Compositions: coating or plastic – Materials or ingredients – Pigment – filler – or aggregate compositions – e.g. – stone,...
Reexamination Certificate
2000-02-02
2001-07-24
Huang, Evelyn Mei (Department: 1625)
Compositions: coating or plastic
Materials or ingredients
Pigment, filler, or aggregate compositions, e.g., stone,...
C106S497000, C544S125000, C544S300000, C544S361000, C546S049000, C546S056000, C546S057000
Reexamination Certificate
active
06264733
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel compounds which can direct and control the growth and/or crystal phase of pigment particles. Such compounds are particularly useful when present during the synthesis of the pigment.
BACKGROUND OF THE INVENTION
A number of patents describe processes for the direct synthesis of pigments in a pigmentary form to avoid the additional expensive and oftentimes environmentally unfriendly pigment finishing processes (e.g. processes for particle size reduction and/or crystal-form modification). For example European Patent No. 643,110 and U.S. Pat. No. 5,424,429 describe a direct synthesis of quinacridone solid solutions and 2,9-dichloroquinacridone in pigmentary form, respectively, in the presence of quinacridone phthalimidomethyl derivatives. European Patent No. 685,530 describes the preparation of a direct synthesis of pigmentary grade dioxazine in the presence of a dioxazine derivative.
It is also known that sulfonic acid derivatives of certain pigments can effectively diminish the crystal growth during the isolation of the pigment from a reaction mixture. Such sulfonic acid derivatives are described, for example, in U.S. Pat. No. 3,386,843. Other patents describe the use of sulfonic acid derivatives of pigments to stabilize against recrystallization and change of crystal modification as, for example, in G.B. Patent No. 1,544,839 which is directed to phthalocyanine pigments.
U.S. Pat. No. 5,755,873 describes a method for the preparation of quinacridone pigments in which a quinacridone derivative is incorporated during synthesis and copending provisional application Ser. No. 60/087,773 describes a direct synthesis of pigmentary diketopyrrolopyrrole pigments in the presence of quinacridone or diketopyrrolopyrrole derivatives.
Although the addition of such known pigment derivatives can be advantageous, pigment synthesis in the presence of such derivatives in many cases does not provide the favored pigmentary crystal size, shape or crystal modification. Therefore many pigments so synthesized may still require finishing steps to obtain pigments with the preferred color characteristics.
SUMMARY OF THE INVENTION
The present invention is based on the discovery that new selected pigment derivatives in which a specific aromatic or hetero aromatic group is linked by a methylene group to a pigment molecule are particularly effective for directing and controlling the growth and/or crystal modification of pigment particles when present during the pigment synthesis step.
Such pigment particle growth directors can be prepared by simple synthesis procedures and offer the pigment manufacturer a means to prepare a pigment providing the preferred color characteristic without requiring additional pigment finishing step. The inventive compounds allow the manufacturer to produce high performance organic pigments in an economical and environmentally friendly manner of producing high performance organic pigments and thus, are of extreme commercial importance.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
The present invention relates to novel compounds of formula I:
(MO
3
S)
m
—Q—[CH
2
—(X)—(Y)
n
]
o
(I)
wherein Q represents a pigment moiety, M represents a metal cation, quatemary N cation or H, X is a aromatic group or a cyclo hetero aliphatic group with at least one 5 or 6 atom ring or a hetero aromatic group with at least one 6 atom ring and which is not a phthalimido group, Y is a sulfonic acid or carboxylic acid or salt thereof, m and n independent of one another are numbers from zero to 2.5, and o is a number from 0.05 to 4. The present invention further relates to a process for the preparation and use of such compounds.
Generally, the pigment moiety Q is a pigment selected from the group of anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioindigo, iminoisoindoline, iminoisoindolinone, quinacridone, flavanthrone, dioxazine, indanthrone, anthrapyrimidine and quinophthalone pigments. Preferably, the pigment moiety Q is a quinacridone or diketo pyrrolo pyrrole pigment. Particularly preferably, the pigment moiety Q is a quinacridone of the general formula II:
wherein A and D are independently 1 or 2 substituents selected from H, F, Cl, C
1
-C
3
alkyl and C
1
-C
3
alkoxy. The pigment moiety Q is not a compound that produces colorless derivatives, such as derivatives of 6,13-dihydroquinacridones. Most preferably the pigment moiety Q is an unsubstituted quinacridone.
