CN1210619C - Red-colouring corrosion-resisting stamp-pad ink and pigment optical filter - Google Patents
Red-colouring corrosion-resisting stamp-pad ink and pigment optical filter Download PDFInfo
- Publication number
- CN1210619C CN1210619C CNB011172347A CN01117234A CN1210619C CN 1210619 C CN1210619 C CN 1210619C CN B011172347 A CNB011172347 A CN B011172347A CN 01117234 A CN01117234 A CN 01117234A CN 1210619 C CN1210619 C CN 1210619C
- Authority
- CN
- China
- Prior art keywords
- pigment
- red
- corrosion
- diketopyrrolo
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- 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
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
Abstract
The present invention relates to a red color resist which can give a high level of lightness and chroma when used in color filters for liquid crystal displays. In the red color resist obtained by dispersing a red pigment into a photosensitive resin composition, (D) a diketopyrrolopyrrole pigment and (E) a diketopyrrolopyrrole-sulfonic acid derivative or (A) a diketopyrrolopyrrole pigment whose surface has been treated with a diketopyrrolopyrrole-sulfonic acid derivative is used as the pigment component, and (B) a graft polymer obtained by reacting (a) a poly(lower alkyleneimine) or (b) a polyallylamine with (i) a polyester having a free carboxylic group, (ii) a polyamide or (iii) a polyesteramide to form an amide or a salt is used as the dispersing agent for dispersing this pigment component, and (C) a sulfonic acid derivative of an organic pigment is used as the crystal growth inhibitor.
Description
The invention relates in LCD (LCD) with the novel red colouring corrosion-resisting stamp-pad ink that uses in the color filter (CF) etc. and use its LCD CF.
As red pigment, the known composition that the painted usefulness of macromolecule organic material of use diketopyrrolo-pyrrole (DKPP) is arranged, can use it, for example make powder, pastel, fast paste (Off テ ッ シ ュ ペ-ス ト) and the correctives done, be applicable to printing-ink, starching colorant, bonding agent colorant and coating material, for example the spy open flat 8-20731 communique and spy open have in the flat 8-27391 communique disclosed.
Yet, use is with the DKPP dispersing of pigments body of above-mentioned prescription in the past modulation, modulation red-colouring corrosion-resisting stamp-pad ink (RCRI), make LCD CF with it, can not reach the bright chroma of the desired high level of nearest high-grade LCD, for this problem, its reason is that former DKPP primary particle size is very big, and, due to the difficult dispersiveness.
Because DKPP crystalline growth under the high temperature more than 250 ℃ is very big, expose to the open air in ITO splash operation in the CF purposes of high temperature more than 250 ℃, because the crystalline growth of DKPP material, crystallization is separated out on the CF surface, becoming the reason that produces haze, is again a problem.
The purpose of this invention is to provide a kind of RCRI that can pay the bright chroma of high level, when being used for CF that LCD uses, do not have the problems referred to above.
Present inventors' the starting point be with DKPP with at present as RCRI with 4,4 of red pigment '-diaminostilbene, 1 '-DIANTHRAQUINONE (DABAQ) compares, and has near the so-called very big characteristic of ascendant trend of dividing the light transmission curve to occur 550-600nm.When using the RCRI that DKPP is suitable for as red pigment; very big with the overlapping area of color matching function Y (λ); promptly; can obtain brightness Y value than the LCD CF that improves significantly in the past; and then; as red pigment, by using the micronize item for disposal of this DKPP, and the increase tendency that further quickens the Y value.Present inventors predict these, and set about studying.Yet crystalline growth makes the CF surface form the difficult problem of haze sometimes when having run into the dispersiveness of DKPP and dispersion stabilization than the difficult problem of pigment difference in the past and high temperature again, and these difficult problems become the reason that hinders the high bright colorize corrosion-resisting stamp-pad ink of exploitation again.
Present inventors have studied the analysis condition of DKPP pigment, and the difficult dispersed and CF when having found the pigment dispersing of above-mentioned problem can suppress the pigment dispersing condition of crystalline growth when being exposed to high temperature, and has finished the present invention thus.
Promptly, red-colouring corrosion-resisting stamp-pad ink of the present invention, be that red pigment is dispersed in the red-colouring corrosion-resisting stamp-pad ink that forms in the photosensitive polymer combination, feature is to carry out surface-treated surface treatment diketopyrrolo-pyrrole pigment (A) through the diketopyrrolo-pyrrole sulfonic acid, with (a) poly-(rudimentary alkylene imines) or (b) polyallylamine be selected from the polyester that (i) has free carboxy, (ii) have the polyamide of free carboxy or (iii) have reacting more than a kind or 2 kinds in the polyesteramide of free carboxy and form acid amides or salt and form graft polymer (B) spreading agent, it is disperseed to constitute.
Red-colouring corrosion-resisting stamp-pad ink of the present invention, it is the red-colouring corrosion-resisting stamp-pad ink of forming red pigment being dispersed in the photosensitive polymer combination, it is characterized in that diketopyrrolo-pyrrole pigment (D), with diketopyrrolo-pyrrole sulfonic acid (E), crystalline growth inhibitor and/or spreading agent, and above-mentioned graft polymer (B) spreading agent disperses and constitutes.
And then color filter of the present invention is to make of above-mentioned red-colouring corrosion-resisting stamp-pad ink.
Below the present invention is described in detail.
Surface treatment DKPP pigment (A) that uses among the present invention and DKPP pigment (D) for example can be made in the following manner.At first, make p-Cyanochlorobenzene and bromine acetate in the presence of zinc powder, react synthetic DKPP pigment (D).Then, surface treatment DKPP pigment (A), be that DKPP pigment (D) is dissolved in the concentrated sulphuric acid, oleum, chlorosulfonic acid or their mixed liquor, be heated to 80-90 ℃, carry out sulfonating reaction, then, behind the suspension that filtration obtains, wash with a large amount of water dilutions, with the filtration cakes torrefaction that obtains, obtain diketopyrrolo-pyrrole sulfonic acid (DKPPS), then DKPP and DKPPS after solvent dissolves simultaneously, are separated out in the impouring water jointly, filter, obtain moisture filter cake, dry, pulverizing can obtain with DKPPS DKPP being carried out surface-treated DKPP.Yet, not only be defined in above-mentioned manufacture method.
Above-mentioned DKPPS can represent with following formula (I).
(wherein, X represents that hydrogen or halogen, m, n represent m+n=1-4)
Surface treatment DKPP (A) and common DKPP comparison have good dispersiveness and dispersion stabilization, and its mechanism is presumed as follows.That is, think the DKPPS that uses in the surface treatment, owing to have the molecular skeleton identical with DKPP, when separating out simultaneously in both the mix sulphur acid solution impouring water, DKPPS is adsorbed on and forms the unification body on the DKPP surface, thereby produces the surface-treated state.At this moment, hydrophilic sulfonic group appears on the unification surface and can increase the negative surface potential of DKPP surface of pigments, repulsive force by static, be expected to increase dispersing of pigments and dispersion stabilization, and then, think DKPPS, because above-mentioned negative potential increases, also increased following adsorbability and absorption affinity with polymer fraction agent of cationic anchor position parts such as amino, also increase simultaneously the steric repulsion power that forms by spreading agent, thereby further increase this dispersing of pigments and dispersion stabilization, brought into play its function as dispersing aid.
