 Evaluation result is shown in the 1st table.
Comparative example 1 (compares control anti-corrosion agent composition)
In addition to being added without fluorine-containing pyrolytic resin (1), operate similarly to Example 3, obtain comparing control use Anti-corrosion agent composition is (1').Evaluated similarly to Example 3, the results are shown in the 1st table.
Comparative example 2 (ibid)
Except using fluorine-containing non-thermal decomposition resin (the fluorine system surfactant MEGAFAC F- of Dainippon Ink Chemicals 560) replace beyond fluorine-containing pyrolytic resin (1), operate similarly to Example 3, obtain comparing control and combined with resist Thing is (2').Operation is evaluated similarly to Example 3, the results are shown in the 1st table.
[table 1]
1st table

Claims (11)

1. a kind of fluorine-containing pyrolytic resin, it is characterised in that have：The main chain of polymer architecture with polymerizable monomer (a) with the side chain (b) with functional group shown in following formulas (1),
In formula, R1、R2And R3The respectively organic group of hydrogen atom or carbon number 1~18, R4For fluorinated alkyl or poly- (perfluor Asia Alkyl ether) chain, Y1For oxygen atom or sulphur atom.
2. fluorine-containing pyrolytic resin according to claim 1, wherein, the R4For the carbon atom of fluorine atom Direct Bonding Number be 1~6 fluorinated alkyl.
3. fluorine-containing pyrolytic resin according to claim 1, wherein, the R4For the carbon atom of fluorine atom Direct Bonding Number be 4~6 fluorinated alkyl.
4. fluorine-containing pyrolytic resin according to claim 1, wherein, the R of the side chain (b)1、R2And R3Respectively hydrogen Atom, R4The fluorinated alkyl for being 1~6 for the number of the carbon atom of fluorine atom Direct Bonding.
5. fluorine-containing pyrolytic resin according to claim 1, wherein, the side chain (b) shown in the formula (1) is by following Shown in formula (1-1),
6. fluorine-containing pyrolytic resin according to claim 1, wherein, the polymerizable monomer (α) with carboxyl will be used as With the polymerizable monomer work having through blocked carboxyl of the reaction product of the vinyl ether compound shown in following formulas (2) For inscape,
In formula, R1、R2And R3The respectively organic group of hydrogen atom or carbon number 1~18, R4For fluorinated alkyl or poly- (perfluor Asia Alkyl ether) chain, Y1For oxygen atom or sulphur atom.
7. fluorine-containing pyrolytic resin according to claim 1, wherein, will be with the polymerizable monomer (α) with carboxyl Vinyl ether compound shown in the polymer of raw material and the formula (2) is used as inscape.
8. a kind of anti-corrosion agent composition, it is characterised in that include fluorine-containing pyrolytic according to any one of claims 1 to 7 Resin.
9. a kind of color filter protecting layer composition, it is characterised in that comprising according to any one of claims 1 to 7 fluorine-containing Pyrolytic resin.
10. a kind of etchant resist, it is characterised in that obtained from being the anti-corrosion agent composition described in usage right requirement 8.
11. a kind of color filter protecting layer, it is characterised in that be the color filter protecting layer composition described in usage right requirement 9 Obtained from.
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