CN102803396B - Green pigment, process for production of same, coloring matter containing same, and method for coloring using same - Google Patents
Green pigment, process for production of same, coloring matter containing same, and method for coloring using same Download PDFInfo
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- CN102803396B CN102803396B CN201080024714.6A CN201080024714A CN102803396B CN 102803396 B CN102803396 B CN 102803396B CN 201080024714 A CN201080024714 A CN 201080024714A CN 102803396 B CN102803396 B CN 102803396B
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- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0017—Influencing the physical properties by treatment with an acid, H2SO4
- C09B67/0019—Influencing the physical properties by treatment with an acid, H2SO4 of phthalocyanines
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- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures of phthalocyanines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Abstract
Disclosed is a green pigment characterized by consisting of a stacked composite which is composed of a polyhalogeno zinc phthalocyanine having an average number of substituent halogen atoms of 12 to 16 and a polyhalogeno non-zinc metal phthalocyanine having an average number of substituent halogen atoms of 12 to 16. The green pigment has both a clear yellowish green color tone and excellent physical properties, particularly, excellent fastnesses to heat and solvent, thus being advantageous for use particularly as a pigment for the green pixel of a color filter.
Description
Technical field
The colorize method that the present invention relates to veridian, its manufacture method, the tinting material that contains this veridian and used the article of this veridian.The colorize method of the article that more particularly, relate to veridian, the green pigment composition that contains this veridian, its manufacture method, the tinting material that contains this veridian that many halos ZnPc molecule and the compound accumulation of the non-zinc metal phthalocyanine of many halos molecule form, used this veridian and the article that are colored.
Background technology
Be accompanied by the development rapidly of nearest Informationization Equipment, liquid color display is used to the display screen of Personal Computer, mobile information apparatus, televisor, projector, watch-dog, auto-navigation system, mobile phone, robot calculator or e-dictionary as information display member; The indicating meters such as Information Bulletin Board, guiding bulletin board, Fumction display plate, marking plate; All information such as the photography screen of digital camera or pick up camera shows the many aspects of relevant device.Accompany therewith, the colour filter carrying on liquid color display (below sometimes referred to as " CF ") is also requiring to have better quality aspect the image properties such as high image quality, wide color development colour gamut, fine, depth of shade, light transmission, contrast gradient.The veridian using in the green pixel of the relevant CF carrying on these liquid color displays, used C.I. pigment 36 (being sometimes called below " PG36 ") in the past always, but when an urgent demand high image quality, wide color development colour gamut, present the green C.I. pigment 58 (be below sometimes called " PG58 ") partially more yellow than PG36 is to evaluate according to the sharpness of its color harmony absorbing wavelength always.
Summary of the invention
The problem that invention will solve
Many bromos-many chloros such as PG58 ZnPc pigment is to use as the special color of the color demonstration for the normally used yellow in painted field such as supplementary coating or printing-ink, redness, blueness, this four primaries of black.In addition as mentioned above, its green pixel as CF enjoys favor to use with pigment recently.But, in the stage or preservation of manufacturing at the tinting material of the organic solvent systems such as coating or printing-ink, or in the operation of painted processing and commercialization, and then at CF in the manufacturing process with colored resist or CF, according to the difference of working conditions, easily generation is because the variation of the caused tone of problem of the fastness such as necessary solvent resistance and thermotolerance is, the problems such as deteriorated and stability decreases of distinctiveness.In the urgent need to improveing the shortcoming in these physical property, develop green tone and the good veridian of physical property of yellow (also referred to as yellowing) partially that keep distinct.
The means of dealing with problems
The people such as present inventor conduct in-depth research repeatedly in order to realize the object of the invention described above, found that, by PG58 molecule and the firm non-zinc metallic pigment packing of molecules (stacking) with similar molecular structure are constructed to novel composite pigment structure, can be when maintaining good chromatic characteristic, give the fastness to organic solvent and heating, thereby can solve above-mentioned problem, thereby complete the present invention.
; according to the first form of the present invention; a kind of veridian is provided, it is characterized in that, this veridian is the compound stores that average halogen radical replaces many halos ZnPc that number is 12～16 and the non-zinc metal phthalocyanine of many halos that on average halogen radical replacement number is 12～16.
In addition, according to another form of the present invention, a kind of manufacture method of above-mentioned veridian is provided, it is characterized in that, in this manufacture method, described many halos ZnPc and the non-zinc metal phthalocyanine of described many halos are dissolved in medium, from this solution, make above-mentioned two kinds of molecules with the form eutectoid of compound stores.
In addition, according to another form of the present invention, provide a kind of veridian dispersive composition, it is characterized in that, this veridian dispersive composition contains: organic solvent system, water system or water-hydrophilic organic solvent mixed solvent are liquid medium; The polymerizability liquid medium that polyreactive oligomers or polymerizable monomer form; The resin medium that softening agent, oligopolymer or synthetic resins form, further contains polymerization system dispersion agent or low molecular dispersion auxiliary agent as required as dispersing auxiliary.
In addition, according to another form of the present invention, a kind of tinting material is provided, it is characterized in that, this tinting material further contains diluent media and is selected from as one or more the material being coated with in thermoplastic polymer, reactive polymer, reactive oligomers, polymerizable monomer and the linking agent of film formation material and forms in above-mentioned veridian dispersive composition, further contains as required curing catalysts or polymerizing catalyst.
According to another form of the present invention, a kind of colorize method of article is provided, it is characterized in that, with above-mentioned pigment dispensing composition or tinting material, to article, carry out painted.The present invention also provides a kind of dyed articles, and it uses above-mentioned colorize method to form.
Invention effect
This veridian, when keeping the partially yellow green tone of distinctness, especially excellent aspect the fastness such as thermotolerance and solvent resistance, particularly can be advantageously used for the green pixel pigment of colour filter in physical property.The above-mentioned action effect of veridian of the present invention cannot use two kinds of pigment to realize by mixing.It is envisaged that, the above-mentioned good action effect of veridian of the present invention is to be provided by novel composite pigment structure, this composite pigment structure is that two kinds of pigment molecules by forming this pigment are piled up together securely, thereby strengthened and formed by molecular interaction.Especially, between two kinds of molecules, by π-π, interacted and piled up, both sides' molecule is compound and form crystal, different from the crystal of original pigment separately, has formed novel pigment.But, above theory is supposition eventually, and the present invention is not subject to the restriction of this theory.
Embodiment
< defines >
In record of the present invention, sometimes average halogen radical is replaced to many halos ZnPc that number is 12～16 and be recited as many (12～16) halo ZnPc, average halogen radical is replaced to the non-zinc metal phthalocyanine of many halos that number is 12～16 and be recited as the non-zinc metal phthalocyanine of many (12～16) halo.That is, " (12～16) " in above-mentioned record represent the mean number of substituted halogen radical in each pigment molecule.In addition, following term " halo ", " bromo " and " chloro " numeral of recording together with bracket before represent " halogen radical ", " bromo " and " chloro " these the substituent mean number in pigment molecule too.