Surface treatment DKPP (A) that uses among the present invention and DKPPS (D) consider from improving brightness Y value aspect, preferably use specific surface area at 90m
2The micronize product that/g is above.This micronize product, by above-mentioned moisture filter cake is mixed with color spreading agent, and continuous strong stirs, and the method that is called imbibition (Off ラ ッ シ Application グ) method that makes DKPPS transfer to the color spreading agent phase from water can obtain.Color spreading agent as new usefulness has surfactant, macromolecule dispersing agent, reaches the organic solvent solution of rosin derivative etc., prevents the cohesion again of surface treatment DKPP, can obtain the micronize product.As the manufacture method of micronize product, the salt polishing that surface treatment DKPP is ground fragmentation in the presence of salt is arranged.Certainly, the autofrettage of particulate product does not have particular determination yet.
And then surface treatment DKPP (A) that uses among the present invention and DKPP (D) adopt with organic solvent and clean the refining DKPP that removes foreign material and from its sulfonic acid fabricator, consider it is preferred from improving problem or the discoloration problem that impurity causes that crystallization is separated out.As impurity the organism such as residue that use raw material when making DKPP are arranged, for example 4-chlorobenzonitrile etc.
Therefore, the organic solvent that uses when cleaning DKPP, so long as can dissolve above-mentioned foreign material and not dissolve diketopyrrolo-pyrrole, it there is not particular determination, aromatic solvents such as toluene, dimethylbenzene and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone etc. are for example arranged.
Red-colouring corrosion-resisting stamp-pad ink of the present invention is made up of red pigment surface treatment DKPP pigment (A) or DKPP pigment (D) and photosensitive polymer combination, spreading agent.Use the pigment dispersion of surface treatment DKPP pigment (A), himself have by above-mentioned electrostatic repulsion forces generation dispersiveness, but in order to pay the steric repulsion effect, the most handy graft polymer (B) is made spreading agent.
As the graft polymer (B) of this spreading agent is to have cationic base section that adsorption pigment plays the anchor position effect and the spreading agent of being paid dispersed macromolecular chain part by the steric repulsion effect.This graft polymer (B) is to make (a) poly-(rudimentary alkylene imines) or (b) polyallylamine, have the polyester of free carboxy acid's base, (ii) have the polyamide of free carboxy acid's base and (iii) have reacting more than a kind or 2 kinds in the polyesteramide of free carboxy acid's base with being selected from (i), form the graft polymer of acid amides or salt.The method for making of this graft polymer can adopt known method (with reference to special public clear 63-30057 communique and the flat 9-169821 communique of Te Kai).(a)～(b) or (i)～(iii) can make a kind that uses respectively separately, also can use separately more than 2 kinds.
(a)～(b) being the cationic base section of anchor position effect, (i)～(iii) is to pay dispersed macromolecular chain part by the steric repulsion effect.Therefore, amino amount (a)～(b) and molecular weight (i)～have (iii) determined dispersing of pigments and dispersion stabilization.Can use the amine value of spreading agent for such dispersing agent performance index, the amine value of used cationic macromolecule dispersing agent is preferably 5-60[KOHmg/g among the present invention], 5-40[KOHmg/g more preferably] scope.If amine value diminishes, then the amino amount of expression in (a)～(b) reduces, and perhaps the molecular weight of (i)～(iii) increases, and at this moment, the adsorbability of pigment played disadvantageous effect, and the steric repulsion effect is played favourable effect.In contrast, big if amine value becomes, can produce and above-mentioned opposite effect, that is to say that the amine value of cationic macromolecule dispersing agent should be present in as above-mentioned optimum range.When the most suitable cationic macromolecule dispersing agent is example with the commercially available product among the present invention, can list the Avecia corporate system: trade name Solsperse 24000GR, same Solsperse24000SC, aginomoto fine techniques company) system: trade name ァ ヅ ス パ-PB-821.
Among the RCRI of the present invention, as the crystalline growth inhibitor of surface-treated DKPP pigment (A) or DKPP pigment (D), the sulfonic acid (C) of the organic pigment beyond the fits best DKPP.The sulfonic acid of above-mentioned organic pigment (C), as long as molecular structure is not the sulfonic acid of the organic pigment of DKPP, then unqualified to it, but consider from form and aspect, preferably red or yellow, for example can be the sulfonic acid (C-2) of benzidine yellow sulfonic acid (C-1) and DABAQ.
(C-1) manufacturing is carried out dichloro-benzidine to carry out sulfonation with the method the same with above-mentioned DKPPS again after quadruple nitrogenize and acetoacetyl acrylate carry out coupling and obtain benzidine yellow.
(C-1) can following formula (2) expression.
(wherein, R
1, R
2Expression hydrogen or chlorine, X represent that hydrogen, methyl or methoxy, Y represent that hydrogen, methyl or chlorine, Z represent hydrogen or methoxyl).
(C-2) manufacturing is with 1-amino-4-chloro-2-sulfonic acid condensation, takes off the DABAQ that sulfonation makes, be dissolved in the concentrated sulphuric acid, oleum, chlorosulfonic acid or their mixed liquor, room temperature is to being heated to 80～90 ℃, then obtain suspension with a large amount of water dilutions, after the filtration, washing will obtain filtration cakes torrefaction, pulverizing.This (C-2) do not have commercially available product.
(C-2) represent with following formula (3).
(wherein, m, n are m+n=1～4).
How the sulfonic acid (C) of the organic pigment beyond the DKPPS can demonstrate the effect that suppresses crystalline growth for (A) or DKPP series pigments (D), though its mechanism is indeterminate, but can think that (C) can be adsorbed on (A), (D) surface, and change (A) or characteristic (D), suppress crystalline growth thus.
RCRI of the present invention has, (1) will carry out surface-treated surface treatment DKPP (A) and the necessary composition of spreading agent graft polymer (B) conduct with DKPPS, (2) with DKPP pigment (D), DKPPS (E) and spreading agent graft polymer (B) as must composition, (3) with surface treatment DKPP (A) and DKPP (D), and DKPPS (E) and the necessary composition of spreading agent graft polymer (B) conduct.(2) RCRI, DKPP pigment do not carry out surface treatment, replace DKPPS as another kind of spreading agent.(3) RCRI can use surface treatment DKPP pigment (A) and DKPP pigment (D) as pigment composition.In any corrosion-resisting stamp-pad ink, preferably cooperate in addition except sulfonic acid (C) as the organic pigment the DKPPS of crystalline growth inhibitor.
The cooperation ratio of each composition, the use level (weight portion) of sulfonic acid (C), DKPP pigment (D) and the DKPPS (E) of the organic pigment beyond surface treatment DKPP (A), graft polymer (B), the DKPPS, with (A), (B), (C), (D) and (E) expression, the most favourable in following scope respectively.
Contain (A) and (B), when the total amount of (A) is taken as 100 weight portions, (B) be 30～45 weight portions.
Containing (A), (B), (C), the total amount of (A)+(C) is taken as at 100 o'clock, (B) is the 30-45 weight portion, (C) is the 3-7 weight portion.
