CN105473666B - Compound and the composition containing the compound - Google Patents

Compound and the composition containing the compound Download PDF

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CN105473666B
CN105473666B CN201480040982.5A CN201480040982A CN105473666B CN 105473666 B CN105473666 B CN 105473666B CN 201480040982 A CN201480040982 A CN 201480040982A CN 105473666 B CN105473666 B CN 105473666B
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carbon atom
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alkyl
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CN105473666A (en
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冈田光裕
松本健
金原有希子
松井依纯
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Adeka Corp
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Asahi Denka Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/34—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/37—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by etherified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/32—Cyanuric acid; Isocyanuric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/008—Triarylamine dyes containing no other chromophores
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Abstract

The present invention provides a kind of new compound of the dyestuff for being suitable as coloring photosensitive combination of heat resistance and excellent in light-resistance and has used the coloring photosensitive combination of the compound, specifically, the present invention provides the following general formula (1) compound represented and coloring photosensitive combination, the coloring photosensitive combination contain：Dyestuff (A) containing the compound, the polymerizable compound (B) with ethylenic bond unsaturated bond with acid value, optical free radical polymerization initiator (C) and the monomer (D) with ethylenic bond unsaturated bond.The particular content of general formula (1) is as recorded in this specification.

Description

Compound and the composition containing the compound
Technical field
The present invention relates to be designed to desired form and aspect and improve the dyestuff of heat resistance and suitable for the novel of the dyestuff Compound.Moreover, it relates to the coloring photosensitive combination polymerizable under energy line effect of the dyestuff is used And the colour filter of the coloring photosensitive combination is used.
Background technology
The compound to specific light with the big absorption of intensity is used as the optics such as CD-R, DVD-R, DVD+R, BD-R Recording layer, liquid crystal display device (LCD), plasma display panel (PDP), the display of organic electroluminescence of recording medium (ELD), the optical parameter of the image display devices such as cathode tube display device (CRT), fluorescent display tube, field emission type display.
In liquid crystal display device (LCD), plasma display panel (PDP), display of organic electroluminescence (ELD), the moon In the optical filters of device used for image display such as pole pipe display device (CRT), fluorescent display tube, field emission type display, 300 are absorbed The various compounds of the light of the wavelength of~1100nm are used as light absorber.
It is required that the light absorption of these light absorbers is especially precipitous, i.e. the half width of λ max is small and light or heat the effects that Under will not loss of function.
There is colour filter in the optical filter for being mainly used for liquid crystal display device (LCD).In colour filter, usually using RGB this 3 Primary colors, but with individual colorant it is difficult to make it have the form and aspect of pure RGB, it is carried out always using a variety of colorants connecing The effort of the form and aspect of nearly pure RGB.Therefore, RGB is not only needed, it is also desirable to the colorants such as yellow, orange, purple.
The light absorber used in colour filter is since heat resistance height uses organic and/or inorganic pigment always, due to for face Material, thus there are problems that making the brightness reduction as display device solve the problems, such as this by the brightness for improving light source.But It is that, with the trend of power reducing, the exploitation for having used the colour filter of dyestuff is gradually prosperous.
In addition, in recent years, it, from the viewpoint of being improved picture quality in the colour filter used in solid-state imager The filming of colored pattern is sought, in order to carry out filming, from the angle for improving colour saturation, needs to improve dye strength.Separately Outside, when the molar absorbance backscatter extinction logarithmic ratio of dyestuff is low, it is also desirable to add a large amount of dyestuff.
But when improving dye strength, after film forming during implementation heat treatment (rear to bake), between adjacent pixel or stacking is tied Interlayer up and down in structure is prone to colour mixture, therefore it is required that with heat resistance.
In addition, the light absorber used in colour filter also there are problems that being easy to deterioration under the action of exterior light, also It asks with light resistance.
The colour filter colored resin composition of the organic pigment containing specific structure is disclosed in Patent Documents 1 to 3.
But the compound used in the color composition for color filter described in these documents is from taking into account heat resistance and resistance to The angle of photosensitiveness is set out unsatisfactory.
Existing technical literature
Patent document
Patent document 1：WO2012/039286
Patent document 2：WO2012/101946
Patent document 3：WO2012/111400
Invention content
Problems to be solved by the invention
Therefore, the purpose of the present invention is to provide the colored photosensitives for having used new compound that can be solved the above problems The coloured compositions such as property composition.In addition, another object of the present invention is to provide to have used above-mentioned coloring photosensitive combination Optical filter, particularly non-reduce brightness, the colour filter suitable for image display devices such as liquid crystal display panels.
Means for solving the problems
The result that further investigation is repeated in present inventor recognizes the heat resistance of the compound with specific structure and resistance to Photosensitiveness is excellent, it is also recognized that, above-mentioned coloring photosensitive combination does not reduce the brightness of optical filter (particularly colour filter), Suitable for the device used for image display colour filter such as liquid crystal display panel, so as to complete the present invention.
The present invention is completed based on above-mentioned cognition, provides the following general formula (1) compound represented.
(in formula, A expressions phenyl ring, naphthalene nucleus or anthracene nucleus, these rings can be by halogen atom, cyano, hydroxyl, nitro, carbon atom numbers Replace for 1~12 alkyl, alkoxy, halogenated alkyl or halogenated alkoxy,
Y represents cyano or-COOR4,
R1Represent the alkyl that hydrogen atom, phenyl, cyano, nitro, halogen atom, carbon atom number are 1~12, carbon atom number 1 The halogenated alkoxy that the halogenated alkyl or carbon atom number that~12 alkoxy, carbon atom number are 1~12 are 1~12,
R2And R3Each independently represent hydrogen atom, the aryl that the alkyl that carbon atom number is 1~12, carbon atom number are 6~20 Or the aralkyl that carbon atom number is 7~20,
R2And R3Alkyl, aryl and the aralkyl of expression can be replaced by halogen atom or nitro,
R2And R3Methylene in the alkyl and aralkyl of expression can be by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- Or-CONH substitutions,
R4Represent the aryl that alkyl, carbon atom number that hydrogen atom, carbon atom number are 1~12 are 6~20, carbon atom number 7 ~20 aralkyl or carbon atom number is 2~35 heterocycle,
R4Methylene in the alkyl and aralkyl of expression can by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- or- CONH replaces,
X represents singly-bound, nitrogen-atoms ,-NR5, oxygen atom, sulphur atom ,-SO2,-SO-, phosphorus atoms ,-PR6Or under meeting It states<1>~<5>The organic group of middle either condition,
R5And R6Each independently represent hydrogen atom, the aryl that the alkyl that carbon atom number is 1~12, carbon atom number are 6~20 Or the aralkyl that carbon atom number is 7~20,
The integer of m=2~6.)
<1>Shown in m=2, X such as following formula (2).
*-Z1-X1-Z2-* (2)
(in formula, X1Expression-NR13, divalent carbon atom number be 1~35 aliphatic alkyl, divalent carbon atom number be 3 It containing fragrant cyclic hydrocarbon radical, the carbon atom number of divalent is 2~35 that~35 alicyclic type hydrocarbon, the carbon atom number of divalent, which are 6~35, Group containing any one expression in heterocyclic group or following (2-1)~(2-3),
X1The aliphatic alkyl of expression can by halogen atom, cyano, hydroxyl, nitro, carbon atom number be 1~8 alkyl, Alkoxy, halogenated alkyl or halogenated alkoxy substitution,
X1Methylene in the aliphatic alkyl of expression can be by-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-SO2-、- NH- or the group substitution that they are composed,
Z1And Z2Each independently represent Direct Bonding ,-O- ,-S- ,-SO2-、-SO-、-NR13Or-PR14,
R13And R14Each independently represent hydrogen atom, the virtue that the alkyl that carbon atom number is 1~8, carbon atom number are 6~20 Base or the aralkyl that carbon atom number is 7~20,
R13And R14Alkyl, aryl and the aralkyl of expression can be replaced by halogen atom, hydroxyl or nitro,
R13And R14Methylene in the alkyl and aralkyl of expression can be by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- Or-CONH- substitutions.
Wherein, the carbon atom number for the group that above-mentioned general formula (2) represents is in the range of 1~35.)
(in formula, R21Represent hydrogen atom, can be by alkyl or the alkoxy phenyl or carbon that replace that carbon atom number is 1~10 Atomicity is 3~10 cycloalkyl,
R22Represent that alkoxy, carbon atom number that alkyl, carbon atom number that carbon atom number is 1~10 are 1~10 are 2~10 Alkenyl or halogen atom,
R21And R22Alkyl, alkoxy and the alkenyl of expression can be replaced or unsubstituted by halogen atom,
D is 0~5 integer.)
(in formula, R23And R24Each independently represent the virtue that alkyl, carbon atom number that carbon atom number is 1~10 are 6~20 The aryl alkenyl that arylthio that aryloxy group that base, carbon atom number are 6~20, carbon atom number are 6~20, carbon atom number are 8~20 Aralkyl that base, carbon atom number are 7~20, carbon atom number be 2~20 containing heterocyclic group or halogen atom,
R23And R24The alkyl of expression, aryl, aryloxy group, arylthio, aromatic yl alkenyl, aralkyl and can containing heterocyclic group To be replaced or unsubstituted by halogen atom,
R23And R24Methylene in the alkyl and aralkyl of expression can be replaced by unsaturated bond ,-O- or-S,
R23It can be in adjacent R23Between form ring,
E represents 0~4 number,
F represents 0~8 number,
G represents 0~4 number,
H represents 0~4 number,
The sum of number of g and h is 2~4.)
<2>Shown in m=3, X such as following formula (3).
(in formula, X2It represents by R25Instead of carbon atom, trivalent carbon atom number be 1~35 aliphatic alkyl, trivalent Carbon atom number be 3~35 alicyclic type hydrocarbon, the carbon atom number of trivalent be 6~35 the carbon containing fragrant cyclic hydrocarbon radical or trivalent Atomicity be 2~35 containing heterocyclic group,
R25Represent that aryl that alkyl, carbon atom number that hydrogen atom, carbon atom number are 1~8 are 6~20 or carbon atom number are 7 ~20 aralkyl,
X2The aliphatic alkyl of expression can by halogen atom, cyano, hydroxyl, nitro, carbon atom number be 1~8 alkyl, Alkoxy, halogenated alkyl or halogenated alkoxy substitution,
X2Methylene in the aliphatic alkyl of expression can be by-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-SO2-、- NH- or the group substitution that they are composed,
Z1~Z3Each independently with the Z in above-mentioned general formula (2)1And Z2The group of expression is identical.