In addition, in this manual, sometimes want when many (12～16) halo ZnPc and the non-zinc metal phthalocyanine of many (12～16) halo are expressed as the pigment as the aggregate of molecule, be recited as respectively many (12～16) halo ZnPc pigment and the non-zinc metal phthalocyanine of many (12～16) halo pigment, or brief note is A pigment and B pigment, in addition, sometimes want statement to form minute period of the day from 11 p.m. to 1 a.m of these pigment, with compound name, be recited as many (12～16) halo ZnPc and the non-zinc metal phthalocyanine of many (12～16) halo respectively, or brief note is A molecule and B molecule.
In this manual, average halogen radical replaces many halos ZnPc that number is 12～16 and the compound stores that average halogen radical replaces the non-zinc metal phthalocyanine of many halos that number is 12～16 and refers to, they are piled up with molecular level and have formed the material of crystal, with the eutectoid thing of these two kinds of pigment synonym in fact.
< manufacture method >
Veridian of the present invention is for example prepared by following method.; to be many, (12～16) halo ZnPc pigment (A pigment) and the non-zinc metal phthalocyanine of many (12～16) halo pigment (B pigment) be dissolved in the medium of two kinds of pigment of solubilized; make these the two kinds of molecule eutectoid of the A molecule of A pigment and the B molecule of B pigment to carry out compound accumulation, thereby obtain veridian.Medium as dissolving two kinds of pigment, can be used acid, is preferably sulfuric acid, more preferably oleum or 100% sulfuric acid etc.
As the eutectoid method of veridian of the present invention, be to make above-mentioned A molecule and above-mentioned B molecule lose solvability simultaneously, and it is separated out by the mode of B packing of molecules (stacking) according to A molecule.For example must avoid A molecule only to separate out and condition that B molecule is not separated out.As the method for eutectoid, for example can list:
(1) in being dissolved with the acid solution (being preferably high concentrated acid solution) of A pigment and B pigment, add aqueous acids to reduce acid concentration, thus the method that two kinds of molecules are separated out;
(2) make to be dissolved with in the high concentrated acid solution of A pigment and B pigment and absorb moisture to reduce acid concentration, thereby reduce solubleness, the method that two kinds of molecules are separated out;
(3) the high concentrated acid solution that is dissolved with A pigment and B pigment is injected in a large amount of water of high degree of agitation or injection or in frozen water, two kinds of molecule moments are separated out and the method for piling up etc.
In above-mentioned (3), water or the frozen water of separating out use also can contain organic solvent.According to preferred configuration of the present invention, the preferred method of above-mentioned (3) in aforesaid method.Particularly be preferably as follows method: with decompression suction device high-velocity jet water such as aspirator, injectors, under its depressurization, attract the high-concentration sulfuric acid solution of pigment and it is contacted with the water of high-velocity jet, thereby make it dilute to separate out pigment particles.In addition, as preferred configuration, can also list following method etc.: use the super mixers such as dissolver, homogenizer, or in possessing the tempering tank of the efficient stirrers such as " MaxBlend " (trade(brand)name, Sumitomo Heavy Industries's system), high degree of agitation is separated out water, drip wherein, flow into or inject (following, use " injections " to represent to comprise the meaning of dropping, inflow) acid solution of pigment, it is spread in water and pigment particles is separated out.
According to preferred configuration of the present invention, in eutectoid operation, or and then eutectoid operation, as pigmenting, process (pigmentation) operation, preferably to rough pigment remove impurity using improve pigment purity operation, make the operation that pigment becomes fine and/or adjust as the operation of the crystal of pigment etc.As the pigmenting in eutectoid operation, process, can list: be injected in the water that contains hydrophobic organic solvent and/or hydrophilic organic solvent or frozen water or the water or the frozen water that make it force contact to contain hydrophobic organic solvent and/or hydrophilic organic solvent, when making its eutectoid, carry out the method for the pigmenting processing of miniaturization, crystal adjustment; Or in the processing water that contains eutectoid thing, add above-mentioned organic solvent so that its contact and the method processed.In addition, and then eutectoid operation, according to solvent-borne type, cover with paint, lacquer, colour wash, etc. (solvent finish) method etc., at organic solvent, for example in xylol, carry out heat treated, or the known pigmenting that carries out the promotion crystallizations such as heat treated in xylol emulsion is processed, as required, can be used together more than one in tensio-active agent, rosin, various resene, macromolecule dispersing agent and pigment derivative.The miniaturization of pigment also can be carried out in eutectoid operation, in addition, when and then eutectoid operation is carried out, also can utilize dry type to grind method or salt mill method, mixing by carrying out together with water-soluble salt and the water-miscible organic solvent that adds as required in the mixing rolls such as kneader, grind, the known pigment miniaturization method such as miniaturization carries out.The median size of the primary particle of the pigment after miniaturization is 5～130nm, is preferably 10～110nm.
< veridian >
In forming many halos ZnPc pigment of veridian of the present invention, as substituent halogen radical, refer to chloro, bromo or this two kinds of groups.Particularly from expecting that the tone of many halos ZnPc pigment is distinct partially yellow green viewpoint, preferably bromo is the phthalocyanine green pigment of main body, (more than 12 and lower than 16, be preferably 12～15.9) that preferably imported bromo and chloro bromo-(over 0 and be below 4, be preferably 0.1～4) chloro ZnPc pigment and the bromo ZnPc pigment that only has bromo (12～16).Preferred pigments is PG58 more specifically.
In addition, as the non-zinc metal that forms the non-zinc metal phthalocyanine of many (12～16) the halo pigment of veridian of the present invention, can list the metal that is selected from copper grade in an imperial examination I family, the metal of magnesium grade in an imperial examination II family, the metal of the III-th families such as aluminium, the metal of titanium, tin grade in an imperial examination IV family, the metal of one or more among the metal of the group VIIIs such as iron, cobalt, nickel.In addition, as halogen radical, refer to chloro, bromo or this two kinds of groups.As the non-zinc metal phthalocyanine of preferred many (12～16) halo of realizing the veridian of the present invention that fastness is higher, can list imported many (more than 12 and lower than 16, be preferably 12～15.9) of bromo and chloro bromo-(surpass 0 and be 4 below, be preferably 0.1～4) the non-zinc metal phthalocyanine of chloro, the non-zinc metal phthalocyanine of many (12～16) chloro that only has the non-zinc metal phthalocyanine of many (12～16) bromo of bromo and only have chloro, the particularly preferably non-zinc metal phthalocyanine of use (14～16) bromo.
The non-zinc metal phthalocyanine of many bromines chloro ZnPc and many bromines chloro can be by obtaining " the rear bromination method " of phthalocyanine pigment bromination.But, generally cannot avoid chlorination occurs in bromination, and the kind of halogen and replace number and be difficult to control completely, so preferably select the pigment of desirable tone to use from the pigment obtaining.
In order further to control the kind of halogen, manufacture veridian with replacing number, preferably: use the different pseudo-indole class of Tetra hydro Phthalic anhydride, phthalic imidine, O-phthalic nitrile or amino imino after bromination, chlorination or the bromo-chlorination that has imported the replacement number of stipulating to carry out condensation reaction as raw material, synthetic bromination or chlorination, bromo-zinc chloride or non-zinc metal phthalocyanine pigment.Particularly, substituting group only has many bromines ZnPc pigment of bromo and the non-zinc metal phthalocyanine of many bromines pigment optimization to obtain by the synthetic method of following pigment: use three or tetrabromophthalic anhydride, three or tetrabromo phthalimide, three or tetrabromo-phthalic diformazan nitrile or three or the different pseudo-indole class of tetrabromo amino imino as raw material, carry out condensation reaction together with zinc salt or non-zinc metal-salt.