Containing (B), (D), (E), the total amount of (D)+(E) is taken as at 100 o'clock, (B) is the 30-45 weight portion.
Containing (B), (C), (D), (E), when the total amount of (D)+(E)+(C) is taken as 100 parts, (B) be the 30-45 weight portion, (C) is the 3-7 weight portion.
Contain (A), (B), (C), (D), (E), when the total amount of (A)+(D)+(E)+(C) is taken as 100 weight portions, (B) be the 30-45 weight portion, (C) be the 3-7 weight portion.
In addition, ratio (D) and (E) when the total amount of (D)+(E) is taken as 100 weight portions, (E) is preferably the scope of 5-30 weight portion.
The use level of spreading agent graft polymer (B) is except that pigment composition with (B), when becoming to grade total 100 weight portions for spreading agent, be preferably 30～45 weight portions, when use level was less than this scope, pigment divided the high viscosity of body can pass viscosity in time to increase, be not suitable for using.Use level than this scope for a long time, in the alkaline development operation when CF makes, figure can disappear sometimes, so inapplicable.
The use level of the sulfonic acid (C) of the organic pigment beyond the DKPPS of crystalline growth inhibitor with respect to pigment composition and spreading agent total 100 weight portions that become to grade, is preferably the 3-7 weight portion.When use level was less than this scope, the effect that suppresses crystalline growth when CF is exposed to high temperature was insufficient, so inapplicable.And use level is dispersed bad during more than this scope, and corrosion-resisting stamp-pad ink is coated with and is easy to generate particle on the face and assembles, and is inapplicable.At this, (A), (D) are calculated as pigment composition, (C), (E) as spreading agent calculatings that becomes to grade, (B) from calculate, deduct.(C) though be the crystalline growth inhibitor, also can be used as dispersing aid and work for (B), so be called dispersing aid sometimes.Equally, though (E) be spreading agent, also can be used as dispersing aid or crystalline growth inhibitor for (B) and work, so be called dispersing aid or crystalline growth inhibitor sometimes.
Among the RCRI of the present invention, as with (A) surface treatment DKPP pigment of red pigment and (D) method of DKPP pigment dispersing in photoresist, following method is arranged, in advance, with above-mentioned pigment dispersing in the organic solvent that has dissolved graft polymer (B) spreading agent, be modulated into red pigment dispersion, again that it is (best with the composition that contains photoresist, remove the composition of Photoepolymerizationinitiater initiater) mix the method for dispersion and above-mentioned pigment directly is distributed to the method that contains in the photosensitive polymer combination etc.Consider that from the stable aspect of colored corrosion-resisting stamp-pad ink preceding a kind of method is better.
As the organic solvent that uses in above-mentioned, consider from the dissolubility of dispersing of pigments and spreading agent, can use ester class, ketone, polyol derivative, nitrogenous series solvent etc., for example, the ester class has ethyl acetate, butyl acetate etc., ketone has cyclohexanone, ethyl butyl ketone etc., and the derivant of polyvalent alcohol has ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate etc.Nitrogenous series solvent has dimethyl formamide etc.
In the surface treatment DKPP pigment (A) or DKPP pigment (D) that uses among the present invention, consider to disperse to cooperate yellow uitramarine simultaneously from toning.By cooperating yellow uitramarine, divide the light transmission curve to low wavelength side shifting, help improving brightness Y value.
Can use C, I face item number to be PY-83, PY-139 etc. as this yellow uitramarine.
During with surface treatment DKPP pigment (A) or diffusing making seal agent of DKPP pigment (D) or red pigment dispersion composition, at first use three-stage roll mill, with pigment, graft polymer (B) spreading agent and organic solvent, or after they and photoresist etc. mix, append organic solvent, disperse with bowl mill again, make seal agent or red pigment dispersion composition, consider it is preferred from eliminating the dispersed aspects of raising such as coarse grain.When the pigment derivative of using as dispersing aid and crystalline growth inhibitor is corase particles, one side owing to need that fine powder is broken mixes on one side, so must use three-stage roll mill.
As this three-stage roll mill, can use the double-roll type muller, 3 three-stage roll mill etc.Consider from the ability of mixing, the service condition of the most handy 3 three-stage roll mill, 3 three-stage roll mill, the preliminary roller rotating speed is 50～200rpm, preliminary roller: central roll: the rotating ratio of back roller is 1.0: 1.5: 5.0～1.0: 3.0: 8.0.By mixing of three-stage roll mill, can further improve dispersion stabilization.
In following Ball milling, can use the rotary-type bowl mill of disk, ring-type type bowl mill etc., the service condition when using the rotary-type bowl mill of disk, consider from the dispersibility aspect, ball footpath 0.1～1.0mm φ preferably, the ball filling rate is more than 80%, and the disk peripheral speed is 10～20m/ second.
RCRI of the present invention is that surface treatment DKPP (A) or the DKPP pigment (D) with red pigment is dispersed in the transparent resin, and this transparent resin is the photoresist that is formed by optical polymerism resin or monomer or oligomer.Said photosensitive polymer combination among the present invention, except above-mentioned resin or monomer or oligomer, usually contain Photoepolymerizationinitiater initiater and organic solvent, the state that also can solidify forms resin, only can contain to form thing by not carrying out resinification composition under uncured state.
Such photoresist, as monomer or oligomer, 2-hydroxyethyl (methyl) acrylate is for example arranged, 2-hydroxypropyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol (methyl) acrylate, TEG two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, trimethylolpropane (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, pentaerythrite two (methyl) acrylate, dipentaerythritol four (methyl) acrylate, two season amylalcohol six (methyl) acrylate, glycerine (methyl) acrylate, bisphenol type epoxy (methyl) acrylate, Bisphenol F type epoxy (methyl) acrylate, (methyl) esters of acrylic acids such as bisphenol fluorene type epoxy (methyl) acrylate etc.These photopolymerization monomers, oligomer can use separately, also can share more than 2 kinds.
As Photoepolymerizationinitiater initiater, acetophenone is for example arranged, 2,2 '-the diethoxy acetophenone, to dimethyl acetophenone, acetophenones such as p-tert.-butyl acetophenone, benzophenone, the 2-chlorobenzophenone, p, p '-benzophenones such as two dimethylamino benzophenone, benzoin methylether, benzoin iso-propylether, benzoin ethers such as benzoin butyl ether, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(the single morpholino phenyl of 4-)-class such as benzophenone such as alpha-aminoalkyl such as butanone-1 grade, the benzyl dimethyl acetal, thioxanthones, the 2-clopenthixal ketone, 2, sulfocompounds such as 4-diethyl thioxanthone etc.These Photoepolymerizationinitiater initiaters can use separately, also can share more than 2 kinds.
As organic solvent, cellosolve classes such as ketones such as methylisobutylketone, diisobutyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate etc. are for example arranged.These organic solvents can use separately, or share more than 2 kinds.