Preferably, m of formula I is a number from about zero to 0.5, most preferably zero to 0.1; n is a number from about zero to 2, most preferably from about zero to 1.2; and o is a number from about 0.1 to 2, most preferably from about 0.2 to 1.5. The values for m, n and o are determined by analytical methods like mass spectrometry such as LCMS, GCMS or the matrix-assisted laser desorption ionization technique (MALDI).
The metal cation M of formula I is preferably sodium, potassium, calcium, magnesium or aluminum. The quatemary N cation of formula 1 is an ammonium or an alkyl ammonium group.
Typically, the group X of formula I is an aromatic group with a 5 carbon or 6 carbon ring; or a polycyclic group containing two to six fused 5 carbon and/or 6 carbon rings; a cyclo-herto aliphatic group including at least one 5 atom or 6 atom ring; or a hetero aromatic group, which is not a phthalimido, and includes a 6 atom ring, fused 6 atom rings or fused 5 and 6 atom rings and in which there are 1 to 4 hetero atoms of N, S and/or O. Suitable aromatic groups include, for example, phenylene, naphthalene, acenaphthylene, anthracene, phenanthrene, naphthacene, chrysene, pyrene or perylene. Preferably the aromatic group is phenylene, naphthalene, anthracene or pyrene, and most preferably the aromatic group is phenylene or naphthalene.
Cyclo-hetero aliphatic groups are, for example, pyrrolidine, imidazolidine, piperidine, piperazine or morpholine.
Appropriate hetero aromatic groups are, for instance, pyridine, pyrazine, pyrimidine, pyridazine, indole, isoindole, quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone or benzothiazole, preferably pyridine or carbazole.
The above exemplified aromatic, cyclo hetero aliphatic or hetero aromatic groups can optionally be substituted with one or more halogen, oxy, hydroxy, imino, amino and/or C
1
-Cl
18
alkyl groups, preferably C
1
-C
3
alkyl or C
1
-C
3
alkoxy groups.
Examples of the large number of such substituted groups are for instance toluene, ortho-, meta- or para-xylene, chlorobenzene, 1- or 2-methylnaphthalene or anthraquinone, barbituric acid, melamine, 1,3,7-trimethylxanthin, hydantoin, 2-methylbenzimidazole, 2,6,8-trihydroxypurine, 1,8-naphtosultam, o-benzoic acid sulfimide or 2,4-dihydroxyprimidine.
Preferred aromatic groups are toluene, ortho-, meta- or para-xylene, chlorobenzene, 1- or 2-methylnaphthalene or anthraquinone. Preferred hetero aromatic groups are melamine, 1,3,7-trimethylxanthin, hydantoin, 2-methylbenzimidazole, 2,6,8-trihydroxypurine, 1,8-naphtosultam, o-benzoic acid sulfimide or 2,4-dihydroxyprimidine.
Commonly the group Y is a carboxylic acid or a sulfonic acid group. Most preferably the group Y is a free sulfonic acid or a sodium, potassium, magnesium, calcium or aluminum salt thereof.
A further embodiment of the present invention is a process for the preparation of compounds of formula I or II, wherein: a) the pigment of the pigment moiety Q is dissolved in concentrated sulfuric acid; b) the intermediate X is added into the solution and dissolved at a temperature below 50° C.; c) para-formaldehyde is added at a temperature below 50° C.; d) and then is heated to a temperature from to 50 to 100° C.; e) and then isolated.
The inventive compounds are prepared for example by a process in which the pigment moiety Q and the intermediate X, a substantial portion of which is the moiety of group X, are reacted with formaldehyde. Preferably the reaction is carried out in concentrated (95-98%) sulfuric acid. In one preferred method, the pigment of the pigment moiety Q is dis
Ciba Specialty Chemicals Corporation
Crichton David R.
Huang Evelyn Mei
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