Veridian of the present invention is good aspect the fastness such as solvent resistance and thermotolerance.Veridian of the present invention heats or seethes with excitement in organic solvent processes front and back, and large elongation does not occur the particle diameter of pigment particles, and the angle of diffraction of X-ray diffraction and also variation substantially of diffracted intensity.As confirming its method, can list the method for carrying out heat treated in organic solvent.If there is many halos ZnPc pigment, crystal particles can be grown up and under the treatment condition of coarsening, veridian of the present invention be carried out to heat treated.The variation of the processing pigment particles obtaining can be passed through electron micrograph, by the particle of pigment further thick the degree that grows into needle-like confirm and evaluate.In addition, according to processing pigment or not demonstrating in fact and only have the diffraction of the feature angle that many halos ZnPc pigment just has or shown degree from the X-ray diffractogram of wherein separated thick pigment part, can confirm the degree that the mixing of this pigment particles exists.
< evaluation experimental >
Prepare PG36 pigment, PG58 pigment and veridian of the present invention.In addition as a comparison, PG36 pigment and PG58 pigment are made and after methyl alcohol is stuck with paste, carried out mixingly, also prepare thus simple pigment composition.Each pigment is added in xylene solvent, and heating makes its boiling, thereby pigment is carried out to solvent treatment, and the particle diameter of pigment and the variation of crystal state are processed in research.
With 60,000 times of electron micrographs of taking PG36 pigment before solvent treatment, PG58 pigment, veridian of the present invention and simple pigment composition.Photo shows that pigment is respectively the microgranular or globe of 30～50nm (0.03～0.05 μ m) size roughly.
Pigment after relevant dimethylbenzene boiling is processed, first, the crystal particles of the processing pigment of PG58 is grown and coarsening greatly.Its electron micrograph is to take under the multiplying power of 10,000 times lower than other pigment in multiplying power.In microphotograph, can't see particulate crystal, is all the crystal of needle-like or thicker glass fibre shape.With " long * wide ", representing its crystal, is the big or small needle-like crystal of about 1 μ m to 7 μ m * 0.2, μ m * 0.05 μ m, and then also observes the thick crystal particles being grown to after its merging.Therefore show that PG58 pigment is very unstable in solvent.The electron micrograph that pigment is processed in the dimethylbenzene boiling of PG36 pigment, simple pigment composition and veridian of the present invention is to take with the multiplying power of 60,000 times.The shape of the pigment particles of the processing pigment of PG36 demonstrates and processes the microgranular or spherical of front 30 same～70nm left and right, shows in solvent it is stable.The mixture of PG36 pigment and PG58 pigment has shown the crystal particles of microgranular particle and needle-like or glass fibre shape, demonstrates the photo that two kinds of pigment mix.
Veridian of the present invention demonstrates and processes the microgranular or spherical of front 30 same～70nm left and right.But difference according to circumstances, although seldom, also can see that width is that roughly 30nm, length are the thin needle-like crystal of 1 μ m left and right, according to estimates, the mixing with the caused PG58 not piling up of deviation that is considered to accumulation condition exists.But, this veridian is when the tinting material, and above-mentioned phenomenon is less to the fastness situation that exerts an influence, and in most cases can use in fact in the same manner.
Above-mentioned dimethylbenzene boiling each pigment has before and after treatment been measured to X-ray diffraction.Table 1 and table 2 are that angle of diffraction is roughly combined to represent main diffraction peak and relative intensity.In table, " 2 θ " expression angle of diffraction (°), " % " hurdle is with %, to represent the relative intensity of diffraction, and " form " hurdle represents that the form of diffraction peak, " s " represent sharp-pointed shape, and " b " represents wide shape.
Main diffraction peak and the relative intensity of the pigment before table 1 xylene solvent is processed
Main diffraction peak and the relative intensity of the processing pigment after table 2 xylene solvent boiling test
By above-mentioned result, demonstrated: PG36 pigment is before and after treatment, and angle of diffraction and relative intensity are all almost unchanged, except crystal habit become slightly sharp-pointed, without other variation.On the other hand, the X-ray diffraction of PG58 pigment demonstrates sharp-pointed and large diffraction pattern under many angle of diffraction, and the crystal that demonstrates pigment is grown greatly, face interval is adjusted.In addition, the diffraction of the mixture of PG36 pigment and PG58 pigment shows as the pattern after the addition of diffraction of two kinds of pigment certainly.
Veridian of the present invention demonstrates the diverse diffraction of diffraction with above-mentioned mixture, shows it is the crystal with the complete different dimensional of mixture.Compare with the diffractogram of PG36 pigment, the figure before solvent treatment and after processing comprises diffraction angle, relative intensity, demonstrates the diffraction pattern approximate with the diffractogram of PG36 pigment.The shape of the diffraction of veridian of the present invention is slightly wide, on sharpness, can see difference, can infer that this point has shown the accumulation of non-zinc pigment molecule.
In addition, from the diffraction pattern of veridian of the present invention, the accumulation of A pigment and B pigment is investigated, result is as described below.That is,, the sharpness of diffractive shape is variant for veridian of the present invention and PG36 pigment, PG58 pigment ratio, slightly wide, although can find these, the whole diffraction pattern of these three kinds of pigment is similar, in angle of diffraction, roughly consistent place occur diffraction respectively, their relative intensity is also similar.Can infer thus, PG36 molecule and PG58 molecule are the molecules of easily mutually piling up on molecular structure.
The green pixel that veridian of the present invention is particularly used as CF forms the veridian of use, can expect to demonstrate distinct partially yellow green.When this purposes, aspect physical property, in organic solvent, carry out before and after heat treated, there is not large elongation in the particle diameter of pigment particles, and the angle of diffraction of X-ray diffraction and diffracted intensity do not have large variation yet, is favourable in these areas.Even if veridian of the present invention mixes, have few many halos ZnPc pigment of not piling up, but in the situation that because formula, treatment condition or the use of tinting material can not exert an influence in fact, it mixes to exist also allows.
Molar ratio about many halos ZnPc and the non-zinc metal phthalocyanine of many halos, first be can keep or the i.e. scope of yellow green tone partially of the good character that do not hinder many halos ZnPc, and in order to improve as the thermotolerance of the shortcoming of many halos ZnPc and solvent resistance etc., be preferably the molar ratio that can form the structure that produces above-mentioned performance, physical property.In addition, for thermotolerance and solvent resistance etc., the kind of the solvent that can use when forming tinting material is carried out suitable decision ratio, and for thermotolerance, the heating condition in can also the aftertreatment when painted etc. carrys out suitable decision ratio.
According to preferred configuration of the present invention, take improve stability as object in the situation that, the molar ratio of the non-zinc metal phthalocyanine of many halos ZnPc (XnZnPc) and many halos (XnMePc) is XnZnPc: XnMePc=30: 70～95: 5, be preferably 40: 60～90: 10.Particularly, in the situation that paying attention to tone, be preferably 82: 18～95: 5.