During in advance with surface treatment DKPP pigment (A) or DKPP pigment (D) formation red pigment dispersion, the cooperation ratio of its amount and photosensitive polymer combination, can suitably select according to the exposure light sensitivity with to the degree of development requirement, usually, with the weight ratio of solid constituent, the former: the latter=5: 95～30: 70 is the most desirable.The seal agent that obtains like this, suitable to CF RCRI, the CF that uses this seal agent to obtain makes it solidify to form film in pixel.As using this seal agent to make the method for CF, can adopt known method.
Followingly be described more specifically the present invention according to embodiment and comparative example.Be shown in following simple number of the pigment that uses in embodiment and the comparative example, pigment derivative, spreading agent, crystalline growth inhibitor and organic solvent.
＜red pigment: (A), (D) composition
(A)-1: with X in the above-mentioned formula (1) is that chlorine, n, m be 0 DKPP with the middle X of above-mentioned formula (1) are that chlorine, n, m are that 1 DKPPS carries out surface treatment, and obtaining specific surface area is 93.8m
2The micronize of/g is handled DKPP pigment.
(D)-1: specific surface area is 93.8m
2The DKPP micronize that the following formula of the usefulness of/g is represented is handled pigment
＜spreading agent: (B) composition 〉
(B)-and A: poly-(allylamine) that the spy is opened put down in writing in the flat 9-169821 communique reacts with the polyester with free carboxy acid's base, the graft polymer of the amine value 7.7 that obtains (aginomoto fine techniques) (strain) system: the 50.0 weight % solution of trade name ァ ヅ ス パ-PB-821)
(B)-and B: make poly-(aziridine) put down in writing in the special public clear 63-30057 communique and polyester react the graft polymer of the amine value 30.6 that obtains (the 50.0 weight % solution of Avecia society system: trade name Solsperse 24000 (GR) with free carboxy acid's base.
(B)-and C: the polyepoxides that the spy is opened put down in writing in the flat 9-87537 communique reacts 49.9 weight % solution (aginomoto fine techniques) (strain) system of the graft polymer of the amine value 35.5 that obtains with the organic amino compounds that has the linear polymer of one-sided terminal carboxyl group and have 1 secondary amino group: ァ ヅ ス パ-PB-711)
(B)-and D: the spy is opened, and polyisocyanate compounds of putting down in writing in the clear 60-166318 communique and the hydrocarbon compound with alcohol hydroxyl group react with the hydrocarbon compound with amino, and the amine value that obtains is 47.0 weight % solution (BYC Chemie corporate systems: disperbyk-163) of 20.1 urethanes
(B)-and E: the spy is opened, and acrylate polymer with alcohol hydroxyl group and polyisocyanate compounds of putting down in writing in the flat 1-164429 communique and the hydrocarbon compound with amino react 42.9 weight % solution (the EFKA Chemical B.V. corporate system: EFKA-46) of the acrylate polymer of the amine value 29.1 that obtains
＜spreading agent, crystalline growth inhibitor, dispersing aid: (E), (C) composition
(E)-1: the DKPPS that represents with above-mentioned formula
(C)-and BY: in the above-mentioned formula (2), R
1Be chlorine, R
2For hydrogen, X, Z are that methoxyl, Y are the benzidine yellow sulfonic acid of chlorine
(C)-AQ: in the above-mentioned formula (3), m, n be 14,4 '-diaminostilbene, 1 '-sulfonic acid of DIANTHRAQUINONE
＜organic solvent 〉
S-1: propylene glycol monomethyl ether acetate
S-2: diethylene glycol dimethyl ether
The pigment dispersion of modulation and the evaluating characteristics condition that colored corrosion-resisting stamp-pad ink is filmed below are shown.
The evaluating characteristics of＜pigment dispersion 〉
＜viscosity 〉
After the dispersion, to leave standstill under the room temperature 1 round the clock red pigment dispersion composition leaves standstill 40 minutes in 23 ℃ Water Tank with Temp.-controlled after,, measure under 23 ℃, with rotating speed 60rpm with Brookfield viscometer [(strain) ト キ メ ッ Network system: trade name BL type] as initial stage viscosity.
Then, this dispersion placed for 1 week in 40 ℃ hot-blast baker after, under same condition, measure viscosity, estimate the variations of 40 ℃ of timeliness of preserving down.
＜TI value (thixotropic index value) 〉
Viscosity when removing revolution 6rpm with the viscosity of rotating speed 60rpm, income value is initial stage TI value.
Then, this dispersion placed for 1 week in 40 ℃ of hot-blast bakers after, under similarity condition, measure TI value, estimates the variations of the timeliness of 40 ℃ times preservations.
＜mean grain size 〉
Red pigment dispersion composition 0.003g is diluted with organic solvent (S-1) 40g, in ultrasonic cleaner, carry out 90 seconds ultrasonic dispersing, test portion is measured in modulation, makes with laser Doppler method particle size distribution device [Da mound electronics (strain): trade name ELS-800] measure.
The evaluating characteristics that＜colouring corrosion-resisting stamp-pad ink is filmed 〉
＜coating is observed (center has or not fault) 〉
Film to the seal agent and to go up the irradiation yellow light, observe the surface, estimate the dense color part that whether has the fault shape in the centre.
＜microscopic examination surface state (have or not cohesion grain and crystallization to separate out 〉
With the surface state that the reflective polarizing microscopic examination seal agent of amplifying 400 times is filmed, do not observe aggregated particle and crystallization is separated out, with (zero) expression; Existence is arranged slightly, with (△) expression; Significantly existence can not be used, with (*) expression, by above-mentioned three grades of evaluations, as A-stage.
Then, will print the agent coated plate and put into heat generator, after exposing 1 hour to the open air under 250 ℃, under above-mentioned identical condition, observe surface state, by three grades of evaluations.
＜brightness Y value and colourity (X, Y) 〉
With the value representation of measuring with colorimeter [Tokyo electricity look (strain) system: trade name カ ラ one ァ Na ラ イ ザ-TC-1800MK2].
＜thickness 〉
In the value representation of measuring with contact pin type surfaceness [Tokyo precision (strain) goods].
Figure deorienting during＜alkaline development 〉
Seal agent after the above-mentioned exposure is filmed with after 0.4% the aqueous sodium carbonate development, whether disappear because of stripping with the photomask pattern line that amplifies 100 times reflective polarizing microscopic examination live width 100 μ m, and estimate, not disappear, do not represent with zero; Disappear usefulness * expression.
Embodiment 1
[modulation of pigment dispersion and evaluating characteristics]
Composition with record in the table 1, promptly, pigment (A)-1 187.0g, spreading agent (B)-A 112.2g, organic solvent S-1 1130.8g are engaged in the 2L aggregation container, with homogenizing mixer (special machine chemical industry (strain) system: trade name ロ ボ ミ ッ Network ス), after mixing 1 hour with 2000rpm, use again the rotary-type bowl mill of disk (the WAB corporate system: trade name DYNO-MILL KDL-Special) carry out pigment dispersing, be modulated into the pigment dispersion of 13.1 weight % such as spreading agent (B) fit rate 30.0 weight %, solid constituent 17.0 weight %, pigment.
Use level (g), fit rate etc. gather with other embodiment and are shown in table 1.Here, the fit rate of spreading agent (B), crystalline growth inhibitor (C) and spreading agent (E), all with (A)+(D)+(C)+(E)=100 weight % as benchmark.