Wherein, the carbon atom number for the group that above-mentioned general formula (3) represents is in the range of 1~35.)
<3>Shown in m=4, X such as following formula (4).
(in formula, X3Represent carbon atom, the carbon atom number of the aliphatic alkyl that the carbon atom number of tetravalence is 1~35, tetravalence is The carbon atom number containing fragrant cyclic hydrocarbon radical or tetravalence that 3~35 alicyclic type hydrocarbon, the carbon atom number of tetravalence are 6~35 is 2~35 Containing heterocyclic group,
X3The aliphatic alkyl of expression can by halogen atom, cyano, hydroxyl, nitro, carbon atom number be 1~8 alkyl, Alkoxy, halogenated alkyl or halogenated alkoxy substitution,
X3Methylene in the aliphatic alkyl of expression can be by-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-SO2-、- NH- or the group substitution that they are composed,
Z1~Z4Each independently with the Z in above-mentioned general formula (2)1And Z2The group of expression is identical.
Wherein, the carbon atom number for the group that above-mentioned general formula (4) represents is in the range of 1~35.)
<4>Shown in m=5, X such as following formula (5).
(in formula, X4Represent that the carbon atom number of aliphatic alkyl, pentavalent that the carbon atom number of pentavalent is 2~35 is 3~35 The carbon atom number containing fragrant cyclic hydrocarbon radical or pentavalent that alicyclic type hydrocarbon, the carbon atom number of pentavalent are 6~35 is 2~35 containing heterocycle Group,
X4The aliphatic alkyl of expression can by halogen atom, cyano, hydroxyl, nitro, carbon atom number be 1~8 alkyl, Alkoxy, halogenated alkyl or halogenated alkoxy substitution,
X4Methylene in the aliphatic alkyl of expression can be by-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-SO2-、- NH- or the group substitution that they are composed,
Z1~Z5Each independently with the Z in above-mentioned general formula (2)1And Z2The group of expression is identical.
Wherein, the carbon atom number for the group that above-mentioned general formula (5) represents is in the range of 2~50.)
<5>Shown in m=6, X such as following formula (6).
(in formula, X5Represent that the carbon atom number of aliphatic alkyl, sexavalence that the carbon atom number of sexavalence is 2~35 is 3~35 The carbon atom number containing fragrant cyclic hydrocarbon radical or sexavalence that alicyclic type hydrocarbon, the carbon atom number of sexavalence are 6~35 is 2~35 containing heterocycle Group,
X5The aliphatic alkyl of expression can by halogen atom, cyano, hydroxyl, nitro, carbon atom number be 1~8 alkyl, Alkoxy, halogenated alkyl or halogenated alkoxy substitution,
X5Methylene in the aliphatic alkyl of expression can be by-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-SO2-、- NH- or the group substitution that they are composed,
Z1~Z6Each independently with the Z in above-mentioned general formula (2)1And Z2The group of expression is identical.
Wherein, the carbon atom number for the group that above-mentioned general formula (6) represents is in the range of 2~50.)
In addition, the present invention provides the coloured composition containing above-mentioned general formula (1) compound represented.
In addition, the present invention provides a kind of coloring photosensitive combination, contain：Contain at least one above-mentioned general formula (1) institute The dyestuff (A) that the compound shown forms, the polymerizable compound (B) with ethylenic bond unsaturated bond with acid value, light are free Base polymerization initiator (C) and the monomer (D) with ethylenic bond unsaturated bond.
In addition, solidfied material and the display that is formed using the solidfied material the present invention also provides above-mentioned coloring photosensitive combination Equipment colour filter.
Invention effect
Coloring photosensitive combination (the coloring alkali-developable photosensitive of the present invention containing the compound with specific structure Composition) heat resistance and excellent in light-resistance.In addition, its solidfied material is suitable for display equipment colour filter,
Specific embodiment
Hereinafter, based on preferred embodiment, the present invention will be described.
In above-mentioned general formula (1) compound represented, m group mutually can it is identical also can be different.The value of m is 2~6, from The angle of synthesis easiness is set out, and preferably 2~3.
As halogen atom, the R that can replace the A in above-mentioned general formula (1)1Shown halogen atom can replace R2And R3Table The alkyl that shows, aryl, aralkyl halogen atom, fluorine, chlorine, bromine, iodine can be enumerated,
As can replace A carbon atom number be 1~12 alkyl or R1~R6The carbon atom number of expression is 1~12 alkane Base can enumerate methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary butyl, isobutyl group, amyl, isopentyl, uncle penta Base, cyclopenta, hexyl, 2- hexyls, 3- hexyls, cyclohexyl, 4- methylcyclohexyls, heptyl, 2- heptyl, 3- heptyl, different heptyl, uncle Heptyl, 1- octyl groups, iso-octyl, t-octyl, adamantyl etc.,
As can replace A carbon atom number be 1~12 alkoxy or R1The carbon atom number of expression is 1~12 alkane Oxygroup, can enumerate methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, Amoxy, isoamoxy, tertiary amoxy, hexyloxy, cyclohexyloxy, cyclohexyl methoxy, tetrahydrofuran base oxygroup, oxinane Base oxygroup etc.,
As can replace A carbon atom number be 1~12 halogenated alkyl or R1The carbon atom number of expression is 1~12 halogen Substituted alkyl, at least one hydrogen atom that can enumerate the alkyl that above-mentioned carbon atom number is 1~12 be substituted by above-mentioned halogen atom and Into group, such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, nona-fluoro butyl group etc.,
As can replace A carbon atom number be 1~12 halogenated alkoxy or R1The carbon atom number of expression is 1~12 Halogenated alkoxy, at least one hydrogen atom that can enumerate the alkoxy that above-mentioned carbon atom number is 1~12 are substituted by above-mentioned halogen The group that atom forms, such as chloromethane epoxide, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, fluoroform Oxygroup, nine fluorine butoxy etc.,
As R2~R6The carbon atom number of expression is 6~20 aryl, can enumerate phenyl, naphthalene, anthryl, 2- methylbenzenes Base, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 4- ethenylphenyls, 3- isopropyl phenyls, 4- isopropyl phenyls, 4- butyl phenyls, 4- isobutyl phenenyls, 4- tert-butyl-phenyls, 4- hexyls phenyl, 4- cyclohexyl phenyls, 4- octyl phenyls, 4- (2- ethylhexyls) Phenyl, 4- stearyls phenyl, 2,3- 3,5-dimethylphenyls, 2,4- 3,5-dimethylphenyls, 2,5- 3,5-dimethylphenyls, 2,6- dimethyl benzenes Base, 3,4- 3,5-dimethylphenyls, 3,5- 3,5-dimethylphenyls, 2,4- di-t-butyls phenyl, 2,5- di-t-butyls phenyl, 2,6- bis-- Tert-butyl-phenyl, bis--tertiary pentyls of 2,4- phenyl, bis--tertiary pentyls of 2,5- phenyl, bis--t-octyls of 2,5- phenyl, 2,4- dicumyls Phenyl, 4- cyclohexyl phenyls, (1,1 '-xenyl) -4- bases, 2,4,5- trimethylphenyls, ferrocenyl etc.,
As R2~R6The carbon atom number of expression is 7~20 aralkyl, can enumerate benzyl, fluorenyl, indenyl, 9- fluorenyls Methyl, 2- phenyl-propane -2- bases, diphenyl methyl, trityl group, styryl, cinnamyl etc.,
As R4The carbon atom number of expression is 3~25 heterocycle, can enumerate pyridyl group, pyrimidine radicals, pyridazinyl, piperidines Base, pyranose, pyrazolyl, triazine radical, pyrrole radicals, quinolyl, isoquinolyl, imidazole radicals, benzimidazolyl, triazolyl, furans Base (furyl), furyl (furanyl), benzofuranyl (benzofuranyl), thienyl, sulfur phenenyl, benzo sulfur phenenyl, Thiadiazolyl group, thiazolyl, benzothiazolyl, oxazolyls, benzoxazolyl, isothiazolyl, isoxazolyls, indyl, 2- pyrroles Alkanone -1- bases, 2- piperidones -1- bases, bis- oxygroup imidazolidine -3- bases of 2,4-, bis- oxygen base oxazolidine -3- bases of 2,4- etc..
As halogen atom, alkyl, alkoxy, the alkyl halide described in above-mentioned general formula (2)~(6) and formula (2-1)~(2-3) Base, halogenated alkoxy, aryl and the respective example of aralkyl can be enumerated with being used as alkyl, alkoxy, alkyl halide in this part The same group of group that base, halogenated alkoxy, aryl and the respective example of aralkyl are hereinbefore enumerated.In addition, these bases In group, the group different from the group enumerated in this part about carbon atom number can be enumerated in the group enumerated in this part The group of carbon atom number as defined in satisfaction.
About-the NR in A2R3Base and-C (R1The position of substitution of)=C (CN) Y bases when A is phenyl ring, usually aligns； When A is naphthalene nucleus, usually 1,4 or 1,5；When A is anthracene nucleus, usually 1,4,1,5,1,10 or 9,10.