< purposes >
Veridian of the present invention as tinting material can be for for example application, press plate printing, dyeing, printing and dyeing, written record, describe picture, ink jet printing, electrophotographic printing, xeroprinting.In addition, except CF pixel forms with ink, can also list as utilized the stationery classes such as tinting material, stationery, drawing pigment such as the application of coating, the coloring resin that has used coloring resin agent, printing-ink, staining agent, printing and dyeing agent, ink for inking, electrophotographic printing with photographic developer or xeroprinting the purposes with the coloring components of information-recording materials such as photographic developer etc.
Therefore,, according to another form of the present invention, provide a kind of tinting material that contains veridian of the present invention.While manufacturing this tinting material of the present invention, prepare color compositions, this color compositions can be set the composition that contains veridian of the present invention for.Therefore,, according to another form of the present invention, also provide a kind of pigment dispensing composition that contains veridian of the present invention.The form of this pigment dispensing composition can be water-based paint dispersive composition, oil colour dispersive composition, resin dispersion type processed pigment or energy ray-curable pigment dispensing composition etc.In addition, pigment concentration is set as 10%～50% compared with highland conventionally, but also can make in advance pigment differential loose, becomes the formation that can easily manufacture tinting material.Color compositions of the present invention contains veridian of the present invention, and contains as medium: the suitable liquid medium of organic solvent system, water system or water-hydrophilic organic solvent mixed solvent system; The polymerizability such as polyreactive oligomers, polymerizable monomer liquid medium; The resin medium that softening agent, oligopolymer, synthetic resins etc. form, further contains polymerization system dispersion agent or low molecular dispersion auxiliary agent as required as dispersing auxiliary.
In pigment dispensing composition of the present invention, further coordinate diluent media, as what be coated with that film formation material plays a role, be selected from suitable material in thermoplastic polymer, reactive polymer, reactive oligomers, polymerizable monomer and linking agent etc. etc., further add as required curing catalysts, polymerizing catalyst etc., mix equably and disperse, thus can manufacturing objective tinting material.According to a form of the present invention, in tinting material of the present invention, pigment (P) can consider that with the fit quality ratio that is coated with film formation material (V) purposes, desired performance etc. suitably determine, are generally P: V=80: 20～1: 99 scope, is preferably 70: 30～10: 90.
In tinting material of the present invention or pigment dispensing composition, during dispersed color, except mulch film formative polymkeric substance, can also add known additive as required.As the example of above-mentioned additive, can list as colo(u)rant dispersion stablizer and known ionic pigment derivative with and the ionic polymers of counterion be the various additives such as dispersion agent, tensio-active agent, defoamer, smooth agent, adhesive agent, silane coupling agent etc.
The colo(u)rant dispersion machine using in manufacture as pigment dispensing composition and tinting material, can use known dispersion machine, vertical medium dispersion machines such as ball mill, sand mill, ball mill; The horizontal medium dispersion machines such as sand mill (Dyno Mill), Horizontal sand mill; Roller mill; Ultrasonic wave grinding machine; Impacting with high pressure dispersion machine etc.By carrying out repeatedly the method for dispersion treatment with a kind of in above-mentioned dispersion machine or the method for compound two kinds of above dispersion machines is carried out dispersion treatment.Median size is generally 5～130nm left and right, is preferably 10～110nm.
As the resin of the contained painting film formation material of tinting material of the present invention, be also to use known resinous principle according to various uses.Such as listing synthetic rubber resin, acrylic resin, Vinylite, chlorinated rubber resin, Synolac, urethane resin, epoxy, be the known painting film formation materials such as resin, silicone resin, fluoro-resin and uv curing resin system; Electrocuring resin system homenergic ray-curable is coated with film formation material etc.Above-mentioned covering film formation material can also further have reactive group, as reactive group, such as listing methylol, alkyl methylol, isocyanate group, the isocyanate group of sheltering, epoxy group(ing) etc.In addition, according to purposes, can use oligopolymer or monomer, can also further and use linking agent, for example melamine methylol system or isocyanate-based, epoxy are linking agent.
When tinting material of the present invention is colour filter while using tinting material, as it, cover film formation material, can use known any material in the past, be not particularly limited.When image formation is photolithography developable with ink, can uses and be collectively referred to as the energy-ray irradiation aggretion type ink of ink for the formation of photosensitivity pixel.As addition polymerization or addition-crosslinked property ink, can list the heating such as hot polymerization mould assembly, LASER HEAT ray polymerization type, polymerizable ultraviolet type, light cationic polymerization type, electron beam polymerization type or energy ray-curable ink etc.The covering film formation material that their use be in the past knownly by containing, there is the unsaturated double-bond of addition polymerization or addition-crosslinked property or monomer, oligopolymer and/or the polymkeric substance of polymerizability ring-type ether and the polymerization starter adding as required, addition polymerization or the addition-crosslinked property sticking agent that liquid medium forms.
As the object lesson that covers film formation material, can list the monomer classes such as tetramethylolmethane two (methyl) acrylate (" (methyl) acrylate " represents acrylate and methacrylic ester), poly-(4～6) (methyl) acrylate of Dipentaerythritol, bisphenol-type epoxy resin-bis-(methyl) acrylate; (methyl) acrylate-(methyl) vinylformic acid (being total to) polymkeric substance, (methyl) Acrylate-styrene bipolymer-(methyl) acrylic copolymer etc.; Polyester acrylate is that resin, poly-epoxy acrylate are that resin, urethane acrylate are that resin, polyether acrylate are that resin, polyalcohol acrylate are resin etc.; Photosensitivity phenol resin, unsaturated polyester are resin etc.They can use separately, also can two kinds of above and use.
In addition, as Photoepolymerizationinitiater initiater, can list known Photoepolymerizationinitiater initiater, for example 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2,2-diethoxy acetophenone, 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholinyl propane-1-ketone, 2-benzyl-2-(N, N-dimethylamino)-1-(4-morpholinyl phenyl)-butanone-1 etc.They can use separately, also can two kinds of above and use.
Can or use the tinting material of said composition to carry out painted to various article with pigment dispensing composition of the present invention.When the green pixel for colour filter forms, will be in the past the colored resist of known green and known yellow ultramarine be used for modulating, and together with red resist, blue resist, utilize in the past the methods such as known photolithography, transfer printing, laminating method, ink-jet printing process, print process on CF substrate, to form green, redness, blue pixel, but be not subject to being particularly limited of they.For example, while forming the pattern of pixels of colour filter on substrate, use such as spinner, sized roller applicator, gap coating device, printing press etc. that this photosensitivity pixel formative ink is carried out to whole coating on substrate, after predrying, make photomask adhere to, use extra-high-pressure mercury vapour lamp to expose, then make pattern sintering.Then develop and wash, as required, by carrying out post-drying, can form the pattern of colour filter.
In colour filter, as the red pixel (R) using, the pigment of blue pixel (B), can use known most pigment in the past together with green pixel (G).Such as using the azo pigments such as insoluble azo system, solubility azo system, high molecular azo system; The quinacridone pigments such as the red system of quinacridone, the pinkish red system of quinacridone; Pyrrolo-pyrrole-dione series pigments; Anthraquione pigmentss; Perylene series pigments; The phthualocyanine pigments such as phthalocyanine blue system; Isoindolinone pigment; The dioxazine series pigments such as dioxazine violet; Quinophthalone yellow pigment; The complex compound pigment such as nickel azophosphine etc.