In all embodiment, comparative example, the weight ratio of ((A)+(D)+(E))/resinous principles ((B)+resin) such as pigment when making the seal agent is taken as constantly 0.49, and solid component concentration is taken as 20.0 constant weight %.
The service condition of bowl mill is as follows.That is, for the medium ball, use zirconia material 0.3mm φ's, filling rate is 80%.Disk peripheral speed 8.6m/ second, the pressure of packing into is 0.5bar, and jitter time is taken as 4 hours.
For this red pigment dispersion composition, carry out evaluating characteristics according to the method described above, evaluating characteristics the results are shown in table 1.
[modulation that colored corrosion-resisting stamp-pad ink is filmed and evaluating characteristics]
As mentioned above, the micronize state and the dispersion stabilization of pigment dispersion are very good, and color modulation corrosion-resisting stamp-pad ink and filming carries out evaluating characteristics.
As resinous principle, use 150.91g bisphenol fluorene Epocryl solution [Nippon Steel's chemistry (strain) system: trade name V-259ME solid constituent 55.3%], 35.76g dipentaerythritol acrylate, 17.88g bisphenol-type epoxy resin (oiling Shell epoxy (strain) system: trade name エ ピ コ one ト YX-4000HK).As the Photoepolymerizationinitiater initiater composition, use 3.58g 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1,1.93g 4,4 '-two-lignocaine benzophenone, 5.36g 2,4-trichloromethyl-(4-methoxy styryl)-6-triazine, 1.79g 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, use 0.12g fluorine are surfactant [Sumitomo 3M (strain) system: trade name Off ロ ラ one De FC-430], be dissolved among the 294.75g organic solvent S-1, be modulated into the photosensitive polymer combination of solid component concentration 29.2%.Then, with the composition of table 1 record, this photosensitive polymer combination of 10.0g, the above-mentioned pigment dispersion of 20.6g, 3.5g organic solvent S-1 and 8.5g organic solvent S-2 mix, and are modulated into red-colouring corrosion-resisting stamp-pad ink.
Should the colour corrosion-resisting stamp-pad ink be coated on 5 inches square, blue or green glass sheet plates that 1mm is thick with spin coated device [ミ カ サ (strain) goods].At this moment adjust the rotating speed of spin coated device, form the seal agent thickness (main oven dry back) of 1.5 μ m, the time is 10 seconds.Then will be coated with seal agent glass plate and carry out preliminary drying, the preliminary drying condition is to carry out under 80 ℃ 3 minutes.Then after putting mask on the coating seal agent glass plate of preliminary drying, carry out 300mJ/cm
2UV exposure.Coating seal agent glass plate with the UV irradiation developed 25 seconds at 0.4% aqueous sodium carbonate neutral and alkali.This alkaline development seal agent coated glass plate, is made into as the seal agent of typical for red filtrator and films after 30 minutes 230 ℃ of down main oven dry.The seal agent that is made into like this filmed make test portion, estimate the look characteristic of colored corrosion-resisting stamp-pad ink according to the method described above, the results are shown in table 1.
Seal agent with the colored corrosion-resisting stamp-pad ink modulation that obtains in the present embodiment is filmed, there is not fault shape look dense part in the centre, screening characteristics good (zero) is to coated film surface microscopic examination result, under the A-stage, do not observe aggregated particle and crystallization is separated out, can use (zero), after exposing 1 hour to the open air under 250 ℃, not have aggregated particle, there is crystallization to separate out slightly but observe, but still is usable range (△).Brightness Y value is 21.9 expression excellent value, the anti-deorienting of figure (zero) also out of question when alkalescence is shown one's color.
Embodiment 2-6
Except cooperate to form press that table 1 puts down in writing, the order that other are identical with embodiment 1, conditioned pigment dispersion and colored corrosion-resisting stamp-pad ink are with the sequence evaluating characteristic identical with embodiment 1.The results are shown in table 1.
Embodiment 7
Cooperate to form as record in the table 1, except with the crystalline growth inhibitor from (C)-BY becomes (C)-AQ, the cooperation composition of other and embodiment 5 is roughly the same, the conditioned pigment dispersion.But, because (the C)-AQ that uses is the coarse grain shape, so after carrying out the micro mist fragmentation and mix with 3 three-stage roll mill, carry out the bowl mill dispersion again.
That is, with 190.0g pigment (A)-1,10.0g crystalline growth inhibitor (C)-AQ, 140.0g spreading agent (B)-A, be engaged in 21 aggregation containers, ((strain) aboveground making is made: trade name C-43/4 * 10) mix with 3 three-stage roll mill.After using 3 three-stage roll mill to mix, because crystalline growth inhibitor AQ-S is the coarse grain shape, thus on one side that its fine powder is broken, Yi Bian mix.The service condition of 3 three-stage roll mill is that preliminary roller rotation speed is 120rpm, preliminary roller: central roll: the speed ratio of back roller is 1.0: 2.6: 6.8, is undertaken 5 times by roller, obtains the 3 rollers thing that mixes.
Then, above-mentioned 3 rollers of 260.0g are mixed after thing and 457.4g organic solvent S-1 cooperate in the 2L aggregation container, use homogenizing mixer (special machine chemical industry (strain) system: trade name ロ ボ ミ ッ Network ス) mix stirring 1 hour, disperse to carry out bowl mill with embodiment 1 identical service condition with 200rpm.Be modulated into pigment dispersion, carry out evaluating characteristics, the results are shown in table 1.
With the cooperation color modulation corrosion-resisting stamp-pad ink of table 1 record, with the sequential system identical with embodiment 1 with becoming corrosion-resisting stamp-pad ink to film, evaluation look characteristic.The evaluation result of seal agent film is shown in table 1.
Embodiment 8-13
Cooperate to form and press table 1 record, the condition with identical with embodiment 7 makes the thing that mixes, and to carry out the bowl mill dispersion with embodiment 1 identical service condition, is modulated into pigment dispersion and colored corrosion-resisting stamp-pad ink, estimates its characteristic.
