CN101955689A - Triarylmethane class and rhodamine class color compositions and the pigment dispersion that uses this color compositions - Google Patents

Triarylmethane class and rhodamine class color compositions and the pigment dispersion that uses this color compositions Download PDF

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CN101955689A
CN101955689A CN2010102335073A CN201010233507A CN101955689A CN 101955689 A CN101955689 A CN 101955689A CN 2010102335073 A CN2010102335073 A CN 2010102335073A CN 201010233507 A CN201010233507 A CN 201010233507A CN 101955689 A CN101955689 A CN 101955689A
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pigment
chemical formula
color compositions
untreated
dispersion
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CN101955689B (en
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菅野敏彦
谷原润一
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Sanyo Color Works Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02Disazo dyes
    • C09B35/039Disazo dyes characterised by the tetrazo component
    • C09B35/205Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene
    • C09B35/21Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene of diarylmethane or triarylmethane
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D498/00Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00Diaryl- or thriarylmethane dyes
    • C09B11/28Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B63/00Lakes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing 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
    • C09B67/006Preparation of organic pigments

Abstract

The object of the present invention is to provide the pigment lake with triarylmethane structure and/or rhodamine structure of a kind of photostabilization and excellent heat resistance and the pigment dispersion that has used this pigment lake.For this reason, the invention provides a kind of color compositions, it is characterized in that, utilize the organic acid that is selected from replacement or unsubstituted aryl sulfonic acid and replacement or unsubstituted aryl carboxylic acid that the pigment that is untreated that is selected from the pigment lake with triarylmethane structure and/or rhodamine structure is handled.