The object lesson of the representative pigment of using as transmission-type R, G, B pixel, red pigment can list PR177, PR242, PR254 etc., complementary color is used or the yellow ultramarine of monochromatic use can list PY83, PY138, PY139, PY150, PY185 etc., blue pigments can list PB15:6, PB60 etc., complementary color is used or the violet pigment of monochromatic use can list PV23 etc., and then can also list co-precipitation pigment, solid solution pigment or mixed crystal pigments above-mentioned red pigment and yellow ultramarine and blue pigments and violet pigment.
In addition, mainly the pixel of colour filter is formed and is illustrated above, pigment dispensing composition of the present invention and tinting material are all applicable to as other various uses, printing-ink such as the resin as synthetic or natural, coating, plastics film, various paper, synthetic paper etc., the tinting material of ink etc. for the printing and dyeing agent of the tinting material of using as paper, the use of weaving cotton cloth, ink, color copy machine toner for notes, printer ink for ink-jet, thermal transfer ribbon, can obtain each good green dyed articles.
Embodiment
Below, enumerate specific embodiment and further describe the present invention.In addition, the portion in literary composition and % unless otherwise specified, are quality criterias.In addition, the bromine of the following non-zinc metal phthalocyanine of many bromos gets the number that Algebraic Expression carrys out the feed molar ratio of self-condensation reaction.
Production Example 1 (manufacture of the compound accumulation veridian of PG58 molecule and ten hexabromo copper phthalocyanine molecules)
Synthesizing of (1) ten hexabromo copper phthalocyanine
As synthesizer, prepare to be provided with reaction vessel and the heating unit of whipping appts, reflux exchanger and thermometer.As raw material, the tetrabromophthalic anhydride that the containing ratio of preparing bromine is 69.0%, the replacement number of bromine is 4.0 in every 1 molecule.To adding 3.4 parts of 140.0 parts, oil of mirbane as reaction medium, above-mentioned 7.1 parts of 27.0 parts, 46.4 parts of tetrabromophthalic anhydrides, urea, titanium tetrachlorides and cupric chlorides in reaction vessel.Temperature of reaction is slowly warming up to 175 ℃ from 100 ℃, stirs and within 4 hours, continue reaction under this state.Temperature of reaction before reaction closes to an end is 195 ℃.The output of rough pigment is 44.8 parts, and the yield of rough pigment is 97.4%.In addition, coordinate 95% sulfuric acid and 20% oleum, modulation 100% sulfuric acid.10 parts of the rough pigment obtaining are dissolved in 100 parts, 100% sulfuric acid, at 70 ℃, stir 1 hour, then in the frozen water of 10 times, separate out, filter and wash (hereinafter referred to as " sulfuric acid treatment ").Then with sodium hydroxide dilute aqueous soln, ethanol and dimethyl formamide washing.The yield of refining pigment is 94.9%.According to ultimate analysis, the containing ratio of copper is 3.44% (theoretical value: 3.456%), the containing ratio of bromine is 69.8% (theoretical value: 69.52%).It is 16.1 that the average bromine of every 1 molecule being calculated by the analytical value of the green pigment of ten hexabromo copper phthalocyanines obtaining replaces number, shows that phthalocyanine frame is replaced by 16 bromines completely.Below be referred to as " ten hexabromo copper phthalocyanine coarse particle pigment ".
(2) accumulation of PG58 and ten hexabromo copper phthalocyanine molecules
By the average replacement number of the bromine of 16.39g, be that approximately 13, the average replacement number of chlorine are that the PG58 of approximately 3 (is 0.00960 mole by average replacing the calculated value that radix obtains, identical below) and be dissolved in 20% oleum 140g by the ten hexabromo copper phthalocyanine coarse particle pigment 3.61g (0.00196 mole) that the building-up reactions of above-mentioned (1) obtains, at 70 ℃, stir 2 hours, naturally cool to room temperature.Use aspirator to make water with high-velocity jet, by the tubule being depressurized, attract the oleum solution of above-mentioned pigment, it is contacted with the water of high-velocity jet, pigment particles is separated out its dilution, filter and wash.Then with dimethylbenzene-emulsion method, carry out pigmenting, obtain veridian.Below be referred to as " rough pigment-1 of green accumulation ".
(3) by salt, grind miniaturization and process the green particulate pigment of the compound accumulationization of preparation
The green obtaining in above-mentioned (2) is piled up to rough pigment-1 to be 100 parts and to be provided with in the kneader that adds gland with joining together with 110 parts of 600 parts, sodium-chlor powder and Diethylene Glycols.In kneader, carry out pre-mixing until can form moistening piece, then close and add gland, one side 6kg/cm
2exert pressure content, Yi Bian carry out mixing and grind.Control temperature and make content reach 92～98 ℃, carry out simultaneously 2 hours mixing and grind processing.The triturate obtaining, heating to the stir process of carrying out 1 hour in 2% sulfuric acid of 3000 parts of 80 ℃, is then filtered and washes to remove sodium-chlor and Diethylene Glycol, obtain the filter cake of the compound accumulation veridian of miniaturization.In order to measure the particle diameter of the pigment obtaining, pigment filter cake is added to the tween that is 200% with respect to pigment, dilute with water, carry out ultrasonic wave dispersion with conditioned pigment dispersion liquid, use particle size analyzer " Model N-4 " (Coulter company system) to measure median size, result median size is about 25～35nm.Filter cake is dried and is pulverized, obtain veridian.Even if the pigment obtaining is carried out in organic solvent to heat treated, the particle diameter of pigment and crystal state do not have substantial variation yet.Be called below " green pigment-1 of piling up ".
Production Example 2 (manufacture of the compound accumulation veridian of PG58 molecule and ten hexabromo copper phthalocyanine molecules)
(1) accumulation of PG58 molecule and ten hexabromo copper phthalocyanine molecules
The PG58 using in Production Example 1 (2) is dissolved in 20% oleum 200g for 16.81g (0.00985 mole) with by the ten hexabromo copper phthalocyanine coarse particle pigment 3.19g (0.00173 mole) that the building-up reactions of Production Example 1 (1) obtains, at 70 ℃, stir 2 hours, naturally cool to room temperature, then be injected in the frozen water of the 2000g that contains 100g ethylene glycol butyl ether in MaxBlend steel basin (Sumitomo Heavy Industries's system), filter and wash.Filter cake is dried and is pulverized, obtain veridian.Below be referred to as " green pigment-2 of piling up ".
Production Example 3 (manufacture of the compound accumulation veridian of PG58 molecule and PG36 molecule)
(1) accumulation of PG58 molecule and PG36 molecule
Same with Production Example 2, the average replacement number that is 18.00g (0.01054 mole) and bromine by the PG58 using in Production Example 1 (2) is that approximately 13, the average replacement number of chlorine are that the PG36 of approximately 3 is that 2.00g (0.00117 mole) is dissolved in 20% oleum 200g, at 70 ℃, stir 2 hours, naturally cool to room temperature.Use aspirator to make water with high-velocity jet, by the tubule being depressurized, attract the oleum solution of above-mentioned pigment, it is contacted with the water of high-velocity jet, pigment particles is separated out its dilution, filter and wash.Then with dimethylbenzene-emulsion method, carry out pigmenting, obtain veridian.Below be referred to as " rough pigment-3 of green accumulation ".