Table 1
| Embodiment number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | ||
| Proportioning (g) | 3 roller mills | ＜pigment〉(A)-1 (D)-1＜crystalline growth inhibitor〉(C)-BY (C)-AQ＜dispersant〉(B)-and A (B)-B (E)-1＜organic solvent〉S-1 | 190.0 10.0 140.0 0 | 180.0 140.0 20.0 20.0 | 170.0 140.0 30.0 20.0 | 160.0 140.0 40.0 40.0 | 180.0 140.0 20.0 20.0 | 170.0 10.0 140.0 20.0 20.0 | 170.0 10.0 140.0 20.0 20.0 | ||||||
| Bowl mill | The mixing product of＜3 rollers〉above-mentioned 3 roller product＜pigment (A)-1 (D)-1 (the crystalline growth inhibitor〉(C)-BY (C)-AQ＜dispersant (B)-A (B)-B＜organic solvent S-1 | 187.0 112.2 1130.8 | 180.0 126.0 1036.5 | 175.0 140.0 1136.4 | 180.0 126.0 1098.6 | 171.0 9.0 126.0 1100.3 | 171.0 9.0 126.0 1133.6 | 260.0 457.4 | 341.1 624.7 | 342.9 633.0 | 360.7 609.0 | 344.7 619.9 | 345.2 554.8 | 348.6 591.0 | |
| Divide (weight %) spreading agent (E) fit rate crystalline growth inhibitor fit rate spreading agent (B) fit rate Gu form | 17.0 0 0 30.0 | 18.1 0 0 35.0 | 17.0 0 0.0 40.0 | 17.3 0 0 35.0 | 17.3 0 5.0 35.0 | 16.9 0 5.0 35.0 | 17.2 0 5.0 35.0 | 17.1 10.0 0 35.0 | 17.4 15.0 0 35.0 | 17.7 20.0 0 35.0 | 16.9 10.0 0 35.0 | 16.5 10.0 5.0 35.0 | 17.4 10.0 5.0 35.0 | ||
| Ink | Bowl mill disperses thing photosensitive polymer combination organic solvent S-1 organic solvent S-2 | 20.6 10.0 3.5 8.5 | 20.6 10.0 4.3 8.7 | 23.5 10.0 2.4 9.0 | 21.6 10.0 3.4 8.8 | 21.6 10.0 3.4 8.8 | 22.1 10.0 2.9 8.7 | 21.6 10.0 3.4 8.7 | 21.8 10.0 3.2 8.7 | 21.5 10.0 3.5 8.7 | 21.1 10.0 3.9 8.7 | 22.1 10.0 2.8 8.7 | 22.3 10.0 2.5 8.7 | 21.2 10.0 3.6 8.7 | |
| Proterties | Pigment dispersion | Mean grain size nm viscosity [mPas] (initial value) the same (after 40 ℃-1 weeks) TI value (initial value) the same (after 40 ℃-1 weeks) | 134 6.40 9.34 1.08 1.07 | 129 6.50 8.25 1.09 1.07 | 118 6.41 7.89 1.03 1.03 | 143 7.64 9.15 1.09 1.08 | 128 5.59 6.09 1.06 1.00 | 134 6.11 6.85 1.16 1.17 | 102 6.85 12.5 1.02 1.00 | 99 6.01 6.96 1.01 1.05 | 107 7125 12.5 1.06 1.04 | 125 8.34 10.9 1.07 1.00 | 102 6.52 7.03 1.05 1.06 | 121 5.30 5.93 1.02 1.04 | 118 5.22 5.82 1.04 1.05 |
| Ink is filmed | The anti-deorienting of figure during the microscopic examination result (initial stage) on screening characteristics (center has or not fault) surface the same (250 ℃-1hr exposes the back) alkaline development | ○ ○ △ ○ | ○ ○ △ ○ | ○ ○ △ ○ | ○ ○ △ ○ | ○ ○ ○ ○ | ○ ○ ○ ○ | ○ ○ ○ ○ | ○ ○ △ ○ | ○ ○ △ ○ | ○ ○ △ ○ | ○ ○ △ ○ | ○ ○ ○ ○ | ○ ○ ○ ○ | |
| X, Y colourity X Y lightness Y thickness (μ m) | 0.614 0.323 21.9 1.54 | 0.626 0.328 22.5 1.54 | 0.612 0.324 23.0 1.42 | 0.632 0.330 22.0 1.56 | 0.618 0.328 22.3 1.52 | 0.616 0.328 22.0 1.60 | 0.620 0.327 22.3 1.58 | 0.610 0.323 22.5 1.48 | 0.622 0.326 21.8 1.54 | 0.620 0.327 21.6 1.54 | 0.612 0.325 22.6 1.50 | 0.620 0.330 22.5 1.53 | 0.618 0.331 22.6 1.51 | ||
Comparative example 1
Cooperate to form as table 2 is put down in writing, with the condition identical with embodiment 1, the conditioned pigment dispersion is carried out evaluating characteristics.
With the cooperation of table 2 record form be modulated into colored corrosion-resisting stamp-pad ink after, film to be modulated into the seal agent with embodiment 1 identical condition, carry out evaluating characteristics, the results are shown in table 2.
Comparative example 2～3
Cooperate to form as table 2 is put down in writing, with the condition identical with embodiment 1, be modulated into pigment dispersion and colored corrosion-resisting stamp-pad ink after, carry out evaluating characteristics, the results are shown in table 2.
Embodiment 1, embodiment 14
Cooperate to form as shown in table 2, with the condition identical with embodiment 1, be modulated into pigment dispersion and colored corrosion-resisting stamp-pad ink after, film to be modulated into the seal agent with embodiment 1 identical condition, carry out evaluating characteristics, the results are shown in table 2.
When the fit rate of spreading agent (B) exceeds optimum range, can not get the product of kilter as can be known.
Embodiment 15
Cooperate forming as shown in table 2ly, still, also is the coarse grain shape in (E)-1 then, is purpose with after embodiment 7 identical modes are made 3 three-stage roll mill and carried out that fine powder is broken and mix with broken the mixing of this fine powder therefore, carries out bowl mill again and disperses, and evaluating characteristics the results are shown in table 2.
With the cooperation of table 2 record form be modulated into colored corrosion-resisting stamp-pad ink after, with embodiment 5 mutually dealer's condition be modulated into the seal agent and film, carry out evaluating characteristics, the results are shown in table 2.
Experimental example 2
Cooperate composition as shown in table 2.That is, except the fit rate with crystalline growth inhibitor (C)-BY increased to 10.0 weight %, other were with the condition identical with embodiment 5, the conditioned pigment dispersion, and evaluating characteristics the results are shown in table 2.
Mean grain size is 123nm, reaches micronize.The viscosity initial value is 8.69mPas, and after 40 ℃ of following 1 weeks of placement, viscosity increases to some extent, is 21.5mPas, but within allowed band, the initial value of TI value is after placing for 1 weeks under 1.04,40 ℃, to be 1.00, and dispersion stabilization is also roughly fine.
With the condition identical with embodiment 5, the agent of modulation seal is filmed, and carries out evaluating characteristics, the results are shown in table 2.
Do not observe look dense part (fault) in the seal agent centre of filming, screening characteristics observations good (zero), but with the result on microscopic examination surface, in the early stage, after exposing 1 hour to the open air under 270 ℃, thinking has aggregated particle to occur, and surface state is near very poor (*).When excessive adding crystalline growth inhibitor exceeds optimum range, can not get the product of superperformance as can be known.
Comparative example 4
Cooperate composition as shown in table 2.That is, except that with pigment from DPP-A becomes DPP-B, other are with the condition identical with embodiment 2, conditioned pigment dispersion and colored corrosion-resisting stamp-pad ink carry out evaluating characteristics, the results are shown in table 2.
Comparative example 5～7
Cooperate composition as shown in table 2.That is, except that with the spreading agent kind from (B)-A becomes (B)-C, (B)-D or (B)-E, the condition that other are identical with embodiment 8, after being modulated into pigment dispersion and colored corrosion-resisting stamp-pad ink, film to modulate the seal agent, carry out evaluating characteristics, the results are shown in table 2 with embodiment 8 identical conditions.
Observe look dense part (fault) in the seal agent centre of filming, screening characteristics is observed very poor (*), therefore no longer carries out the evaluation of thickness characteristic of the same colour.