Description

Triarylmethane class and rhodamine class color compositions and the pigment dispersion that uses this color compositions
Technical field
The present invention relates to triarylmethane class and rhodamine class color compositions, particularly, the pigment dispersion that the present invention relates to the triarylmethane class of photostabilization and excellent heat resistance and rhodamine class color compositions and used these color compositions.
Background technology
All the time, triarylmethane class dye well pigment has obtained application (patent documentation 1~4) at toning agent, spray printing with fields such as printing ink, colour filters.
But, to compare with phthalocyanine pigment etc., there is the defective of thermotolerance, photostabilization difference in triarylmethane class dye well pigment.For this reason, existing about overcoming the trial of this defective.For example, attempted developing the colour filter (patent documentation 5) that uses the polymkeric substance that contains triphenhlmethane dye.In addition, (patent documentations 6) such as use triarylmethane and organic acid salt have also been attempted.
The prior art document:
Patent documentation 1: Japanese kokai publication sho 61-006659 communique
Patent documentation 2: Japanese kokai publication sho 61-036758 communique
Patent documentation 3: international disclosing No. 2002/100959
Patent documentation 4: Japanese kokai publication hei 11-223720 communique
Patent documentation 5: TOHKEMY 2000-162429 communique
Patent documentation 6: TOHKEMY 2006-306933 communique
Summary of the invention
The problem that invention will solve
But practical situation are that the photostabilization of triarylmethane class pigment and the thermotolerance of above-mentioned acquisition is still not enough, and its manufacturing process is also comparatively complicated, still can't realize practicability at present.
Based on this, the object of the present invention is to provide the triarylmethane class color compositions of photostabilization and excellent heat resistance and use the pigment dispersion of this color compositions and the rhodamine class color compositions of photostabilization and excellent heat resistance and use the pigment dispersion of this color compositions.
The method of dealing with problems
The present invention is based on following discovery and finish: the sulfonic acid or the carboxylic acid that have aryl by utilization are handled pigment lake with triarylmethane structure and the pigment lake with rhodamine structure, and the photostabilization of pigment and thermotolerance are largely increased.
Promptly, color compositions of the present invention is characterised in that, utilization is selected from and replaces or the organic acid or the following pigment that is untreated of its salt pair of unsubstituted aryl sulfonic acid and replacement or unsubstituted aryl carboxylic acid are handled, and the described pigment that is untreated is selected from the pigment lake of the rhodamine structure with triarylmethane structure that Chemical formula 1 represents and/or chemical formula 3 expressions.
[Chemical formula 1]
In Chemical formula 1, R 1, R 2, R 3, R 4Independently of one another representative-H ,-CH 3,-C 2H 5,-Ph (phenyl) ,-PhCH 3,-CH 2Ph (SO 31/2Ba) or-CH 2Ph (SO 31/2Al), R is replacement shown in the Chemical formula 2 or unsubstituted phenyl or naphthyl,
[Chemical formula 2]
In Chemical formula 2, R 5Representative-H ,-NHCH 3,-N (CH 3) 2,-N (C 2H 5) 2,-NHPh or-NHPh (CH 3) (SO 3H) or its salt, R 6Representative-H ,-Cl or-SO 3H or its salt, R 7For-NHC 2H 5,
[chemical formula 3]
In chemical formula 3, R 8, R 9, R 10, R 11Representative-H or alkyl independently of one another, R 12Be-H, alkyl or replacement or unsubstituted phenyl.
Pigment dispersion of the present invention is by using above-mentioned color compositions to carry out the pigment dispersion that dispersion treatment obtains.
In addition, pigment dispersion of the present invention can also by be selected from replace or the organic acid of unsubstituted aryl sulfonic acid and replacement or unsubstituted aryl carboxylic acid in the presence of the pigment that is untreated that is selected from the pigment lake with rhodamine structure that triarylmethane structure that Chemical formula 1 represents and/or chemical formula 3 represent carried out dispersion treatment obtain.
The effect of invention
By utilizing aryl sulfonic acid or aryl carboxylic acid triarylmethane class of the present invention and rhodamine class color compositions are handled, so that some change of state takes place in the pigment particles surface, re-use this color compositions and prepare pigment dispersion, when utilizing this dispersion for example to make colour filter, can obtain filming of photostabilization and excellent heat resistance.
Embodiment
The triarylmethane class pigment that uses among the present invention is the ionic pigment lake with the chemical structural formula shown in the above-mentioned formula 1, particularly, can enumerate the C.I. pigment blue 1, C.I. pigment blue 1: 2, C.I. Pigment blue 9, C.I. pigment blue 14, C.I. Pigment blue 24, C.I. pigment violet 3, C.I. pigment violet 3: 1, C.I. pigment violet 3: 3, C.I. pigment violet 27, C.I. pigment violet 39, C.I. Pigment blue 78, C.I. Pigment green 1, C.I. Pigment green 2, C.I. Pigment green 4, C.I. Pigment blue 56, C.I. Pigment blue 56:1, C.I. pigment Blue-61, C.I. pigment Blue-61: 1, C.I. color lake pigment such as Pigment blue 62.
In addition, the rhodamine class pigment that uses among the present invention is the ionic pigment lake with the chemical mechanism formula shown in the above-mentioned chemical formula 3, particularly, can enumerate pigment violet 1, pigment violet 1: 1, pigment violet 2, pigment violet 2:2, pigment violet 81, pigment red 81: 1, pigment red 81: 2, pigment red 81: 3, pigment red 81: 4, color lake pigment such as Pigment red 169, Pigment red 173.
As the color lake agent in triarylmethane class pigment and/or the rhodamine class pigment, can enumerate phospho-wolframic acid, phospho-molybdic acid, phosphotungstomolybdic acid, copper ferrocyanide, silicomolybdic acid, aluminium.
In the present invention, being used for to the organic acid that triarylmethane class pigment and/or rhodamine class pigment are handled is to replace or unsubstituted aryl sulfonic acid and/or replacement or unsubstituted aryl carboxylic acid.Wherein, described replacement or unsubstituted aryl sulfonic acid are meant, contain the sulfonic acid that has substituting group or do not have substituent aryl; Described replacement or unsubstituted aryl carboxylic acid are meant, contain the carboxylic acid that has substituting group or do not have substituent aryl.As replacing or unsubstituted aryl sulfonic acid, can enumerate alkyl benzene sulphonate (ABS)s such as Phenylsulfonic acid, naphthene sulfonic acid, toluene sulfonic acide, acid dimethyl, alkyl naphthalene sulfonic acid, dialkyl group naphthene sulfonic acid etc., in addition, also can be that pyridine-sulfonic acid etc. contains the heterocyclic aryl sulfonic acid.In addition, above-mentioned aryl sulfonic acid also all can be replaced by amino, hydroxyl, can also be the salt of sodium, calcium, potassium etc.As these sour concrete examples, can enumerate the 2-sodium naphthalene sulfonate shown in the chemical formula 4,2-naphthene sulfonic acid hydrate, 3-(2H-benzotriazole-2-yl)-5-sec-butyl-4-DHBS, sodium p styrene sulfonate, 3-methyl isophthalic acid-(4-sulfophenyl)-5-pyrazolone etc.As replacing or unsubstituted aryl carboxylic acid, it can be the naphthalene-2 shown in phenylformic acid, phthalic acid, trimellitic acid, naphthoic acid, the chemical formula 4, naphthalic acids such as 3-dioctyl phthalate), in addition, can also be the salt of the sodium, calcium, potassium etc. of substituted carboxylic acids such as tolyl acid, mesitylenic acid, Whitfield's ointment (hydroxy-benzoic acid), phthalonic acid (2-(carboxyl carbonyl) phenylformic acid), hydroxynaphthoic acid and above-mentioned carboxylic acid.
[chemical formula 4]
Figure BSA00000203846300051
" processing " that utilizes aryl sulfonic acid and/or aryl carboxylic acid to carry out among the present invention, be included in the processing of the above-mentioned acid of surface applied of the above-mentioned pigment that is untreated, typically " processing " be meant, the above-mentioned pigment that is untreated is put in the solution of aryl sulfonic acid and/or aryl carboxylic acid, under assigned temperature, stir after the fixed time, filter pigment to implement separation.In the sulfonic acid at this moment and/or the solution of carboxylic acid, preferably be added with acid such as acetate, citric acid, formic acid, oxalic acid in advance.By adding these acid, can make the cationic moiety activation of surface of pigments, thereby promote the absorption of sulfonic acid, so that pigment-dispersing is improved.Preferred concentration when adding acetate is more than the 0.5 quality % and does not make the scope of pigment dissolved.In addition, the temperature range of above-mentioned processing is preferably 60~100 ℃.
Dispersion of the present invention is following color compositions to be dispersed in the solvent and the dispersion that obtains, and described color compositions is with aryl sulfonic acid and/or aryl carboxylic acid triarylmethane class pigment and/or rhodamine class pigment to be handled the resulting color compositions in back.As dispersing method, can enumerate the method for for example using coating modulator (paint conditioner), sand mill, apex mill, dispersion machine (dispermat).
In addition, in the present invention, can also when disperseing triarylmethane class pigment and/or rhodamine class pigment, utilize the processing of aryl sulfonic acid and/or aryl carboxylic acid.At this moment, with respect to the 100 mass parts pigment that is untreated, the addition of aryl sulfonic acid and/or aryl carboxylic acid is 1~20 mass parts, preferred 5~20 mass parts.Concrete dispersing method is identical with the dispersing method of above-mentioned color compositions.
When preparing color compositions of the present invention and pigment dispersion, can also be to wherein adding tensio-active agent.By the interpolation tensio-active agent, thereby can make SURFACTANT ADSORPTION improve dispersing of pigments in surface of pigments.As the tensio-active agent that can use in the present invention, can enumerate sulfonic acid class tensio-active agents such as naphthalene sulfonic acidformaldehyde condensation product, lignin sulfonic acid.
As the solvent that can in pigment dispersion of the present invention, use, so long as the conventional solvent that uses can not have particular restriction, but because the photostabilization of known pigment is better than dyestuff usually, thereby consider that from thermotolerance, photostabilization aspect preferred use does not make the solvent of pigment dissolved.
Embodiment
Below, the present invention will be described in conjunction with specific embodiments, but the present invention is not limited to following record.It is pointed out that is not having under the situation of specified otherwise, and described " part " in this specification sheets reaches " % " and represents " mass parts ", " quality % " respectively.
(embodiment 1)
As shown in table 1, in 250 parts of 2.5% acetic acid aqueous solutions, add 10 parts of untreated C.I. pigment blue 1s and 1 part of 2-sodium naphthalene sulfonate, utilize dispersion machine fully to stir after, be warming up to 80 ℃ and stirred 2 hours.Filter the gained slurry, after precipitation is washed,, thereby obtained 9.9 parts of the color compositions of target in 80 ℃ of dried overnight.
(BYK 170 with 5 parts of this color compositions, 36.7 parts of propylene glycol methyl ether acetates and high score subclass dispersion agent, the manufacturing of BYK Chemie Japan company) 8.3 parts of zirconium oxide beads together with φ 0.5mm add in lacquer (lacquer) bottle, after disperseing 1 hour with the coating modulator, add acrylic resin (SPC-2000, clear and polymer (strain)) 0.2 part, obtained blue pigment dispersion.
(embodiment 2~11)
Use each composition shown in the table 1, obtained the blue pigment dispersion of embodiment 2~11 according to the method identical with embodiment 1.It is pointed out that in embodiment 9 and 10, tensio-active agent is added in the acetic acid aqueous solution for 1 part together with C.I. pigment blue 1 and 2-sodium naphthalene sulfonate.
(comparative example 1~2)
The pigment that is untreated shown in the direct use table 1, and with 36.7 parts of propylene glycol methyl ether acetates and high score subclass dispersion agent (BYK 170, the manufacturing of BYK Chemie Japan company) 8.3 parts of zirconium oxide beads together with φ 0.5mm add in the lacquer bottle, after disperseing 1 hour with the coating modulator, add acrylic resin (SPC-2000, clear and polymer (strain)) 0.2 part, obtained blue pigment dispersion.
Figure BSA00000203846300071
(evaluation)
[the test making of glass coated plate]
Utilize spinner that pigment dispersion is coated on the square square glass plate of 10cm, make test glass coated plate thus.
[stable on heating evaluation]
The glass coated plate is statically placed in the air bath (air bath) that is warming up to 200 ℃, kept 1 hour.Utilize colorimeter (CM3700D, KONIKA MINOLTA makes) that the aberration (Δ Eab) that drops into air bath front and back glass coated plate is measured.Coated plate with the dispersion of comparative example 1 and 2 is put into them in the air bath simultaneously as standard test specimen, and when being standard with its aberration (1.00), the aberration of each glass coated plate is as shown in table 1 with respect to the ratio of this standard aberration.
[sunproof evaluation]
Use light fastness test machine (XL75 type low temperature xenon arc lamp weather resistance test machine, Suga Test), under the xenon lamp of 180W, expose 24 hours.Utilize colorimeter (CM3700D, KONIKA MINOLTA makes) that the aberration (Δ Eab) of glass coated plate before and after exposing is measured.Coated plate with the dispersion enumerated in comparative example 1 and 2 is put into them in the air bath simultaneously as standard test specimen, and when being standard with its aberration (1.00), the aberration of each glass coated plate is as shown in table 1 with respect to the ratio of this standard aberration.
[evaluation result]
In thermotolerance and sunproof test subject, the ratio of the aberration (Δ Eab) of the test usefulness glass coated plate that the dispersion of use embodiment 1~11 is made is all less than 1, as seen, compare with each comparative example that does not utilize organic acid to handle, the coated plate of embodiment 1~11 has excellent thermotolerance and photostabilization.
(embodiment 12~13)
As shown in table 2, with 4.65 parts of untreated C.I. pigment blue 1s, 0.35 part of 2-sodium naphthalene sulfonate, 36.7 parts of propylene glycol methyl ether acetates, (BYK 170 for 8.3 parts of high score subclass dispersion agents, BYK Chemie Japan company makes) and the zirconium oxide bead of φ 0.5mm add in the lacquer bottle, after disperseing 1 hour with the coating modulator, add acrylic resin (SPC-2000, clear and polymer (strain)) 0.2 part, obtained blue pigment dispersion.
(comparative example 3~4)
As shown in table 2, except having used untreated pigment, do not used the organic acid, obtained blue pigment dispersion according to the method identical with embodiment 12~13.
(comparative example 5)
Stirring and dissolving 5.0g Blue 7 in 250g water has been prepared the aqueous solution of Blue 7.In addition, in 200g water,, prepared the naphthene sulfonic acid aqueous solution in 200 ℃ of stirring and dissolving 2.5g sodium naphthalene sulfonates.Under 50 ℃ of stirrings, the above-mentioned naphthene sulfonic acid aqueous solution is slowly added in the aqueous solution of above-mentioned Blue 7, continue to stir 2 hours, to precipitate filter, dry, pulverize, thereby obtained color compositions.
[table 2]
Figure BSA00000203846300091
*1), *2) ... with identical in the table 1
(evaluation)
Make test according to method same as described above and used the glass coated plate, and utilized method same as described above to carry out thermotolerance and light fastness test.Its result is as shown in table 2.
[evaluation result]
In thermotolerance and sunproof test subject, the ratio of the aberration (Δ Eab) of the test usefulness glass coated plate that the dispersion of use embodiment 12~13 is made is all less than 1, as seen, compare with each comparative example that does not utilize organic acid to handle, the coated plate of embodiment 12~13 has excellent thermotolerance and photostabilization.
Industrial applicibility
When using triarylmethane class of the present invention and rhodamine class pigment and having used the dispersion of these pigment, can obtain to have excellent heat resistance and sunproof filming, therefore, not only can use it for the fields such as colour filter such as liquid crystal indicator, colour filter, OLED display, can also use with ink area at toner, spray printing.

Claims (11)

1. color compositions, it is characterized in that, utilization is selected from the organic acid or the following pigment that is untreated of its salt pair of replacement or unsubstituted aryl sulfonic acid and replacement or unsubstituted aryl carboxylic acid and handles, the described pigment that is untreated is selected from the pigment lake of the rhodamine structure with triarylmethane structure that Chemical formula 1 represents and/or chemical formula 3 expressions
[Chemical formula 1]
Figure FSA00000203846200011
In Chemical formula 1, R 1, R 2, R 3, R 4Independently of one another representative-H ,-CH 3,-C 2H 5,-Ph ,-PhCH 3,-CH 2Ph (SO 31/2Ba) or-CH 2Ph (SO 31/2Al), R is replacement shown in the Chemical formula 2 or unsubstituted phenyl or naphthyl,
[Chemical formula 2]
Figure FSA00000203846200012
In Chemical formula 2, R 5Representative-H ,-NHCH 3,-N (CH 3) 2,-N (C 2H 5) 2,-NHPh or-NHPh (CH 3) (SO 3H) or its salt, R 6Representative-H ,-Cl or-SO 3H or its salt, R 7For-NHC 2H 5,
[chemical formula 3]
Figure FSA00000203846200021
In chemical formula 3, R 8, R 9, R 10, R 11Representative-H or alkyl independently of one another, R 12Be-H, alkyl or replacement or unsubstituted phenyl.
2. color compositions according to claim 1, wherein, the described pigment that is untreated is the C.I. pigment blue 1.
3. color compositions according to claim 1, wherein, the described pigment that is untreated is the C.I. pigment violet 1.
4. according to each described color compositions in the claim 1~3, wherein, described organic acid is selected from the compound shown in the chemical formula 4,
[chemical formula 4]
Figure FSA00000203846200022
5. according to each described color compositions in the claim 1~4, wherein also contain tensio-active agent.
6. a pigment dispersion has wherein used each described color compositions in the claim 1~5.
7. pigment dispersion, its be selected from replace or the organic acid of unsubstituted aryl sulfonic acid and replacement or unsubstituted aryl carboxylic acid in the presence of the following pigment that is untreated is carried out dispersion treatment and the pigment dispersion that obtains, the described pigment that is untreated is selected from the pigment lake with rhodamine structure that triarylmethane structure that Chemical formula 1 represents and/or chemical formula 3 represent.
8. pigment dispersion according to claim 7, wherein, the described pigment that is untreated is the C.I. pigment blue 1.
9. pigment dispersion according to claim 7, wherein, the described pigment that is untreated is the C.I. pigment violet 1.
10. according to each described pigment dispersion in the claim 7~9, wherein, described organic acid is selected from the compound shown in the chemical formula 4.
11. according to each described pigment dispersion in the claim 7~11, wherein, described dispersion treatment is carried out in the presence of described organic acid and tensio-active agent.
CN201010233507.3A 2009-07-17 2010-07-19 Pigment composition of triarylmethane and rhodamine, and pigment dispersion using same Active CN101955689B (en)

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