As the X in above-mentioned general formula (2)1The carbon atom number of the divalent of expression is 1~35 aliphatic alkyl, can be enumerated Methane, ethane, propane, isopropyl alkane, butane, secondary butane, tertiary butane, iso-butane, hexane, 2- methyl hexanes, 3- methyl hexanes, heptan Alkane, 2- methyl heptanes, 3- methyl heptanes, isoheptane, tertiary heptane, 1- methyloctanes, isooctane, tertiary octane, cyclopropane, ring fourth The groups such as alkane, pentamethylene, hexamethylene, cycloheptane, 2,4- dimethylcyclobutanes, 4- hexahydrotoluenes are by Z1And Z2What substitution formed The group of divalent, the methylene in these groups can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-SO2,-NH- or their groups Close the group substitution formed, group that they are composed represent such as-COO-O- ,-COO-S- ,-O-OCO- ,-S-OCO- ,- CO-NH- ,-NH-CO- etc., wherein, preferably by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- ,-CONH- ,-O-CONH- ,- The group of NHCO-O- substitutions,
The alicyclic type hydrocarbon that carbon atom number as divalent is 3~35, can enumerate cyclopenta, cyclohexyl, suberyl, ring Octyl group, cyclodecyl, 1- adamantyls, 2- adamantyls, noradamantyl, 2- methyl adamantanes base, norborny, different norborneol It is base, hydronaphthyl, perhydrogenating anthryl, bicyclic [1.1.0] butyl, bicyclic [1.1.1] amyl, bicyclic [2.1.0] amyl, double Ring [3.1.0] hexyl, bicyclic [2.1.1] hexyl, bicyclic [2.2.0] hexyl, bicyclic [4.1.0] heptyl, bicyclic [3.2.0] heptan It is base, bicyclic [3.1.1] heptyl, bicyclic [2.2.1] heptyl, bicyclic [5.1.0] octyl group, bicyclic [4.2.0] octyl group, bicyclic [4.1.1] octyl group, bicyclic [3.3.0] octyl group, bicyclic [3.2.1] octyl group, bicyclic [2.2.2] octyl group, spiral shell (4,4) nonyl, spiral shell (4,5) groups such as decyl, decahydronaphthalenes, tricyclodecyl, tetracyclododecyl group, cedrol, cyclo-dodecyl are by Z1And Z2Substitution Group of the divalent formed etc.,
The cyclic hydrocarbon radical containing fragrance that carbon atom number as divalent is 6~35, can enumerate phenylene, naphthylene, xenyl Groups are waited by Z1And Z2Replace group of divalent formed etc.,
Carbon atom number as divalent is 2~35 containing heterocyclic group, can enumerate pyridine, pyrazine, piperidines, piperazine, phonetic The groups such as pyridine, pyridazine, triazine, Hexahydrotriazine, furans, tetrahydrofuran, chroman, xanthene, thiophene, thiophane are by Z1And Z2Substitution The group of the divalent formed.
These groups can also further be replaced by the alkoxy that halogen atom, cyano, nitro or carbon atom number are 1~8.
In above-mentioned formula (2-1), as R21The carbon atom number of expression is 3~10 cycloalkyl, can enumerate cyclopropyl, ring fourth Base, cyclopenta, suberyl, cyclooctyl etc. and these groups are 1~10 by the alkyl or carbon atom number that carbon atom number is 1~10 Group for forming of alkoxy substitution etc.,
As carbon atom number be 2~10 alkenyl, can enumerate vinyl, pi-allyl, 1- acrylic, isopropenyl, 2- cyclobutenyls, 1,3-butadiene base, 2- pentenyls, 2- octenyls etc.,
Above-mentioned R22In alkyl, alkoxy and alkenyl can be replaced by halogen atom, the position of substitution there is no limit.
In above-mentioned formula (2-3), as R23And R24The carbon atom number of expression is 6~20 aryloxy group, can enumerate benzene oxygen Base, naphthoxy, 2- methylphenoxies, 3- methylphenoxies, 4- methylphenoxies, two oxygroup of 4- ethenylphenyls, 3- isopropyls Phenoxy group, 4- cumenes oxygroup, 4- butyl phenoxies, 4- tert-butyl benzenes oxygroup, 4- hexyls phenoxy group, 4- cyclohexyl benzene oxygen Base, 4- Octylphenoxies, 4- (2- ethylhexyls) phenoxy group, 2,3- dimethyl phenoxies, 2,4- dimethyl phenoxies, 2,5- Dimethyl phenoxy, 2,6- dimethyl phenoxies, 3,4- dimethyl phenoxies, 3,5- dimethyl phenoxies, 2,4- di-t-butyls Phenoxy group, 2,5- di-t-butyls phenoxy group, 2,6- di-t-butyls phenoxy group, bis--tert-amyl benzenes of 2,4- oxygroup, 2,5- tertiary pentyls The groups such as phenoxy group, 4- cyclohexyl benzenes oxygroup, 2,4,5- trimethylbenzenes oxygroup, ferrocenyl oxygroup and these groups are by halogen atom Replace the group formed,
As the arylthio that carbon atom number is 6~20, it can be 6 by the carbon atom number that halogen atom replaces that can enumerate above-mentioned The oxygen atom of~20 aryloxy group is substituted by group that sulphur atom forms etc.,
As the aromatic yl alkenyl that carbon atom number is 8~20, can enumerate by it is above-mentioned can be by carbon that halogen atom replace original Subnumber is that the oxygen atom of the aryloxy group of 6-20 is substituted by vinyl, pi-allyl, 1- acrylic, isopropenyl, 2- cyclobutenyls, 1,3- Group that the alkenyls such as butadienyl, 2- pentenyls, 2- octenyls form etc.,
It can enumerate pyridine containing heterocyclic group for 2~20 as carbon atom number, pyrazine, piperidines, piperazine, pyrimidine, rattle away The groups such as piperazine, triazine, Hexahydrotriazine, furans, tetrahydrofuran, chroman, xanthene, thiophene, thio-furan and these groups are by halogen original Group that son substitution forms etc..
As the X in above-mentioned general formula (3)2The carbon atom number of the trivalent of expression is 3~35 aliphatic alkyl, can be enumerated X in above-mentioned general formula (2)1Explanation in the aliphatic alkyl that illustrates by Z1、 Z2And Z3Replace the group of trivalent formed, this Methylene in a little groups can be by-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-SO2,-NH- or they be composed Group replaces, and the group that they are composed can enumerate such as-COO-O- ,-COO-S- ,-O-OCO- ,-S-OCO- ,-CO- NH- ,-NH-CO- etc., wherein, preferably by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- ,-CONH- ,-O-CONH- ,-NHCO- The group of O- substitutions,
The alicyclic type hydrocarbon that carbon atom number as trivalent is 3~35, can enumerate the X in above-mentioned general formula (2)1's The alicyclic type hydrocarbon illustrated in explanation is by Z1、Z2And Z3Replace the group of trivalent formed,
The cyclic hydrocarbon radical containing fragrance that carbon atom number as trivalent is 6~35, can enumerate the X in above-mentioned general formula (2)1 Explanation in illustrate containing fragrant cyclic hydrocarbon radical by Z1、Z2And Z3Replace the group of trivalent formed,
Carbon atom number as trivalent, containing heterocyclic group, can enumerate the X in above-mentioned general formula (2) for 2~351's What is illustrated in explanation contains heterocyclic group by Z1、Z2And Z3Replace the group of trivalent formed.
As the X in above-mentioned general formula (4)3The carbon atom number of the tetravalence of expression is 1~35 aliphatic alkyl, can be enumerated X in above-mentioned general formula (2)1Explanation in the aliphatic alkyl that illustrates by Z1、 Z2、Z3And Z4Replace the group of tetravalence formed, Methylene in these groups can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-SO2,-NH- or they be composed Group replaces, group that they are composed represent such as-COO-O- ,-COO-S- ,-O-OCO- ,-S-OCO- ,-CO-NH- ,- NH-CO- etc., wherein, preferably replaced by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- ,-CONH- ,-O-CONH- ,-NHCO-O- Group,
The alicyclic type hydrocarbon that carbon atom number as tetravalence is 3~35, can enumerate the X in above-mentioned general formula (2)1's The alicyclic type hydrocarbon illustrated in explanation is by Z1、Z2、Z3And Z4Replace the group of tetravalence formed,
The cyclic hydrocarbon radical containing fragrance that carbon atom number as tetravalence is 6~35, can enumerate the X in above-mentioned general formula (3)1 Explanation in illustrate containing fragrant cyclic hydrocarbon radical by Z1、Z2、Z3And Z4Replace the group of tetravalence formed,
Carbon atom number as tetravalence, containing heterocyclic group, can enumerate the X in above-mentioned general formula (2) for 2~351's What is illustrated in explanation contains heterocyclic group by Z1、Z2、Z3And Z4Replace the group of tetravalence formed,
As the X in above-mentioned general formula (5)4The carbon atom number of the pentavalent of expression is 2~35 aliphatic alkyl, can be enumerated X in above-mentioned general formula (2)1Explanation in the aliphatic alkyl that illustrates by Z1、 Z2、Z3、Z4And Z5Replace the base of pentavalent formed , the methylene in these groups can be by-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-SO2,-NH- or they be composed Group substitution, group that they are composed represent such as-COO-O- ,-COO-S- ,-O-OCO- ,-S-OCO- ,-CO-NH-, - NH-CO- etc., wherein, preferably taken by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- ,-CONH- ,-O-CONH- ,-NHCO-O- The group in generation,
The alicyclic type hydrocarbon that carbon atom number as pentavalent is 3~35, can enumerate the X in above-mentioned general formula (2)1's The alicyclic type hydrocarbon illustrated in explanation is by Z1、Z2、Z3、Z4And Z5Replace the group of pentavalent formed,
The cyclic hydrocarbon radical containing fragrance that carbon atom number as pentavalent is 6~35, can enumerate the X in above-mentioned general formula (2)1 Explanation in illustrate containing fragrant cyclic hydrocarbon radical by Z1、Z2、Z3、Z4And Z5Replace the group of pentavalent formed,
Carbon atom number as pentavalent, containing heterocyclic group, can enumerate the X in above-mentioned general formula (2) for 2~351's What is illustrated in explanation contains heterocyclic group by Z1、Z2、Z3、Z4And Z5Replace the group of pentavalent formed.