Table 2
Red-colouring corrosion-resisting stamp-pad ink of the present invention owing to have high score photopermeability and high Y value, is extremely useful so require the LCD CF of high bright colored for manufacturing.The pigment dispersion composition that uses among the present invention except do colored corrosion-resisting stamp-pad ink with, can also be used for the requirement high-luster coating, require high transparent pen with printing ink, ink-jet printer with China ink, printing ink.
Claims (16)
1. red-colouring corrosion-resisting stamp-pad ink, red pigment is dispersed in constitutes in the photosensitive polymer combination, feature is that usefulness diketopyrrolo-pyrrole sulfonic acid is carried out surface-treated surface treatment diketopyrrolo-pyrrole pigment (A), so that (a) poly-(rudimentary alkylene imines) or (b) polyallylamine and the polyester that (i) has free carboxy acid's base react graft polymer (B) spreading agent that forms acid amides or salt and constitute it disperseed to constitute, wherein the amine value of spreading agent is 5-60KOH mg/g.
2. according to the red-colouring corrosion-resisting stamp-pad ink of claim 1 record, feature is for 100 weight portion surface treatment diketopyrrolo-pyrrole pigments (A), and the use level of graft polymer (B) spreading agent is 30～45 weight portions.
3. according to the red-colouring corrosion-resisting stamp-pad ink of claim 1 record, feature is red pigment to be dispersed in the red-colouring corrosion-resisting stamp-pad ink that forms in the photosensitive polymer combination, with surface treatment diketopyrrolo-pyrrole pigment (A), disperse to constitute with organic pigment sulfonic acid (C) the crystalline growth inhibitor outside graft polymer (B) spreading agent, the diketopyrrolo-pyrrole.
4. according to the red-colouring corrosion-resisting stamp-pad ink of claim 3 record, feature be the sulfonic acid (C) of the organic pigment of crystalline growth inhibitor be benzidine yellow sulfonic acid (C-1) or 4,4 '-diaminostilbene, 1 '-DIANTHRAQUINONE sulfonic acid (C-2).
5. according to the red-colouring corrosion-resisting stamp-pad ink of claim 3 record, feature is that the total amount with the sulfonic acid (C) of surface treatment diketopyrrolo-pyrrole pigment (A) and organic pigment is when being taken as 100 weight portions, the use level of the sulfonic acid of organic pigment (C) is the 3-7 weight portion, and the use level of graft polymer (B) is the 30-45 weight portion.
6. according to the red-colouring corrosion-resisting stamp-pad ink of claim 1 or 3 records, feature is that surface treatment diketopyrrolo-pyrrole pigment (A) is that specific surface area is 90m
2The micronize pigment that/g is above.
7. red-colouring corrosion-resisting stamp-pad ink, red pigment is dispersed in forms in the photosensitive polymer combination, feature with diketopyrrolo-pyrrole pigment (D) with diketopyrrolo-pyrrole sulfonic acid (E), and by (a) poly-(rudimentary alkylene imines) or (b) polyallylamine and the polyester that (i) has free carboxy acid's base react graft polymer (B) spreading agent that forms acid amides or salt and constitute it disperseed to constitute, wherein the amine value of spreading agent is 5-60KOH mg/g.
8. according to the red-colouring corrosion-resisting stamp-pad ink of claim 7 record, feature is that the use level of graft polymer (B) is 30～45 weight portions to diketopyrrolo-pyrrole pigment of total amount 100 weight portions (D) and diketopyrrolo-pyrrole sulfonic acid (E).
9. according to the red-colouring corrosion-resisting stamp-pad ink of claim 7 record, red pigment is dispersed in the photosensitive polymer combination and constitutes, feature is with diketopyrrolo-pyrrole pigment (D), with diketopyrrolo-pyrrole sulfonic acid (E) crystalline growth inhibitor and/or spreading agent, organic pigment sulfonic acid (C) crystalline growth inhibitor beyond graft polymer (B) spreading agent, diketopyrrolo-pyrrole disperses to constitute.
10. according to the red-colouring corrosion-resisting stamp-pad ink of claim 9 record, feature is that the sulfonic acid (C) of organic pigment is benzidine yellow sulfonic acid (C-1), or 4,4 '-diaminostilbene, 1 '-DIANTHRAQUINONE sulfonic acid (C-2).
11. red-colouring corrosion-resisting stamp-pad ink according to claim 9 record, feature is that the total amount with the sulfonic acid (C) of diketopyrrolo-pyrrole pigment (D), diketopyrrolo-pyrrole sulfonic acid (E) and organic pigment is taken as 100 weight portions, the use level of organic pigment sulfonic acid (C) is the 3-7 weight portion, and the use level of graft polymer (B) is the 30-45 weight portion.
12. according to the red-colouring corrosion-resisting stamp-pad ink of claim 7 or 9 records, feature is that diketopyrrolo-pyrrole pigment (D) is that specific surface area is 90m
2The micronize pigment that/g is above.
13. manufacture method according to the red-colouring corrosion-resisting stamp-pad ink of record in the claim 1～6, feature is with surface treatment diketopyrrolo-pyrrole pigment (A), with graft polymer (B) is that spreading agent disperses to form pigment dispersion, so makes it disperse to make in photosensitive resin composition again.
14. manufacture method according to the red-colouring corrosion-resisting stamp-pad ink of record in the claim 7～12, feature is with diketopyrrolo-pyrrole pigment (D) and diketopyrrolo-pyrrole sulfonic acid (E), with graft polymer (B) is that spreading agent disperses to form pigment dispersion, so makes it disperse to make in photosensitive resin composition again.
15. pigment dispersion according to claim 13 or 14 records.