(2) by salt, grind miniaturization and process the green particulate pigment of the compound accumulationization of preparation
Same with Production Example 1 (3), the green obtaining in above-mentioned (1) is piled up to 100 parts of rough pigment-3 and is provided with in the kneader that adds gland with joining together with 110 parts of 600 parts, sodium-chlor powder and Diethylene Glycols, similarly go mixing with grind.Similarly in 2% sulfuric acid, carry out stir process, then filter and wash to remove sodium-chlor and Diethylene Glycol, obtain the filter cake of the compound accumulation veridian of miniaturization.Median size is about 30nm.Filter cake is dried and is pulverized, obtain veridian.Even if the pigment obtaining is carried out in organic solvent to heat treated, the particle diameter of pigment and crystal state do not have substantial variation yet.Be called below " green pigment-3 of piling up ".
Production Example 4 (manufacture of the compound accumulation veridian of PG58 molecule and ten hexabromo aluminium Phthalocyanines)
Synthesizing of (1) ten hexabromo aluminium phthalocyanine pigment
Same with Production Example 1 (1), in reaction vessel, add oil of mirbane, tetrabromophthalic anhydride, urea and the titanium tetrachloride of equal parts, and add 3.34 parts of aluminum chloride to replace cupric chloride.Temperature of reaction is slowly warming up to 175 ℃ and stir 5 hours from 100 ℃, and final temperature of reaction is 200 ℃.The output of rough pigment is 40.0 parts, and the yield of rough pigment is 87.1%.Similarly the rough pigment obtaining is carried out to sulfuric acid treatment with Production Example 1 (1), filter pigment lye, washing, dry, pulverize.Below pigment obtained above is called to " ten hexabromo aluminium phthalocyanine pigments ".
(2) accumulation of PG58 and ten hexabromo aluminium Phthalocyanines
Same with Production Example 1 (2), the ten hexabromo aluminium phthalocyanine pigment 5.24g (0.00288 mole) that are 14.75g (0.00864 mole) and above-mentioned (1) by PG58 are dissolved in 20% oleum 140g, at 70 ℃, stir and naturally cooling.Use aspirator to attract the oleum solution of above-mentioned pigment, it is contacted with the water of high-velocity jet, pigment particles is separated out its dilution.Filter lye, wash, then with dimethylbenzene-emulsion method, carry out pigmenting, obtain veridian.Below be referred to as " rough pigment-4 of green accumulation ".
(3) by salt, grind miniaturization and process the green particulate pigment of the compound accumulationization of preparation
Same with Production Example 1 (3), the green obtaining in above-mentioned (2) is piled up to rough pigment-4 and join together with Diethylene Glycol in kneader with sodium-chlor powder, after pre-mixing, carry out mixing and grind processing.The triturate obtaining is carried out in 2% dilute sulphuric acid to stir process, then filter and wash, dry, pulverize, obtain veridian.Even if the pigment obtaining is carried out in organic solvent to heat treated, the particle diameter of pigment and crystal state do not have substantial variation yet.Be called below " green pigment-4 of piling up ".
Production Example 5 (manufacture of the compound accumulation veridian of PG58 molecule and ten hexabromo magnesium Phthalocyanines)
Synthesizing of (1) ten hexabromo magnesium phthalocyanine pigment
Same with Production Example 1 (1), in reaction vessel, add oil of mirbane, tetrabromophthalic anhydride, urea and the titanium tetrachloride of equal parts, and add 2.39 parts of magnesium chlorides to replace cupric chloride.Temperature of reaction is slowly warming up to 175 ℃ and stir 4 hours from 100 ℃, and final temperature of reaction is 195 ℃.The output of rough pigment is 39.9 parts, and the yield of rough pigment is 88.7%.Similarly the rough pigment obtaining is carried out to sulfuric acid treatment with Production Example 1 (1), filter pigment lye, washing, dry, pulverize.Below pigment obtained above is called to " ten hexabromo magnesium phthalocyanine pigments ".
(2) accumulation of PG58 and ten hexabromo magnesium Phthalocyanines
Same with Production Example 1 (2), the ten hexabromo magnesium phthalocyanine pigment 13.57g (0.00754 mole) that are 6.43g (0.00377 mole) and above-mentioned (1) by PG58 are dissolved in 20% oleum 140g, at 70 ℃, stir and naturally cooling.Use aspirator to attract the oleum solution of above-mentioned pigment, it is contacted with the water of high-velocity jet, pigment particles is separated out its dilution.Filter lye, wash, then with dimethylbenzene-emulsion method, carry out pigmenting, obtain veridian.Below be referred to as " rough pigment-5 of green accumulation ".
(3) by salt, grind miniaturization and process the green particulate pigment of the compound accumulationization of preparation
Same with Production Example 1 (3), the green obtaining in above-mentioned (2) is piled up to rough pigment-4 and join together with Diethylene Glycol in kneader with sodium-chlor powder, after pre-mixing, carry out mixing and grind processing.The triturate obtaining is carried out in 2% dilute sulphuric acid to stir process, then filter and wash, dry, pulverize, obtain veridian.Even if the pigment obtaining is carried out in organic solvent to heat treated, the particle diameter of pigment and crystal state do not have substantial variation yet.Be called below " green pigment-5 of piling up ".
Embodiment 1 (modulation of veridian high concentration dispersion)
In advance, as the dispersion agent of pigment, prepare 30% propylene glycol methyl ether acetate (following brief note is " the PGMA ") solution of BA-St-Hydroxyethyl Acrylate-methacrylic acid (mass ratio is 50: 15: 10: 10: 25, molecular-weight average are 12000) multipolymer.Hereinafter referred to as " pitch dispersant PGMA solution-1 ".
By " green pigment-1 of piling up " that obtains in Production Example 1 (3) 19 parts, 1 part of veridian sulfonated derivative, cationic macromolecular dispersion agent (polyesteramide polymine, 50% solution) 12 parts, 18 parts of 50 parts of " pitch dispersant PGMA solution-1 " shown in above-mentioned and PGMA mix, with dissolver, stir 2 hours, confirmation is without after pigment piece, in Horizontal ring pearl mill dispersion machine, use zirconium white microballon processed (diameter 0.65mm), circumferential speed with 14m/s is carried out dispersion treatment, obtain green high density dispersible pigment dispersion, " green pigment high concentration dispersion-1 of piling up ".
Embodiment 2 (modulation of the high concentration dispersion of pigment of all kinds)
(1) by miniaturization, process preparation particulate pigment of all kinds
Prepare PR254, PY138, PB15-6 and PV23.Salt mill miniaturization according to the compound accumulation veridian of Production Example 1 (3) is processed, and each pigment powder and sodium-chlor powder are joined and be provided with in the kneader that adds gland together with Diethylene Glycol, carries out mixing and grinds.The triturate obtaining is similarly dissolved in salt, solvent, filters and wash, obtain the filter cake of each miniaturization pigment.The median size of the miniaturization pigment that this is of all kinds is 30～40nm.The miniaturization powder pigment of each pigment will be obtained after filtration cakes torrefaction, pulverizing.
(2) modulation of pigment high concentration dispersion
Similarly to Example 1, replace greenly piling up pigment-1 and veridian sulfonated derivative and using particulate pigment and each the known pigment sulfonated derivative of PR254, the PY138, PB15-6 and the PV23 that in above-mentioned (1), obtain, similarly coordinate cationic macromolecular dispersion agent, acrylic resin and PGMA, with dissolver, stir and dispergation, with annular pearl mill dispersion machine, carry out dispersion treatment, obtain the high concentration dispersion of each pigment.Below " high concentration dispersion-1 " is represented with various color names.
(3) modulation of pixel formative ink for pixel
In order to form rgb pixel on the glass substrate of colour filter, according to the proportioning of following table 3, obtain " veridian photosensitivity dispersion liquid-1 ", " red pigment photosensitivity dispersion liquid-1 " and " blue pigments photosensitivity dispersion liquid-1 ".
The modulation of table 3RGB pixel formative ink
In upper table, TMPTA represents Viscoat 295, and HEMPA represents propionic acid 2-hydroxyethyl-2-methyl esters, and DEAP represents 2,2-diethoxy acetophenone.
Embodiment 3 (modulation of colour filter)
The glass substrate that has carried out silane coupling agent processing is arranged on spinner, at first under the rotating speed of 300rpm, the condition in 5 seconds, then under the rotating speed of 1200rpm, the condition in 5 seconds, " red pigment photosensitivity dispersion liquid-1 " of above-described embodiment 2 (3) is carried out to spin coating.Then at 80 ℃, carry out the prebake conditions of 10 minutes, make to have the photomask stickup of inlaying (mosaic) shape pattern, use extra-high-pressure mercury vapour lamp also to use 100mJ/cm
2light quantity expose.Then use special-purpose developing solution and special-purpose rinsing liquid develop and wash, thereby on glass substrate, form red zyklopisch pattern.
Then, use " veridian photosensitivity dispersion liquid-1 " and " blue pigments photosensitivity dispersion liquid-1 " of table 3, according to above-mentioned method, be coated with and toast to form green zyklopisch pattern and blue zyklopisch pattern, obtain the colour filter of RGB.The colour filter obtaining has good light splitting character of curve, and the fastness such as photostabilization, thermotolerance are good, and also has good character aspect light transmission, as liquid color display, with colour filter, demonstrates good character.
Embodiment 4 (modulation of colour filter)
Substitute the green of using in above-described embodiment 1 and pile up pigment-1, by the green that obtains in Production Example 2～5, piling up pigment-2～5 carries out and above-described embodiment 1 and the same operation of embodiment 2, obtain veridian photosensitivity dispersion liquid, then use together with blue pigments photosensitivity dispersion liquid-1 with red pigment photosensitivity dispersion liquid-1, modulate similarly to Example 3 colour filter, obtained following liquid color display colour filter, it has good light splitting character of curve, photostabilization, the fastness such as thermotolerance are good, and aspect light transmission, also there is good character.
Embodiment 5 (gravure ink and intaglio printing)
12 parts of vinylchlorid-vinyl-acetic ester-vinylformic acid (89: 6.7: 4.3) multipolymers (weight-average molecular weight is approximately 30,000) with carboxyl are dissolved in 68 parts of butylacetate-methyl iso-butyl ketone (MIBK)-dimethylbenzene (43: 20: 20) mixed solvents, add the green obtaining in 5 parts of Production Examples 1 (3) to pile up pigment-1, be then fed in ball mill it is disperseed 16 hours.Add 3 parts of silicon-dioxide, adding multiple branch polycarbodiimide is 12 parts of linking agent (reaction product of polyhexamethylene carbodiimide/vulcabond and Dipentaerythritol list lauryl) 20% toluene solutions again, mixes and makes yellow-green colour gravure ink.As the gravure ink of the yellowish green special look of distinctness, on vinyl chloride film etc., carry out intaglio printing together with other redness, blueness, yellow, dark brown and black gravure ink, obtained the film of the printing vinylchlorid etc. of distinct multiple color.
In addition, the green that substitutes above-mentioned use is piled up pigment-1, uses the green obtaining in Production Example 2～5 to pile up pigment-2～5, and according to modulating yellow-green colour gravure ink with above-mentioned same step, similarly on film, carry out intaglio printing, obtained the printing film of distinct multiple color.
Embodiment 6 (coating and application)
Add the methyl methacrylate-β-dimethyl-aminoethylmethacrylate-Octyl methacrylate-hydroxyethyl methylacrylate-methacrylic acid (44: 20: 10: it is 15 parts of 5 parts and titanium oxide white pigments that the green 5) obtaining in 45 parts of the ethyl acetate solutions of multipolymer (solids component 60%), 19.9 parts of dimethylbenzene, Production Example 1 (3) is piled up pigment-1 with carboxyl, be fed in ball mill, it is disperseed 16 hours.According to the multiple branch polycarbodiimide using in embodiment 5, be that linking agent 20% solution is that 15 parts and anti-flooding agent are that the formula of 0.1 part is modulated yellowish green acrylic coating.On various woodworks, metal products, the plastics such as information related products, office appliance or household supplies such as mobile phone, Personal Computer, carry out yellowish green application, and can carry out the good applications such as weathering resistance, weather resistance, water tolerance.
In addition, the green that substitutes above-mentioned use is piled up pigment-1, uses the green obtaining in Production Example 2～5 to pile up pigment-2～5, and according to modulating yellowish green acrylic coating with above-mentioned same step, similarly on various members, carry out application, obtained distinct yellowish green application product.
Claims (27)
1. a veridian, it is characterized in that, this veridian is the compound stores that average halogen radical replaces many halos ZnPc that number is 16 and the non-zinc metal phthalocyanine of many halos that on average halogen radical replacement number is 16, the non-zinc metal of the non-zinc metal phthalocyanine of described many halos is to be selected from aluminium, magnesium, titanium, tin, iron, cobalt, the metal of one or more in nickel and copper, described compound stores is that average halogen radical replaces many halos ZnPc that number is 16 and the non-zinc metal phthalocyanine of many halos that on average halogen radical replacement number is 16 piled up the material that has formed crystal with molecular level.
2. veridian according to claim 1, wherein, the molar ratio of described many halos ZnPc and the non-zinc metal phthalocyanine of described many halos is 30:70～95:5.
3. veridian according to claim 1 and 2, wherein, the halogen radical of described many halos ZnPc be chloro or bromo or chloro and bromo the two.
4. veridian according to claim 3, wherein, described many halos ZnPc is that average bromo replaces the bromo ZnPc that number is 16.
5. veridian according to claim 3, wherein, described many halos ZnPc be average bromo replace number be more than 12 and lower than 16 and average chloro replace number for over 0 and be the bromine chloro ZnPc below 4.
6. veridian according to claim 3, wherein, described many halos ZnPc is C.I. Pigment green 58.
7. veridian according to claim 1 and 2, wherein, the halogen radical of the non-zinc metal phthalocyanine of described many halos be chloro or bromo or chloro and bromo the two.
8. veridian according to claim 7, wherein, the non-zinc metal phthalocyanine of described many halos is that average bromo replaces the non-zinc metal phthalocyanine of bromo that number is 16.
9. veridian according to claim 7, wherein, the non-zinc metal phthalocyanine of described many halos be average bromo replace number be more than 12 and lower than 16 and average chloro replace number for over 0 and be the non-zinc metal phthalocyanine of bromine chloro below 4.
10. veridian according to claim 7, wherein, the non-zinc metal phthalocyanine of described many halos is to be selected from one or more in many halogenated aluminum phthalocyanine, many halos magnesium phthalocyanine, many halos titanium phthalocyanines, many halos tin phthalocyanine and many halogenated copper phthalocyanines.
11. veridians according to claim 1 and 2 wherein, heat or seethe with excitement and process front and back in organic solvent, and large elongation does not occur the particle diameter of pigment particles, and the angle of diffraction of X-ray diffraction and also variation substantially of diffracted intensity.
12. 1 kinds of manufacture method of manufacturing the veridian described in claim 1, it is characterized in that, in medium, from resulting solution, make the non-zinc metal phthalocyanine of many halos ZnPc and many halos with the form eutectoid of compound stores described many halos ZnPc pigment and the non-zinc metal phthalocyanine of described many halos pigment dissolved.
13. 1 kinds of manufacture method of manufacturing the veridian described in claim 2, it is characterized in that, molar ratio by described many halos ZnPc pigment and the non-zinc metal phthalocyanine of described many halos pigment with 30:70～95:5 is dissolved in acid, by reducing acid concentration in resulting solution, makes many halos ZnPc and the non-zinc metal phthalocyanine of many halos with the form eutectoid of compound stores.
The manufacture method of 14. veridians according to claim 13, wherein, the reduction of the acid concentration in described solution is to be undertaken by adding aqueous acids or make this solution absorb moisture in this solution, or is carried out in a large amount of water of high degree of agitation or injection or in frozen water by this solution is injected into.
The manufacture method of 15. veridians according to claim 13, wherein, described acid is oleum or 100% sulfuric acid.
16. according to the manufacture method of the veridian described in claim 12 or 13, wherein, in described eutectoid or after eutectoid, carries out the miniaturization operation of pigmenting processing and/or pigment.
The manufacture method of 17. veridians according to claim 16, wherein, it is following processing that described pigmenting is processed, described processing is: in eutectoid or after eutectoid, make product in eutectoid or after eutectoid and the water that contains hydrophobic organic solvent and/or hydrophilic organic solvent or frozen water contacts or contact with described organic solvent.
18. 1 kinds of veridian dispersive compositions, is characterized in that, it contains: the veridian described in claim 1 or 2; Organic solvent system, water system or water-hydrophilic organic solvent mixed solvent are liquid medium; The polymerizability liquid medium that polyreactive oligomers or polymerizable monomer form; The resin medium that softening agent, oligopolymer or synthetic resins form, further contains polymerization system dispersion agent or low molecular dispersion auxiliary agent as dispersing auxiliary.
19. 1 kinds of tinting materials, it is characterized in that, it contains: veridian dispersive composition, the diluent media described in claim 18 and being selected from as one or more the material being coated with in thermoplastic polymer, reactive polymer, reactive oligomers, polymerizable monomer and the linking agent of film formation material, further contains curing catalysts or polymerizing catalyst.
20. tinting materials according to claim 19, it forms with ink, coating, coloring resin agent, printing-ink, staining agent, stationery, drawing pigment, photographic developer or xeroprinting photographic developer for electrophotographic printing as color filter pixel.
21. tinting materials according to claim 19, it is as printing and dyeing agent.
22. tinting materials according to claim 20, described printing-ink is ink for inking.
The colorize method of 23. 1 kinds of article, is characterized in that, right to use requires veridian dispersive composition described in 18 or the tinting material described in claim 19 to carry out painted to article.
24. require the colorize method of the article described in 23 as requested, and wherein, described article painted is that the method by utilizing known photolithography, transfer printing, laminating method, ink-jet printing process, print process to form pixel on filter substrate is carried out.
25. require the colorize method of the article described in 23 as requested, and wherein, described article painted is by application, coloring resin, press plate printing, dyeing, written record, describes picture, ink jet printing, electrophotographic printing or xeroprinting and carry out.
26. require the colorize method of the article described in 23 as requested, and wherein, the painted of described article is to be undertaken by printing and dyeing.
27. 1 kinds of dyed articles, its right to use requires the colorize method described in 23 to form.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009-135972 | 2009-06-05 | ||
| JP2009135972 | 2009-06-05 | ||
| PCT/JP2010/058908 WO2010140519A1 (en) | 2009-06-05 | 2010-05-26 | Green pigment, process for production of same, coloring matter containing same, and method for coloring using same |
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| CN102803396A CN102803396A (en) | 2012-11-28 |
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| JP (1) | JP5297527B2 (en) |
| KR (1) | KR101361859B1 (en) |
| CN (1) | CN102803396B (en) |
| TW (1) | TWI458783B (en) |
| WO (1) | WO2010140519A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012053183A (en) * | 2010-08-31 | 2012-03-15 | Dainippon Printing Co Ltd | Color filter and display device |
| JP5817099B2 (en) * | 2010-09-28 | 2015-11-18 | 三菱化学株式会社 | Green pigment colored resin composition, color filter, liquid crystal display device, and organic EL display device |
| KR101892948B1 (en) | 2010-11-24 | 2018-08-29 | 엠. 테크닉 가부시키가이샤 | Solid solution pigment nanoparticles and method for producing solid solution pigment nanoparticles having controlled solid solution ratio |
| CN102618065A (en) * | 2012-03-05 | 2012-08-01 | 丽王化工(南通)有限公司 | Method for manufacturing phthalocyanine blue pigment with high temperature resistance |
| KR102029354B1 (en) * | 2015-02-03 | 2019-10-07 | 토요잉크Sc홀딩스주식회사 | Phthalocyanine Pigment, Coloring Composition and Color Filter |
| JP6172221B2 (en) * | 2015-07-16 | 2017-08-02 | 三菱ケミカル株式会社 | Green pigment colored resin composition, color filter, liquid crystal display device, and organic EL display device |
| JP6645859B2 (en) * | 2016-02-05 | 2020-02-14 | サカタインクス株式会社 | Green pigment dispersion for color filters |
| JP7234513B2 (en) * | 2018-06-13 | 2023-03-08 | 東洋インキＳｃホールディングス株式会社 | Coloring composition, color filter and liquid crystal display device |
| JP6809649B2 (en) * | 2018-08-31 | 2021-01-06 | Dic株式会社 | Halogenated zinc phthalocyanine pigments, coloring compositions and color filters |
| JP6744002B1 (en) * | 2019-12-09 | 2020-08-19 | Dic株式会社 | Zinc halide phthalocyanine pigment for color filter and method for producing zinc halide phthalocyanine pigment for color filter |
| KR102286873B1 (en) * | 2019-12-09 | 2021-08-09 | 디아이씨 가부시끼가이샤 | Halogenated zinc phthalocyanine pigment for color filter and manufacturing method of halogenated zinc phthalocyanine pigment for color filter |
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- 2010-05-26 CN CN201080024714.6A patent/CN102803396B/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102803396A (en) | 2012-11-28 |
| TW201107425A (en) | 2011-03-01 |
| JPWO2010140519A1 (en) | 2012-11-15 |
| JP5297527B2 (en) | 2013-09-25 |
| KR20120036902A (en) | 2012-04-18 |
| TWI458783B (en) | 2014-11-01 |
| WO2010140519A1 (en) | 2010-12-09 |
| KR101361859B1 (en) | 2014-02-13 |
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