As the X in above-mentioned general formula (6)5The carbon atom number of the sexavalence of expression is 2~35 aliphatic alkyl, can be enumerated X in above-mentioned general formula (2)1Explanation in the aliphatic alkyl that illustrates by Z1、 Z2、Z3、Z4、Z5And Z6Replace the sexavalence formed Group, the methylene in these groups can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-SO2,-NH- or they combine and Into group substitution, group that they are composed represents such as-COO-O- ,-COO-S- ,-O-OCO- ,-S-OCO- ,-CO- NH- ,-NH-CO- etc., wherein, preferably by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- ,-CONH- ,-O-CONH- ,-NHCO- The group of O- substitutions,
The alicyclic type hydrocarbon that carbon atom number as sexavalence is 3~35, can enumerate the X in above-mentioned general formula (2)1's The alicyclic type hydrocarbon illustrated in explanation is by Z1、Z2、Z3、Z4、Z5And Z6Replace the group of sexavalence formed,
The cyclic hydrocarbon radical containing fragrance that carbon atom number as sexavalence is 6~35, can enumerate the X in above-mentioned general formula (2)1 Explanation in illustrate containing fragrant cyclic hydrocarbon radical by Z1、Z2、Z3、Z4、Z5And Z6Replace the group of sexavalence formed,
Carbon atom number as sexavalence, containing heterocyclic group, can enumerate the X in above-mentioned general formula (3) for 2~351's What is illustrated in explanation contains heterocyclic group by Z1、Z2、Z3、Z4、Z5And Z6Replace the group of sexavalence formed.
In above-mentioned general formula (1) compound represented, A is the compound of phenyl ring；R1Compound for hydrogen atom；R2And R3 Compound for the alkyl that carbon atom number is 1~12；R4Compound for the alkyl that carbon atom number is 1~12；M be 2 when, X such as X shown in general formula (2), in the formula (2)1Compound for the group in following groups 1；When m is 3, shown in X such as general formulas (3), X in the formula (3)2Compound for the group in following groups 2；When m is 4, X is as shown in general formula (4), in the formula (4) X3Compound for the group in group 3；When m is 5, Xs of the X such as shown in general formula (5), in the formula (5)4For in following groups 4 Group compound；When m is 6, Xs of the X such as shown in general formula (6), in the formula (6)5Change for the group in following groups 5 Object is closed due to the acquisition of raw material and manufactures easy, heat resistance height, preferably.
<Group 1>
(in formula, R5For with the R in above-mentioned general formula (1)5Identical group, can be identical when having 2 or more in group Can be different, p represents that 1~3 integer, q represent that 0~3 integer, r represent 1~19 integer.)
<Group 2>
<Group 3>
<Group 4>
<Group 5>
As the specific example of above-mentioned general formula (1) compound represented, following [chemical formulas 15]~[chemistry can be enumerated Formula 20B] compound represented, but the present invention is not limited to these compounds.
[chemical formula 15]
[chemical formula 15A]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
[chemical formula 20A]
[chemical formula 20B]
The compound for structure shown in above-mentioned general formula (1) that there are one at least tools of the present invention as dyestuff in addition to being described below The coloured compositions such as coloring photosensitive combination in other than use, be additionally operable to the optical filtering used in display or optical lens Device, silver salt photo photosensitive material, dye object, coating, ink, electrophotographic photoconductor, toner, thermal recording paper, transfer belt, In optical recording pigment, solar cell, organic semiconductor, clinical examination reagent, laser therapy pigment, dyeing etc..
The manufacturing method of above-mentioned general formula (1) compound represented is not particularly limited, such as m=2, A are phenyl ring, Y is cyanogen Base, X such as *-Z1-X1-Z2When shown in-*, as shown in following reaction equations, by making aldehyde compound anti-under alkaline condition with malononitrile It should manufacture.During m=3~6, it may be based on this and manufactured.As alkali, Piperazine anhydrous etc. can also be used to replace following shown Triethylamine.
(in formula, R1、R2And R3With identical, the Z in above-mentioned general formula (1)1、Z2And X1It is identical in above-mentioned general formula (2).)
The dyestuff (A) of the present invention can contain at least one above-mentioned general formula (1) compound represented, can be used alone or Multiple combinations are used.In addition, in addition to above-mentioned general formula (1) compound represented, well known dyestuff also can be used.As known Dyestuff, can enumerate for example azo dyes, anthraquinone dye, indigoid, triarylmethane dye, xanthene dye, alizarin dyes, Acridine dye stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamines dyestuff, oxazine dyes, phthalocyanine dye Dyestuffs such as material, cyanine dye etc. can will use after a variety of mixing of these dyestuffs.
Here, " dyestuff " is used after being dissolved in organic solvent, after with the dispersions such as dispersion resin in use, being known as after " pigment " stated.
In the dyestuff (A) of the present invention, the content of above-mentioned general formula (1) compound represented be preferably 50~100 mass %, More preferably 70~100 mass %.When the content of above-mentioned general formula (1) compound represented is less than 50 mass %, sometimes in solvent In dissolubility reduce, heat resistance reduce.
Then, the coloured composition of the present invention is illustrated.The coloured composition of the present invention contains above-mentioned general formula (1) institute The compound shown.In the coloured composition, with the above-mentioned dyestuff (A) containing the compound, with acid value with ethylenic bond not The polymerizable compound (B) of saturated bond, optical free radical polymerization initiator (C) and there is ethylenic bond in addition to above-mentioned (B) ingredient The monomer (D) of unsaturated bond is that the composition of required ingredient is coloring photosensitive combination of the invention.Below to the present invention's Coloring photosensitive combination illustrates.
In above-mentioned coloring photosensitive combination, the content of above-mentioned dyestuff (A) is preferably 0.1~20 mass %, is more preferably 0.5~15 mass %.When the content of dyestuff (A) is less than 0.1 mass %, coloring is insufficient, when for 20 mass %, color sensation Dyestuff (A) is it is possible that can be precipitated in photosensitiveness composition.
As the above-mentioned polymerizable compound with ethylenic bond unsaturated bond with acid value, (methyl) third can be enumerated Olefin(e) acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid (himic acid), crotonic acid, different bar Beans acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, mono succinate [2- (methyl) acryloyl-oxy Base ethyl] ester, phthalic acid list [2- (methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) propylene Two end such as acid esters has list (methyl) acrylate, (methyl) acrylic acid malic acid hydroxyl of the polymer of carboxyl and hydroxyl Ethyl ester, (methyl) acrylic acid malic acid hydroxy propyl ester, bicyclopentadiene malate have 1 carboxyl and 2 or more The unsaturation polyacid such as multifunctional (methyl) acrylate of (methyl) acryloyl group；Phenol and/or cresol novalac Epoxy resin, xenyl skeleton, novolak epoxy resins, the bisphenol A novolac type epoxy with naphthalene skeleton The novolac type epoxies compounds such as compound, bicyclopentadiene novolac type epoxy compound have more officials The polyphenyl methylmethane type ring oxygen resin of energy epoxy group makes unsaturated monoacid act on the epoxy compound shown in the following general formula (7) The epoxy group of the epoxy resin such as object so make multi-anhydride act on obtained from resin, as pentaerythritol triacrylate, two The polyfunctional acrylic ester of the hydroxyls such as five acrylate of pentaerythrite and succinic anhydride, phthalic anhydride, tetrahydrochysene neighbour benzene two The polymer of the polyfunctional acrylic ester with acid value of the reactant of the dibasic acid anhydrides such as formic anhydride etc..
(in formula, X41Represent that alkylidene, carbon atom number that Direct Bonding, methylene, carbon atom number are 1~4 are 3~20 Alicyclic type hydrocarbon ,-O- ,-S- ,-SO2,-SS- ,-SO- ,-CO- ,-OCO- or above-mentioned formulas (2-1)~(2-3) represent group, The alkylidene can be replaced by halogen atom, R41、R42、 R43And R44Each independently represent hydrogen atom, the alkane that carbon atom number is 1~5 The alkenyl or halogen atom that alkoxy that base, carbon atom number are 1~8, carbon atom number are 2~5, abovementioned alkyl, alkoxy and chain The integer that alkenyl can be replaced by halogen atom, s is 0~10.)
These polymerizable compounds can be used alone or be used in mixed way two or more, furthermore it is also possible to without acid The polymerizable compound with ethylenic bond unsaturated bond of value is applied in combination.It, can be pre- by them when two or more is used in mixed way It is first copolymerized and is used in the form of copolymer.
As the above-mentioned polymerizable compound with ethylenic bond unsaturated bond without acid value, such as (first can be enumerated Base) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, following chemical combination Object No.A1~No.A4, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) third Olefin(e) acid-the tert-butyl ester, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) The different nonyl ester of acrylic acid, (methyl) stearyl acrylate, (methyl) lauryl acrylate, (methyl) methoxyethyl acrylate, (first Base) acrylate methyl esters, (methyl) acrylate, (methyl) acrylic-amino propyl ester, (first Base) acrylate propyl ester, (methyl) ethoxyethyl acrylate, poly- (ethyoxyl) ethyl ester of (methyl) acrylic acid, (methyl) acrylate, butoxy ethoxy ethyl ester, (methyl) ethylhexyl acrylate, (methyl) phenoxyethyl acrylate, (first Base) acrylic acid tetrahydrofuran ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, second Glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, poly- second two Alcohol two (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, 1,6- oneself two Alcohol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid Ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, pentaerythrite four (methyl) propylene Acid esters, pentaerythrite three (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, three [(methyl) propylene Methylaminosulfonylethyl] the unsaturated monoacid such as chlorinated isocyanurates, polyester (methyl) acrylate oligomer and polyalcohol or polyphenol Ester；The metal salt of the unsaturation polyacid such as (methyl) zinc acrylate resin, (methyl) Magnesium Acrylate Prepared；Maleic anhydride, itaconic anhydride, lemon health Acid anhydrides, methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, trialkyl tetrabydrophthalic anhydride, 5- (2,5- dioxies Miscellaneous tetrahydrofuran base) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydrides, trialkyl tetrabydrophthalic anhydride-maleic anhydride add Into the acid anhydrides of the unsaturated polyacid such as object, dodecenyl succinic anhydride, methylnadic anhydride；(methyl) acrylamide, Asia Methyl pair-(methyl) acrylamide, diethylenetriamines three (methyl) acrylamide, bis- (methyl) acryloyls of phenylenedimethylidyne The amide of the unsaturation monoacid such as amine, α-chloroacrylamide, N-2- hydroxyethyls (methyl) acrylamide and polyamine；Methacrylaldehyde Wait unsaturated aldehydes；The unsaturated nitriles such as (methyl) acrylonitrile, α-chloroacrylonitrile, vinylidene dinitrile, allyl cyanide；Styrene, 4- first Base styrene, 4- ethyl styrenes, 4- methoxy styrenes, 4-Vinyl phenol, 4- chlorostyrenes, divinylbenzene, ethylene Base toluene, vinyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4- vinylbenzenesulfonic acids, vinyl benzyl methyl ether, second The unsaturation aromatic compound such as alkenyl benzyl glycidyl ether；The beta-unsaturated ketones such as ethylene methacrylic ketone；Vinyl amine, pi-allyl The unsaturated amine compounds such as amine, n-vinyl pyrrolidone, vinylpiperidine；Methoxy ethylene, vinyl ethyl ether, normal-butyl second The vinyl ethers such as alkene ether, isobutyl vinyl ether, allyl glycidyl ether；Maleimide, N-phenylmaleimide, The unsaturated acyls imines such as N- N-cyclohexylmaleimides；The indenes such as indenes, 1- methyl indenes；1,3- butadiene, isoprene, chlorine The aliphatic conjugated dienes class such as pentadiene；Polystyrene, poly- (methyl) methyl acrylate, poly- (methyl) n-butyl acrylate, The end of the polymer molecular chains such as polysiloxanes has the macromonomer class of single (methyl) acryloyl group；(methyl) acrylonitrile, Other vinyl compounds such as ethylene, propylene, butylene, vinyl chloride, vinyl acetate and polymethyl methacrylate macromolecular list The macromonomers such as body, Group-capped Polystyrene Macromer class, the monomethacrylates of tricyclodecane skeleton, N- phenyl Malaysia acyl The copolymer of imines, methacryloxymethyl -3- Ethyloxetanes etc. and (methyl) acrylic acid and make they with it is clear (first obtained from being reacted with isocyanate compounds with unsaturated bond such as electrician's (strain) corporation Karenz MOI, AOI Base) copolymer of acrylic acid, vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, three Pi-allyl phosphate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, Yi Xi oxazolins, vinyl click Azoles, vinyl pyrrolidone, vinylpyridine, the vinyl monomer of hydroxyl and polyisocyanate compounds ethyleneamino Formic acid ester compound, the vinyloxirane of the vinyl monomer of hydroxyl and polyepoxides, pentaerythrite 3 third Polyfunctional acrylic ester and first phenylene diisocyanate, six methylenes of the hydroxyls such as olefin(e) acid ester, Dipentaerythritol Pentaacrylate Reactant of the polyfunctional isocyanates such as group diisocyanate etc..
Compound N o.A1
Compound N o.A2
Compound N o.A3
Compound N o.A4
In order to adjust acid value to improve the developability of above-mentioned photosensitive composite, with it is above-mentioned with acid value with ethylenic bond The polymerizable compound of unsaturated bond can further use simple function or multi-functional epoxy compound together.It is above-mentioned that there is acid value The polymerizable compound with ethylenic bond unsaturated bond solid constituent acid value be preferably 5~120mgKOH/g range, The dosage of simple function or multi-functional epoxy compound are preferably selected in the way of above-mentioned acid value is met.
As above-mentioned monofunctional epoxy compound, can enumerate glycidyl methacrylate, methyl glycidyl ether, Ethyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl Ether, tertiary butyl glycidyl ether, amyl glycidol ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl Ether, nonyl glycidol ether, decyl glycidyl ether, undecyl glycidol ether, lauryl diglycidyl ether, tridecane Base glycidol ether, myristyl glycidol ether, pentadecyl glycidol ether, cetyl glycidyl ether, 2- ethyls Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidol ether, to methoxy ethyl glycidol ether, phenyl Glycidol ether, to methoxyl group glycidol ether, p-butylphenol glycidol ether, cresyl glycidol ether, 2- methyl first Phenolic group glycidol ether, 4- nonyl phenyl glycidyls glycerin ether, benzyl glycidyl ether, to cumyl phenyl glycidol ether, triphen Methyl glycidyl ether, methacrylic acid 2,3- epoxy groups propyl ester, epoxidised soybean oil, epoxidized linseed, butyric acid shrink sweet Grease, single ethylene oxide butylcyclohexane, 1,2- epoxy -4- vinyl cyclohexanes, styrene oxide, pinene oxide, oxidation methyl Styrene, cyclohexene oxide, propylene oxide etc..
As above-mentioned multi-functional epoxy compound, it is selected from when using by biphenol type epoxy compound and glycidol ethers group Into one or more of group when, due to can the more good coloring alkali-developable photosensitive composition of acquired character, It is preferred that.As the biphenol type epoxy compound, other than it can use the epoxide shown in above-mentioned general formula (7), may be used also Enumerate the biphenol type epoxy compound such as A Hydrogenated Bisphenol A type ring oxygen compound.As the glycidol ethers, can enumerate Ethylene glycol diglycidylether, propylene glycol diglycidylether, 1,4- butanediol diglycidyl ethers, 1,6-HD two shrink Glycerin ether, 1,8- ethohexadiols diglycidyl ether, 1,10- decanediols diglycidyl ether, 2,2- dimethyl -1,3- propylene glycol two Glycidol ether, diethylene glycol diglycidyl glycerin ether, Triethylene Glycol Diglycidyl Ether, tetraethylene glycol diglycidyl ether, six Ethylene glycol diglycidylether, 1,4 cyclohexane dimethanol diglycidyl ether, 1,1,1- tri- (glycidyl oxy methyl) Propane, 1,1,1- tri- (glycidyl oxy methyl) ethane, 1,1,1- tri- (glycidyl oxy methyl) methane, 1,1,1, 1- tetra- (glycidyl oxy methyl) methane.
In addition, phenol novolak resin type ring oxygen compound, xenyl novolac type epoxy also can be used Close object, cresol novolak type epoxide, bisphenol A novolac type epoxy compound, bicyclopentadiene line The novolac type epoxies compound such as type novolak type epoxy compounds；3,4- epoxy -6- methylcyclohexylmethyl -3, 4- epoxy -6- methylcyclohexanecarboxylic acids ester, 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylates, 1- epoxy second The cycloaliphatic epoxy of base -3,4- 7-oxa-bicyclo[4.1.0s etc.；O-phthalic acid diglycidyl ester, tetrahydrophthalic acid two The glycidols esters such as ethylene oxidic ester, dimer acid glycidyl ester ester；Four glycidyl group diaminodiphenyl-methane, three contractings Water glyceryl-para-aminophenol, the glycidyls amine such as N, N- diglycidylanilines；1,3- diglycidyl -5, The hetero ring types epoxides such as 5- dimethyl hydantoins, triglycidyl group chlorinated isocyanurates；Dicyclopentadiene Wait dioxide compounds；Naphthalene type ring oxygen compound, triphenylmethane type epoxy compound, dicyclopentadiene type epoxy compound Deng.
In above-mentioned coloring photosensitive combination, the above-mentioned polymerizable compound with ethylenic bond unsaturated bond with acid value (B) content is preferably 0.1~90 mass %, more preferably 1~80 mass % in coloring photosensitive combination.When above-mentioned poly- When the content of conjunction property compound (B) is less than 0.1%, developing property is it is possible that become inadequate, when more than 90%, cured film Intensity is it is possible that can become inadequate.
As long as above-mentioned optical free radical polymerization initiator can cause the compound of free radical polymerization by being irradiated by light , such as acetophenone based compound, benzyl based compound, benzophenone based compound, thioxanthones based compound can be exemplified Ketone based compound, oxime compound etc. is waited to be used as preferred initiator.
As acetophenone based compound, such as diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl third can be enumerated Alkane -1- ketone, 4'- isopropyl -2- hydroxy-2-methyls acetophenone, 2- hydroxymethyl -2- methyl acetophenones, 2,2- dimethoxy -1, 2- diphenylethane -1- ketone, to dimethylamino benzoylformaldoxime, to tertiary butyl dichloroacetophenone, to tertiary butyl trichloroacetophenone, right Nitrine benzylidene acetophenone, 1- hydroxycyclohexylphenylketones, 2- methyl-1s-[4- (methylsulfany) phenyl] -2- morpholinopropanones - 1,2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone -1, benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- Hydroxy-2-methyl -1- propane -1- ketone etc..
As benzyl based compound, benzyl, anisyl etc. can be enumerated.
As benzophenone based compound, such as benzophenone, o-benzoyl yl benzoic acid methyl esters, rice Chi can be enumerated The bis- diethylamino benzophenone of ketone, 4,4'-, 4,4'- dichloro benzophenones, 4- benzoyl -4'- methyldiphenyl sulfides Deng.
As oxime compound, 1,2- acetyl caproyls can be enumerated, 1- [4- (phenylsulfartyl)-, 2- (O- benzoyl oximes)], Ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -, 1- (O- acetyl group oxime), ketone, (2- methyl Phenyl) [6- nitros -9- [3- (trimethylsilyl) propyl] -9H- carbazole -3- bases] -, 1-O- acetyl group oxime), ketone, (9- Ethyl -6- nitro -9H- carbazole -3- bases) (2- aminomethyl phenyls), O- acetyl group oxime, ketone, (9- ethyl -6- nitro -9H- carbazoles - 3- yls) [2- methyl -4- (4- morpholinyls) phenyl), O- acetyl group oxime, ketone, (3,5- dinitrophenyls) (9- ethyl -6- nitre Base -9H- carbazole -3- bases) (2- aminomethyl phenyls), O- acetyl group oxime, ketone, (9- ethyl -6- nitro -9H- carbazole -3- bases) (3- nitrobenzophenones), O- acetyl group oxime, 1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, [2- (the acetyl group oxygen of 1,3,5- tri- Base) -3- [3- [(1E) -1- [(acetyl group oxygroup) Iminoethyl] -6- nitro -9H- carbazole -9- bases] propyl] -, 1,2- fourths Alkane diketone, 1- [4- (phenylsulfartyl) phenyl]-, 2- (O- acetyl group oxime), 1,2- butanediones, 1- [4- [[4- (2- '-hydroxyethoxies Base) phenyl] sulfenyl] phenyl] -, 2- (O- acetyl group oxime), 1,2- butanediones, 1,1 '-(two -4,1- phenylenes of sulfenyl) be double -, 2,2- bis- (O- acetyl group oximes), 1,2- acetyl caproyls, 1- [4- (phenylsulfartyl) phenyl]-, 2- [O- (4- methyl benzoyls) oxime] Deng.
As thioxanthones based compound, thioxanthones, 2- methyl thioxanthones, 2- ethyls thioxanthones, 2- diuril tons can be enumerated Ketone, 2-isopropylthioxanthone, 2,4- diethyl thioxanthones etc..
As other optical free radical polymerization initiators, the oxidation of 2,4,6- trimethyl benzoyl diphenyl bases can be enumerated Phosphine, bis- (cyclopentadienyl groups)-bis- [bis- fluoro- 3- of 2,6- (pyrroles -1- bases)] titanium etc..
These optical free radical polymerization initiators can be according to desired performance with the use of one kind or two or more.
In above-mentioned coloring photosensitive combination, the content of above-mentioned optical free radical polymerization initiator (C) is in coloring phototonus group Close preferably 0.1~30 mass %, particularly preferably 0.5~10 mass % in object.The content of above-mentioned Photoepolymerizationinitiater initiater (C) is small When 0.1 mass %, curing caused by exposing may become inadequate, and when more than 30 mass %, cause in resin combination Agent (C) may be precipitated.
In the coloring photosensitive combination of the present invention, as the monomer (D) with ethylenic bond unsaturated bond, it can use not The polymerizable compound with ethylenic bond unsaturated bond with above-mentioned acid value.Monomer (D) with ethylenic bond unsaturated bond Content is preferably 10~1000 matter relative to the 100 mass % of polymerizable compound with ethylenic bond unsaturated bond with acid value Measure %, more preferably 20~800 mass %.
Inorganic pigment or organic pigment can also be further added in above-mentioned coloring photosensitive combination, such as can be used Nitroso compound, nitro compound, azo-compound, two azo-compounds, xanthene compound, quinoline compound, anthraquinone Close object, coumarin compound, phthalocyanine compound, isoindolinone compound, isoindoline compounds, quinoline azone compound, two And anthrone compound, purple cyclic ketone compound, compound, diketopyrrolo-pyrrole compound, thioindigo compound, dioxazine chemical combination Object, triphenylmethane compounds, quinophthalone compound, naphthalene tetracarboxylic acid；The metal complex chemical combination of azo dyes, cyanine dye Object；Mordant pigment；Carbon black or acetylene carbon black, section's qin conductive black or the lamp black method obtained by oven process, channel process, pyrolysis method The carbon blacks such as carbon black；Adjusted with epoxy resin, be coated above-mentioned carbon black obtained from pigment, in advance by above-mentioned carbon black in a solvent with set Fat carry out decentralized processing, make its adsorb the resin of 20~200mg/g obtained from pigment, above-mentioned carbon black is subjected to acid or alkalinity Pigment, average grain diameter are more than 8nm obtained from surface treatment and DBP oil absorptions are below 90ml/100g pigment, by 950 CO, CO in volatile ingredient at DEG C2The total oxygen demand of calculating is every 100m of carbon black2Surface area is the pigment of more than 9mg；Stone Ink, Graphon, activated carbon, carbon fiber, carbon nanotube, micro- coiled carbon fibers, carbon nanohorn, carbon aerogels, fullerene；Benzene Amido black, pigment black 7, titanium are black；Hydrophobic resin, chrome oxide green, milori blue, cobalt green, cobalt blue, manganese systems, ferrocyanide, phosphoric acid Salt ultramarine, Prussian blue, ultramarine, cerulean blue, chrome green, emerald green, lead sulfate, yellow lead, zinc yellow, iron oxide red (red oxidization Iron (III)), cadmium red, synthesis iron oxide black, inorganic pigments or the organic pigment such as umber.These pigment can be individually or by a variety of mixing It uses.
As above-mentioned inorganic pigment or organic pigment, commercially available pigment can also be used, can enumerate such as paratonere 1, 2、3、9、10、14、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、 169、170、171、177、 179、180、184、185、192、200、202、209、215、216、217、220、223、 224、 226、227、228、240、254；Pigment orange 13,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62, 64、65、71；Pigment yellow 1,3,12,13,14,16,17,20,24,55,60,73,81,83,86,93,95,97,98,100, 109、110、113、114、117、120、125、126、127、129、137、138、 139、147、148、150、151、152、153、 154、166、168、175、180、185；Pigment Green 7,10,36；Pigment blue 15,15：1、15：2、15：3、15：4、15：5、15： 6、22、24、56、60、61、62、64；Pigment violet 1,19,23,27,29,30,32,37,40,50 etc..
Above-mentioned coloring photosensitive combination can be made to dissolve or be distributed in organic solvent, the masking liquid that will be obtained as needed The means well known to spin coater, roll coater, bar coater, die coating machine, curtain coater, various printings, impregnating are applied to sodium glass In the support substrates such as glass, quartz glass, semiconductor substrate, metal, paper, plastics, carrying out light irradiation makes its curing.
As above-mentioned organic solvent, can enumerate generally according to the solvent that is required to dissolve or disperse above-mentioned each ingredient, Such as the ketones such as methyl ethyl ketone, methyl amylketone, diethyl ketone, acetone, methyl isopropyl ketone, methylisobutylketone, cyclohexanone, 2-HEPTANONE；Ether, The ether series solvents such as dioxane, tetrahydrofuran, 1,2- dimethoxy-ethanes, 1,2- diethoxyethane, dimethyl ether； Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, succinic acid The ester series solvents such as dimethyl ester, alcohol ester；The cellosolves series solvent such as glycol monoethyl ether, ethylene glycol monoethyl ether；Methanol, ethyl alcohol, exclusive or The alcohol series solvents such as normal propyl alcohol, exclusive or n-butanol, amylalcohol；Ethylene glycol monomethyl acetic acid esters, ethylene glycol list ethylhexoate, the third two Alcohol -1- monomethyl ether -2- acetic acid esters (PGMEA), dipropylene glycol monomethyl ether acetic acid esters, 3- methoxybutyls acetic acid esters, ethyoxyl second The ether-ethers series solvent such as base propionic ester；The BTX series solvents such as benzene,toluene,xylene；The fat of hexane, heptane, octane, hexamethylene etc. Race's hydrocarbon system solvent；The terpenic series hydrocarbon ils such as turpentine oil, D- limonenes, firpene；Mineral spirits, Swasol#310 (Cosmo Guia Hills oil (Co., Ltd.)), the paraffin series solvent such as Solvesso#100 (Exxon chemistry (Co., Ltd.))；Carbon tetrachloride, chloroform, trichlorine The halogenated aliphatics hydrocarbon system solvents such as ethylene, vinyl chloride, 1,2- dichloroethanes；Chlorobenzene etc. contains halogenated aromatic rings hydrocarbon system solvent；Card must Alcohol series solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N, N- dimethyl second Amide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), water etc., these solvents can be with a kind of uses or with mixed solvent of more than two kinds Form uses.Wherein, ketone, ether-ether series solvent etc., particularly propylene glycol -1- monomethyl ether -2- acetic acid esters, cyclohexanone etc. due to The compatibility of resist and Photoepolymerizationinitiater initiater is good in photosensitive composite, therefore preferably.
Inorganic compound can also further be contained in above-mentioned coloring photosensitive combination.It, can as the inorganic compound Enumerate such as nickel oxide, iron oxide, yttrium oxide, titanium oxide, zinc oxide, magnesia, calcium oxide, potassium oxide, silica, oxygen Change the metal oxides such as aluminium；Layered clay mineral, milori blue, calcium carbonate, magnesium carbonate, cobalt system, manganese systems, glass powder, mica, Talcum, kaolin, ferrocyanide, various metal sulfates, sulfide, selenides, alumina silicate, calcium silicates, aluminium hydroxide, Platinum, gold, silver, copper etc..
In above-mentioned coloring photosensitive combination, when using pigment and/or inorganic compound, dispersant can be added in.Make For the dispersant, as long as colorant, inorganic compound dispersion, stabilized dispersant then any dispersant can be made, Can use commercially available dispersant, such as BYK corporations, BYK series, it is preferable to use by the polyester with basic functionality, Macromolecule dispersing agent that polyethers, polyurethane are formed, with nitrogen-atoms as basic functionality and the functional group with nitrogen-atoms is Amine and/or its quaternary salt, the dispersant that amine value is 1~100mgKOH/g.
In addition, it can also be added as needed in above-mentioned coloring photosensitive combination to methyl phenyl ethers anisole, hydroquinone, burnt catechu The thermal polymerization inhibitors such as phenol, tert-butyl catechol, phenthazine；Plasticizer；Adhesion promoters；Filler；Antifoaming agent；Levelling agent； Surface conditioner；The antioxidants such as phenol system antioxidant, phosphite ester system antioxidant, thioether antioxidant；Ultraviolet light Absorbent；Dispersing aid；Anticoalescent；Catalyst；Effect accelerating agent；Crosslinking agent；The common additive such as thickener.
In addition, by being used together other with the above-mentioned polymerizable compound with ethylenic bond unsaturated bond with acid value Organic polymer can improve the characteristic of the solidfied material of above-mentioned coloring photosensitive combination.As above-mentioned organic polymer, can arrange Enumerate such as polystyrene, polymethyl methacrylate, Eudragit NE30D, poly- (methyl) third Olefin(e) acid, styrene-(methyl) acrylic copolymer, (methyl) acryl acid-methyl methacrylate copolymer, ethylene-vinyl chloride Copolymer, ethylene-vinyl base co-polymer, Corvic, ABS resin, nylon 6, nylon66 fiber, nylon 12, polyurethane tree Fat, makrolon polyvinyl butyral, cellulose esters, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamides Amine imide resin, polyamic acid resin, epoxy resin etc., wherein, preferably polystyrene, (methyl) acrylic acid-metering system Sour methyl terpolymer, epoxy resin.
In above-mentioned coloring photosensitive combination can also and with hot radical polymerization initiator, chain-transferring agent, sensitizer, table Face activating agent, silane coupling agent, melamine etc..
As above-mentioned hot radical polymerization initiator, 2 can be enumerated, 2 '-azodiisobutyronitrile, 2, the bis- (first of 2 '-azo Base isobutyrate), the double -2,4- methyl pentane nitriles of 2,2 '-azo, the idol such as 1,1 '-azo bis- (1- acetoxyl group -1- diphenylphosphino ethanes) Nitrogen series initiators；Benzoyl peroxide, di-tertiarybutyl benzoyl, t-butylperoxy pivarate, two (the tertiary fourths of 4- Butylcyclohexyl) persulfuric acid such as peroxide series initiators, ammonium persulfate, sodium peroxydisulfate, the potassium peroxydisulfate such as peroxy dicarbonate Salt etc..They can a kind of use or two kinds of uses mixed above.
As above-mentioned chain-transferring agent, sensitizer, the compound of usual sulfur atom-containing can be used.Such as thioacetic acid, sulfydryl Succinic acid, sulfydryl salicylic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids, 3- mercaptobutyric acids, N- (2- mercapto radical propionyl groups) glycine, 2- Sulfydryl niacin, 3- [N- (2- mercaptoethyls) carbamoyl] propionic acid, 3- [N- (2- mercaptoethyls) amino] propionic acid, N- (3- Mercapto radical propionyl group) alanine, 2- mercapto ethane sulfonic acids, 3- mercaptopropanesulfonic acids, 4- sulfydryl butane sulfonic acid, dodecyl (4- first Base sulfenyl) phenylate, 2 mercapto ethanol, 3- sulfydryl -1,2- propylene glycol, 1- sulfydryl -2- propyl alcohol, 3- sulfydryl -2- butanol, sulfydryl benzene Phenol, 2-MEA, 2- mercaptoimidazoles, 2-mercaptobenzimidazole, 2- sulfydryl -3- pyridols, 2-mercaptobenzothiazole, sulfydryl The sulfhydryl compounds such as acetic acid, trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), by the mercapto Di-sulphide compounds, iodoacetic acid, iodopropionic acid, ethylene iodohydrin, 2- iodoethane sulfonic acid, 3- iodine third obtained from based compound oxidation The iodine such as alkyl sulfonic acid alkyl compound, trimethylolpropane tris (3- mercaptoisobutanoics acid esters), butanediol bis- (3- mercaptoisobutanoics acid esters), Hexanedithiol, decanedithiol, 1,4- dimethyl sulfydryls benzene, butanediol disulfide group propionic ester, butanediol disulfide group acetic acid esters, Ethylene glycol disulfide group acetic acid esters, trimethylolpropane tris ethyl thioglycollic acid ester, butanediol disulfide group propionic ester, trimethylolpropane tris Thiohydracrylic acid ester, trimethylolpropane tris ethyl thioglycollic acid ester, four thiohydracrylic acid ester of pentaerythrite, four ethyl thioglycollic acid of pentaerythrite Ester, three sulfenyl propionic ester of trihydroxy ethyl, following compound N o.C1, tri-thiol propionic acid three (2- hydroxyethyls) chlorinated isocyanurates Etc. aliphatic multi-functional thiol compound, Showa electrician's corporation Karenz MTBD1, PE1, NR1 etc..
As above-mentioned surfactant, the fluorine surface-actives such as perfluoralkyl phosphate, perfluoroalkyl carboxylate can be used The anionic surfactants such as agent, higher fatty acids basic salt, alkylsulfonate, alkyl sulfate, higher amines halate, season The cationic systems such as ammonium salt surfactant, polyethylene glycol alkyl ether, cithrol, sorbitan-fatty acid It lives on the surfaces such as the nonionic surfactants such as ester, glycerine monofatty ester, amphoteric surfactant, silicone based surfactants Property agent, they can also be applied in combination.
As above-mentioned silane coupling agent, such as chemical company of SHIN-ETSU HANTOTAI silane coupling agent can be used, wherein it is preferable to use KBE-9007, KBM-502, KBE-403 etc. have the silane coupling agent of isocyanate group, methylacryloyl, epoxy group.
As above-mentioned melamine compounds, (poly-) methylol melamine, (poly-) methylol glycoluril, (poly-) methylol benzene can be enumerated And active methylol (the CH in the nitrogen compounds such as guanamine, (poly-) methylolurea2OH yls) all or part of (at least 2 It is a) compound obtained from alkyl etherified.Here, as the alkyl for forming alkyl ether, methyl, ethyl or fourth can be enumerated Base mutually can be the same or different.In addition, can not be condensed by alkyl etherified methylol in an intramolecular oneself, Can also two intermolecular condensations, result formed oligomer ingredient.Specifically, can use hexa methoxy methyl melamine, Six butoxymethyl melamines, tetramethoxymethylglycoluril, four butoxymethyl glycolurils etc..Wherein, preferably hexamethoxy methyl is close Amine, six butoxymethyl melamines etc. are through alkyl etherified melamine.
In above-mentioned coloring photosensitive combination, except dyestuff (A), the polymerism with ethylenic bond unsaturated bond with acid value Compound (B), optical free radical polymerization initiator (C) and with ethylenic bond unsaturated bond monomer (D) other than any ingredient (its In not include organic solvent) content can suitably be limited using purpose according to it, but preferably with respect to acid value with It is below mass part that 100 mass parts of polymerizable compound (B) of ethylenic bond unsaturated bond add up to 500.
In addition, as the light source of active light used when curing above-mentioned coloring photosensitive combination, hair can be used Go out the light source of the light of 300~450nm of wavelength, such as ultrahigh pressure mercury lamp, Mercury arc lamp, carbon arc lamp, xenon arc lamp etc..
In addition, it is directly formed from computer digital information without using mask as exposure light source by using laser The direct picture of laser of image is not only from productivity but also from the angle for the raising for seeking clarity, positional precision etc. It is also useful, as the laser, the light of the wavelength of 340~430nm preferably can be used, it is possible to use argon laser, He-Ne Laser, YAG laser and semiconductor laser etc. send out the laser of the light from visible ray to infrared region.When using these laser, Addition has absorption from visible ray to the sensitizing coloring matter in the infrared region.
Above-mentioned coloring photosensitive combination (or its solidfied material) is available for photo-curable coating or varnish, photo-curable bonding The liquid crystal display of the colored display such as agent, printed base plate or color TV, PC monitors, portable data assistance, digital camera The colour filter of colour filter, ccd image sensor in panel, the electrode material of plasma display panel, powder coated, print Brush ink, galley, bonding agent, dental composition, light appearance resin, gel paint, electronics engineering photoresist, Both resistance to platedresist, etch-resistant coating, liquid and desciccator diaphragm, soldering resist, the colour filter for various display purposes The manufacture of device is used to form structure in the manufacturing process of plasma display panel, electrical luminous display unit and LCD Resist, the composition for enclosed electrical and electronic unit, solder mask, magnetic recording material, milli machine component, waveguide, Photoswitch, plating mask, etching mask, color test system, glass fiber cable coatings, screen painting template, for leading to Cross the stereolithography manufacture material of three-dimension object, holographic recording material, image recording material, fine circuits, decoloring material, use Decoloring material in image recording material is used up using decoloring material, the printing distributing board of the image recording material of microcapsules Cause anticorrosive additive material, the photo anti-corrosion agent material of UV and visible laser through image system, for printed circuit board gradually Various uses, the purposes such as photo anti-corrosion agent material or protective film that the dielectric layer in stacking is formed are not particularly limited.
Above-mentioned coloring photosensitive combination can use to form the pixel of colour filter, especially as being used to form liquid The photosensitive composite of the display equipment colour filter of the device used for image display such as LCD panel is useful.
Above-mentioned display equipment is preferably formed with colour filter by following processes：(1) above-mentioned colored photosensitive is formed on substrate Property the process of film of composition, (2) film is irradiated via the mask with predetermined pattern shape active light process, (3) process for heating process that the envelope after exposure is developed with developer solution, (4) to the envelope after development.Separately Outside, above-mentioned coloring photosensitive combination is also useful as the coloring photosensitive combination of the ink-jetting style of nonvisualization process.
Embodiment
Embodiment etc. is enumerated below the present invention is further described in detail, but the present invention is not limited to these embodiments Deng.
O.1 and the synthesis of No.2 [embodiment 1-1 and 1-2] compound N
Aldehyde compound (4mmol), malononitrile (8mmol), Piperazine anhydrous (0.03g) and diformazan are added in into reaction vessel Yl acetamide (5g) dissolves them, is stirred 5 hours at 80 DEG C.Ethyl alcohol 7g, which is added dropwise, makes its partial crystallization, the solid mistake that will be obtained Filter, concentrates after ethyl alcohol washing is carried out, passes through silica gel column chromatography (developping solution：Toluene) it is refined, drying respectively obtains Huang Color solid.With1The yellow solid that H-NMR, IR confirm is object.In addition, measure absorbing wavelength characteristic.Result is shown In [table 1] and [table 2].
O.3 and the synthesis of No.4 [embodiment 1-3 and 1-4] compound N
Into reaction vessel add in aldehyde compound (4mmol), cyan-acetic ester (8mmol), Piperazine anhydrous (0.03g) and Dimethylacetylamide (5g) makes its dissolving, is stirred 5 hours at 50 DEG C.Ethyl alcohol 7g, which is added dropwise, makes its partial crystallization, the solid mistake that will be obtained Filter, ethyl alcohol washing, respectively obtain yellow solid.With1The yellow solid that H-NMR, IR confirm is object.In addition, it surveys Determine absorbing wavelength characteristic.It shows the result in [table 1] and [table 2].
The synthesis of [embodiment 1-5] compound N o.5
Aldehyde compound (4mmol), malononitrile (12mmol), Piperazine anhydrous (0.04g) and diformazan are added in into reaction vessel Yl acetamide (5g) makes its dissolving, is stirred 3 hours at 50 DEG C.Ethyl alcohol 7g, which is added dropwise, makes its partial crystallization, obtained solid is filtered, Ethyl alcohol washs, and obtains yellow solid.With1The yellow solid that H-NMR, IR confirm is object.Wave is absorbed in addition, measuring Long characteristic.It shows the result in [table 1] and [table 2].
[table 1]
1H-NMR (solvents：CDCl3)
[table 2]
[evaluation example 1-1~1-5] absorbing wavelength evaluating characteristics
Use CHCl3Solution evaluate compound N obtained above o.1~No.5 and above-mentioned comparative compound No.1 and 2 Absorbing wavelength characteristic.It shows the result in [table 3].
[table 3]
λmax/nm ε
Compound N is o.1 448 1.22×105
Compound N is o.2 449 1.32×105
Compound N is o.3 426 9.5×104
Compound N is o.4 420 9.72×104
Compound N is o.5 442 3.30×105
Comparative compound No.1 437 1.20×105
Comparative compound No.2 438 1.63×105
From the result of above-mentioned [table 3] it is found that the dyestuff of the present invention formed containing above-mentioned general formula (1) compound represented (A) there is appropriate absorbing wavelength.
The preparation of [embodiment 2-1~2-5] coloring photosensitive combination No.1~No.5
<Step 1>The preparation of photosensitive composite No.1
By the A-9300- as SPC-1000 (the Showa electrician corporation) 39.7g of (B) ingredient and as (D) ingredient 1-CL (chemical industrial company of Xin Zhong villages system) 9.2g, as (C) ingredient Irgacure OXE-01 (BASF AG's system) 0.8g, PGMEA 28.0g as the solvent and FZ2122 as other compositions (TorayDowCorning corporations) 2.31g mixing, Stirring obtains photosensitive composite No.1 until insoluble matter disappearance.
<Step 2>The preparation of dye solution No.1~No.5
Respectively to the compound N obtained above as (A) ingredient o.1~each 0.10g of No.5 in add in dimethylacetamide Amine 1.90g, stirs to dissolve.
<Step 3>The preparation of coloring photosensitive combination No.1~No.5
Dye solution No.1~the No.5 that will be obtained in the 5.0g of the photosensitive composite No.1 obtained in step 1 and step 2 Each 1.0g mixing respectively obtains coloring photosensitive combination No.1~No.5 of the present invention.
[comparative example 2-1 and 2-2] compares the preparation of coloring photosensitive composite No.1 and No.2
In addition to by the compound N of (A) ingredient in the step 2 of embodiment 2-1 be o.1 changed to comparative compound No.1 and Other than No.2, using with the same gimmicks of embodiment 2-1, obtain comparing coloring photosensitive combination No.1 and No.2.
[evaluation example 2-1~2-5 and comparative evaluation example 2-1 and 2-2] is by being burnt into the Evaluation of Heat Tolerance carried out
By coloring photosensitive combination No.1~No.5 obtained above and compare coloring photosensitive combination No.1 and No.2 is applied under conditions of 410rpm × 7 second on glass substrate respectively, is made it dry (90 DEG C, 90 seconds) with heating plate.With Ultrahigh pressure mercury lamp is exposed (150mJ/cm to obtained film2).By condition of the film after exposure at 230 DEG C × 30 minutes Lower firing.The suction of film before the firing of the maximum absorption wavelength (λ max) of compound (dyestuff) used in measuring (after exposure) The absorbance of film after luminosity and firing, after the firing when absorbance of the film before firing (after exposure) is denoted as 100 The ratio of the absorbance of film is evaluated as relative intensity.Wherein, the absorbance of the film after firing is closer to 100 tables Show that heat resistance is higher.It shows the result in [table 4].
[table 4]
By the above results it is found that the heat resistance of the coloring photosensitive combination of the present invention is high.
[evaluation example 3-1~3-5 and comparative evaluation example 3-1 and 3-2] Investigation on Photodegradation
By coloring photosensitive combination No.1~No.5 obtained above and compare coloring photosensitive combination No.1 and No.2 is respectively coated under conditions of 410rpm × 7 second on glass substrate, is made it dry (90 DEG C, 90 seconds) with heating plate.With Ultrahigh pressure mercury lamp is exposed (150mJ/cm to obtained film2).Film after exposure is resistance to Suga test system xenons Photosensitiveness testing machine table San XT-1500L implement 12 hours light fastness tests.Measure the very big of compound (dyestuff) used The absorbance of film after the absorbance and light fastness test of the film before light fastness test in absorbing wavelength (λ max), with The ratio of the absorbance of the film after light fastness test when the absorbance of film before light fastness test is denoted as 100 is opposite Intensity is evaluated.Wherein, the absorbance of the film after light fastness test represents that light resistance is higher closer to 100.Evaluation will As a result it is shown in [table 5].
[table 5]
Compound (dyestuff) Relative intensity
Evaluate example 2-1 Compound N is o.1 94
Evaluate example 2-2 Compound N is o.2 94
Evaluate example 2-3 Compound N is o.3 92
Evaluate example 2-4 Compound N is o.4 92
Evaluate example 2-5 Compound N is o.5 94
Comparative evaluation example 2-1 Comparative compound No.1 90
Comparative evaluation example 2-2 Comparative compound No.2 79
By the above results it is found that the light resistance of the coloring photosensitive combination of the present invention is high.
It is inhaled by result above it is found that the dyestuff of the new compound of the present invention has been used to have in appropriate wavelength region It receives, has used the photosensitive composite of the dyestuff and its heat resistance of solidfied material and light resistance high.Therefore, newcooperative medical system of the invention Close object and coloring photosensitive combination is for display equipment colour filter and using the liquid crystal display panel that the colour filter forms Useful.

Claims (5)

1. a kind of compound, be the following general formula (1) compound represented or following [chemical formulas 15],
[chemical formula 16], [chemical formula 20A] and compound N o.3, at least one of No.4 compounds represented,
In general formula (1), A represents phenyl ring, which can be by halogen atom, cyano, hydroxyl, nitro, the alkane that carbon atom number is 1~12 Base, alkoxy, halogenated alkyl or halogenated alkoxy substitution,
Y represents cyano or-COOR4,
R1Represent hydrogen atom,
R2And R3Each independently represent the aryl or carbon atom number that alkyl, carbon atom number that carbon atom number is 1~12 are 6~20 For 7~20 aralkyl,
R2And R3Alkyl, aryl and the aralkyl of expression can be replaced by halogen atom or nitro,
R2And R3Methylene in the alkyl and aralkyl of expression can be by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- or-CONH Substitution,
R4Represent the alkyl that carbon atom number is 1~12,
R4Methylene in the alkyl of expression can be replaced by-COO- ,-O- ,-OCO- ,-NHCO- ,-NH- or-CONH,
X represents singly-bound, nitrogen-atoms ,-NR5, oxygen atom, sulphur atom ,-SO2,-SO-, phosphorus atoms ,-PR6Or meet following<1> Or<2>The organic group of condition,
R5And R6Each independently represent hydrogen atom, the aryl or carbon that the alkyl that carbon atom number is 1~12, carbon atom number are 6~20 Atomicity is 7~20 aralkyl,
The integer of m=2~3；
<1>Shown in m=2, X such as following formula (2),
In formula (2), X1It is 6~35 to contain to represent the carbon atom number of aliphatic alkyl, divalent that the carbon atom number of divalent is 1~35 Fragrant cyclic hydrocarbon radical or selected from following groups 1 of group,
The aliphatic alkyl that the carbon atom number of the divalent is 1~35 is ethane, propane, isopropyl alkane, butane, secondary butane, tertiary fourth Alkane, iso-butane, hexane, 2- methyl hexanes, 3- methyl hexanes, heptane, 2- methyl heptanes, 3- methyl heptanes, isoheptane, tertiary heptan Alkane, 1- methyloctanes, isooctane, tertiary octane, cyclopropane, cyclobutane, pentamethylene, hexamethylene, cycloheptane, 2,4- diformazan basic ring fourths The group of alkane or 4- hexahydrotoluenes is by Z1And Z2Replace the group of divalent formed,
X1The aliphatic alkyl of expression can be by cyano, nitro, alkyl, alkoxy, halogenated alkyl or the halogen that carbon atom number is 1~8 Replace for alkoxy,
X1Methylene in the aliphatic alkyl of expression can be replaced by-CO- ,-CO-O- or group that they are composed,
Z1And Z2Each independently represent Direct Bonding ,-O- ,-S- ,-SO2-、-SO-、-NR13Or-PR14,
R13Represent the aryl that carbon atom number is 6~20 or the aralkyl that carbon atom number is 7~20,
R14Represent that aryl that alkyl, carbon atom number that hydrogen atom, carbon atom number are 1~8 are 6~20 or carbon atom number are 7~20 Aralkyl,
R14Alkyl, the R of expression13And R14The aryl and aralkyl of expression can be replaced by halogen atom, hydroxyl or nitro,
R14Alkyl, the R of expression13And R14Methylene in the aralkyl of expression can by-COO- ,-O- ,-OCO- ,-NHCO- ,- NH- or-CONH- substitutions,
Wherein, the carbon atom number for the group that above-mentioned general formula (2) represents is in the range of 1~35；
<Group 1>
In formula, R5For with the R in above-mentioned general formula (1)5Identical group, when there are in group 2 or more, can it is identical can also Difference, p represent that 1~3 integer, q represent that 0~3 integer, r represent 1~19 integer；
<2>Shown in m=3, X such as following formula (3),
In formula (3), X2The carbon atom number for representing trivalent be 6~35 containing fragrant cyclic hydrocarbon radical or selected from following groups 2 of group,
Z1~Z3Each independently with the Z in above-mentioned general formula (2)1And Z2The group of expression is identical,
Wherein, the carbon atom number for the group that above-mentioned general formula (3) represents is in the range of 1~35；
<Group 2>
[chemical formula 15]
[chemical formula 16]
[chemical formula 20A]
2. a kind of coloured composition contains compound described in claim 1.
3. a kind of coloring photosensitive combination, contains：The dyestuff formed containing at least one compound described in claim 1 (A), the polymerizable compound (B) with ethylenic bond unsaturated bond with acid value, optical free radical polymerization initiator (C) and with The monomer (D) of ethylenic bond unsaturated bond.
4. the solidfied material of the coloring photosensitive combination described in claim 3.
5. a kind of display equipment colour filter, is formed using the solidfied material described in claim 4.
CN201480040982.5A 2013-12-05 2014-11-27 Compound and the composition containing the compound Active CN105473666B (en)

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JP6740705B2 (en) * 2016-05-20 2020-08-19 Jsr株式会社 Coloring composition for color filter material, colored cured film for color filter material, color filter, display element and light receiving element
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US4925782A (en) * 1985-02-06 1990-05-15 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive element containing water soluble dye compounds
US5371266A (en) * 1990-02-15 1994-12-06 Basf Aktiengesellschaft Bichromophoric cyano-containing methine dyes and transfer thereof

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