16. make the color filter that forms of the red-colouring corrosion-resisting stamp-pad ink putting down in writing among the claim 1-12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52985/2000 | 2000-02-29 | ||
| JP2000052985A JP4476417B2 (en) | 2000-02-29 | 2000-02-29 | Red color resist ink and color filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1312475A CN1312475A (en) | 2001-09-12 |
| CN1210619C true CN1210619C (en) | 2005-07-13 |
Family
ID=18574429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011172347A Expired - Fee Related CN1210619C (en) | 2000-02-29 | 2001-02-28 | Red-colouring corrosion-resisting stamp-pad ink and pigment optical filter |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4476417B2 (en) |
| KR (1) | KR100731468B1 (en) |
| CN (1) | CN1210619C (en) |
| TW (1) | TW588215B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004010838A (en) * | 2002-06-10 | 2004-01-15 | Nippon Steel Chem Co Ltd | Pigment dispersion, color resist ink and color filter |
| JP4407175B2 (en) * | 2003-06-30 | 2010-02-03 | 東洋インキ製造株式会社 | Pigment dispersion and use thereof |
| JP2006206626A (en) * | 2005-01-25 | 2006-08-10 | Toray Ind Inc | Water-based pigment dispersion and ink composition using the same |
| JP4668801B2 (en) * | 2005-02-22 | 2011-04-13 | 大日精化工業株式会社 | Pigment dispersant and use thereof |
| KR100921149B1 (en) * | 2005-03-30 | 2009-10-12 | 신닛테츠가가쿠 가부시키가이샤 | Photosensitive resin composition and circuit substrate employing the same |
| CN102974264B (en) * | 2005-04-13 | 2015-09-02 | 路博润高级材料公司 | dispersant |
| US7763672B2 (en) | 2005-07-01 | 2010-07-27 | Toyo Ink Mfg. Co., Ltd. | Red colored film, red colored composition, color filter and liquid crystal display device |
| JP5239143B2 (en) * | 2006-09-29 | 2013-07-17 | 大日本印刷株式会社 | Manufacturing method of color filter and manufacturing method of liquid crystal display device |
| JP5291893B2 (en) * | 2007-05-08 | 2013-09-18 | 太陽ホールディングス株式会社 | Photocurable resin composition and cured product thereof |
| JP5059499B2 (en) * | 2007-06-29 | 2012-10-24 | 協立化学産業株式会社 | Method for forming positive pattern on substrate and composition for forming negative pattern used in the method |
| JP5268394B2 (en) * | 2008-03-11 | 2013-08-21 | 富士フイルム株式会社 | Pigment composition, ink composition, printed matter, inkjet recording method, and polyallylamine derivative |
| JP5662034B2 (en) * | 2010-02-12 | 2015-01-28 | サカタインクス株式会社 | Red pigment dispersion for color filter, method for producing the same, and pigment dispersion resist composition for color filter containing the same |
| JP5659761B2 (en) * | 2010-12-13 | 2015-01-28 | 大日本印刷株式会社 | Red pigment dispersion for color filter, red photosensitive resin composition for color filter, color filter, and liquid crystal display device |
| JP6179075B2 (en) * | 2011-09-02 | 2017-08-16 | 大日本印刷株式会社 | Red pigment dispersion for color filter and production method thereof, red photosensitive resin composition for color filter and production method thereof, color filter, liquid crystal display device and organic light emitting display device |
| JP2013238859A (en) * | 2013-06-10 | 2013-11-28 | Nippon Steel & Sumikin Chemical Co Ltd | Ink composition for inkjet color filter superior in storage stability, and cured film of inkjet color filter and color filter obtained by using ink composition |
| JP6463018B2 (en) * | 2014-07-11 | 2019-01-30 | 日鉄ケミカル＆マテリアル株式会社 | Method for producing photosensitive resin composition for color filter and photosensitive resin composition for color filter |
| JP2017032748A (en) * | 2015-07-31 | 2017-02-09 | 桂 入交 | Coloring radiation-sensitive composition for color filter of solid imaging device |
| JP6392725B2 (en) * | 2015-10-05 | 2018-09-19 | 大日精化工業株式会社 | Pigment dispersant, pigment composition, and pigment colorant |
| JP6532410B2 (en) * | 2016-01-12 | 2019-06-19 | 大日精化工業株式会社 | Pigment additive, pigment composition, and pigment colorant |
| JP6977712B2 (en) * | 2016-03-31 | 2021-12-08 | Dic株式会社 | Polyarylene sulfide composition, its production method and coating film |
| KR102165470B1 (en) | 2017-10-27 | 2020-10-14 | 다이니치 세이카 고교 가부시키가이샤 | Pigment dispersant, pigment composition and pigment colorant |
| JP7025939B2 (en) * | 2018-01-23 | 2022-02-25 | サカタインクス株式会社 | Pigment dispersion composition for color filter and resist composition for color filter |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ187714A (en) * | 1977-07-15 | 1980-09-12 | Ici Ltd | Dispersing agent reaction product of a polyalkylene imine and a polyester |
| JP3313897B2 (en) * | 1994-08-01 | 2002-08-12 | ダイセル化学工業株式会社 | Pigment dispersant |
| JP3718915B2 (en) * | 1995-10-16 | 2005-11-24 | 味の素株式会社 | Pigment dispersant |
| JPH11217514A (en) * | 1998-02-03 | 1999-08-10 | Toray Ind Inc | Red paste for color filter, and color filter using the same, liquid crystal display device |
| JP4021057B2 (en) * | 1998-06-30 | 2007-12-12 | 新日鐵化学株式会社 | Red color resist ink |
-
2000
- 2000-02-29 JP JP2000052985A patent/JP4476417B2/en not_active Expired - Fee Related
-
2001
- 2001-02-15 TW TW90103465A patent/TW588215B/en not_active IP Right Cessation
- 2001-02-28 CN CNB011172347A patent/CN1210619C/en not_active Expired - Fee Related
- 2001-02-28 KR KR20010010314A patent/KR100731468B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR100731468B1 (en) | 2007-06-21 |
| JP4476417B2 (en) | 2010-06-09 |
| KR20010085706A (en) | 2001-09-07 |
| CN1312475A (en) | 2001-09-12 |
| JP2001240780A (en) | 2001-09-04 |
| TW588215B (en) | 2004-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1210619C (en) | Red-colouring corrosion-resisting stamp-pad ink and pigment optical filter | |
| CN1279374C (en) | Colored composition, method of manufacturing color filter, and method of manufacturing black matrix substrate | |
| TWI445769B (en) | Pigment dispersion composition, colored photocurable composition, and color filter and method for manufacturing the same | |
| CN1495236A (en) | Ink composition for UV curing ink-jet recording | |
| KR101018324B1 (en) | Pigment composition for color filters, manufacturing method and color filter | |
| US20090007820A1 (en) | Processed Pigment and Use Thereof | |
| CN1928714A (en) | Black photosensitive resin composition | |
| JPH09176511A (en) | Pigment dispersion composition and color resist ink | |
| CN1077908C (en) | Pigment dispersing agent, pigment dispersing liquid and pigment dispersing liquid for colour filter | |
| CN1993429A (en) | Pigment | |
| CN1934196A (en) | Violet colorant for colour filters, inks for ink-jet, electrophotographic toners and developers and e-inks | |
| CN1854202A (en) | Pigment dispersants and their use | |
| JP2009227839A (en) | Pigment dispersion composition, photocurable composition, color filter, liquid crystal display and solid image sensor | |
| JP4489196B2 (en) | Red color resist ink | |
| CN1900172A (en) | Organic pigments for colour filters | |
| TWI395797B (en) | Pixel-forming colorant compositions and their use | |
| JPWO2007142293A1 (en) | Red coloring composition for color filter | |
| CN1975471A (en) | Black composition and its production method | |
| CN1118522C (en) | Process for preparing green pigment composition containing no halogen | |
| JP4021057B2 (en) | Red color resist ink | |
| CN1211672C (en) | Optical filter and manufacture thereof | |
| JP5180939B2 (en) | Red color resist ink and pigment dispersion | |
| CN1590468A (en) | Dispersants for organic pigments | |
| JP2009280741A (en) | Red pigment dispersion product and red pigment dispersing resist composition for color filter containing the same | |
| JP2016038463A (en) | Red colorant composition for color filter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: NIPPON STEEL + SUMITOMO METAL CORPORATION Free format text: FORMER NAME: NIPPON SEEL CHEMICAL CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: Nippon Steel Chemical Co. Address before: Tokyo, Japan Patentee before: Nippon Seel Chemical Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050713 Termination date: 20170228 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |