CA2052704A1 - Anthraquinones containing long-chain acylamino groups and use thereof - Google Patents
Anthraquinones containing long-chain acylamino groups and use thereofInfo
- Publication number
- CA2052704A1 CA2052704A1 CA002052704A CA2052704A CA2052704A1 CA 2052704 A1 CA2052704 A1 CA 2052704A1 CA 002052704 A CA002052704 A CA 002052704A CA 2052704 A CA2052704 A CA 2052704A CA 2052704 A1 CA2052704 A1 CA 2052704A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- plastics material
- material according
- radical
- compounds
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/516—N-acylated derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/36—Dyes with acylated amino groups
- C09B1/40—Dyes with acylated amino groups the acyl groups being residues of an aliphatic or araliphatic carboxylic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paper (AREA)
Abstract
Anthraquinones containing long-chain acylamino groups and use thereof Abstract of the Disclosure Anthraquinones containing long-chain acylamino groups of formula I or II
(I)
(I)
Description
205;~
Anthraquinones containing long-chain acylamino ~roups and use thereof The present invention relates to specific anthraquinones containing long-chain acylamino groups, to plastics materials which are mass coloured with such compounds, and to the use of said anthraquinones for the mass colouration of plastics materials.
Very stringent demands are made of compounds which are used for the mass colouration of plastics materials. Thus they must have good dispersibility in the plastics material to be coloured, but they may not exhibit a tendency to migrate. Because of the very high processing temperatures of plastics materials (in practice often in the range from c.
250-300C), such compounds must additionally have high heat stability. Depending on their use, the coloured products must also have good fastness to light and weathering.
Certain anthraquinone derivatives containing long-chain acylamino substituents for mass colouring plastics materials are disclosed in US 3 899 504, GB 1 338 886, DF-A 2 132 394 and DE-A 2 123 963. These compounds do not, however, in all respects meet current requirements regarding dispersibility, transparency, heat stability and fastness properties.
It has now been found that specific anthraquinone pigments containing long-chainacylamino groups have all these desired properties for the mass colouration of plastics materials, and that the products coloured therewith have very good fastness properties.
Specifically, the invention relates to plastics materials which are mass coloured with an anthraquinone containing long-chain acylamino groups of formula I or II
(I), ~X~Br)m (Il), O NHR~ Rg O R8 20~70~
Anthraquinones containing long-chain acylamino ~roups and use thereof The present invention relates to specific anthraquinones containing long-chain acylamino groups, to plastics materials which are mass coloured with such compounds, and to the use of said anthraquinones for the mass colouration of plastics materials.
Very stringent demands are made of compounds which are used for the mass colouration of plastics materials. Thus they must have good dispersibility in the plastics material to be coloured, but they may not exhibit a tendency to migrate. Because of the very high processing temperatures of plastics materials (in practice often in the range from c.
250-300C), such compounds must additionally have high heat stability. Depending on their use, the coloured products must also have good fastness to light and weathering.
Certain anthraquinone derivatives containing long-chain acylamino substituents for mass colouring plastics materials are disclosed in US 3 899 504, GB 1 338 886, DF-A 2 132 394 and DE-A 2 123 963. These compounds do not, however, in all respects meet current requirements regarding dispersibility, transparency, heat stability and fastness properties.
It has now been found that specific anthraquinone pigments containing long-chainacylamino groups have all these desired properties for the mass colouration of plastics materials, and that the products coloured therewith have very good fastness properties.
Specifically, the invention relates to plastics materials which are mass coloured with an anthraquinone containing long-chain acylamino groups of formula I or II
(I), ~X~Br)m (Il), O NHR~ Rg O R8 20~70~
wherein R is a radical R2 or R3, and R2 is C10-C3salkyl or C1O-C3salkenyl, and R3 is a radical of formula III
Rc (III) wherein R4 is a radical -NHR2, -N(R2~2, -OR2 or -SR2, Rs and R6 are each independently of the other H, Cl-C4alkyl, Cl-C4alkoxy, halogen or nitro, and n is 0, 1 or 2, Rl is Cl-Csalkyl or a radical of formula IV
~CH2 ~ (IV), and wherein, in formula II, two of R7, R8, R9 and Rlo are -OH and the other two are -NHCOR, R is as defined for formula I and l and m are each independently of the other 0, 1 or 2.
Individual further anthraquinones which also contain, inter alia, long-chain acylamino substituents have also been disclosed, but they are used exclusively for other utilities.
Thus DE-OS 3 240 036 discloses 1,4-bis(acylamino)anthraquinones and the use thereof as liquid crystals. In US 4 614 804 there are disclosed 8-amino-1-acylamino-4,5-dihydroxy-anthraquinones which are used in dyebaths for dyeing cellulosic fabrics. Specific 1-amino-4-alkylaminoanthraquinones (containing 1-6 carbon atoms in the alkyl moiety) which contain branched and in some cases long-chain substituents in 2-position, and the use thereof as dyes for dyeing synthetic fibres with dye solutions, are disclosed in US 3 963 763.
Specific anthraquinone derivatives of formula I above (compounds wherein R = Cl-Cl7alkyl), are disclosed in GB 1 271 040, where it is said that they are suitable for use as dyes in a process for the continuous dyeing of synthetic fibre materials by impregnating said materials with dye solutions in water-immiscible organic solvents. The synthetic fibre materials may be used in the form of woven and knitted fabrics, especially 2~5;~7 polyesters, polyamides, polyurethanes or polyolefins.
The compounds of forrnula I of this invention in which R is Cl8-C35alkyl or Cl8-C3s-alkenyl, or in which R has the same meaning as R3, and the compounds of formula II, are novel. The invention therefore further relates to anthraquinones containing long-chain acylamino groups of formula Ia or II
~COR11 (B~Br)m(II), O NHRl Rg R8 wherein Rll is a radical Rl2 or has the meaning of R3, and Rl2 is Cl8-C3salkyl or Cl8-C3s-alkenyl, and R1, R3, R7 to R1o and I and m are as de~lned above.
Where R is a radical R2, the C10-C3salkyl or C1O-C35alkenyl radicals may be straight-chain or branched. Typical suitable alkyl or alkenyl radicals are n-decyl, n-undecyl, n-dodecyl, n-tridecyl, iso~idecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, l-methylpentadecyl, n-octadecyl, n-icosyl, n-tetracosyl, n-hexacosyl, n-triacontyl, 8-heptadecenyl and 8-pentadecenyl. The same applies to the R2 groups of the substituents R4 of the radicals of formula III.
R2 is preferably straight chain. A preferred meaning of R2 is C1O-C20alkyl, most preferably Cll-Cl8alkyl.
Where R is a radical R3 of formula III, n is preferably 0, R4 is preferably a radical -OR2, and Rs and R6 are each independently of the other preferably fluoro, chloro or bromo, Cl-C3alkyl such as methyl, ethyl, propyl or isopropyl, Cl-C3alkoxy and, preferably, H.
Particularly preferred are radicals of formula III, wherein R5 and R6 are ~I and the substituent R4 is in para-position.
Cl-CsAlkyl radicals Rl may be straight-chain or branched and are, typically, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or isopentyl. R1 is preferably methyl or ethyl or, preferably, a radical of formula IV, wherein n is O and Rs and R6 are - 4 - 205~
each independently of the other fluoro, chloro or bromo, Cl-C3alkyl, Cl-C3alkoxy and, preferably, H.
Among the compounds of formula II, those compounds are especially preferred wherein R8 and Rto are -OH and R7 and Rg are -NHCOR, and particularly those wherein R is p-decanoxyphenyl, heptadecyl or undecyl. The sum of 1~ m is preferably not greater than 2, and is more particularly 1 or, most preferably, 0.
Among the compounds of formula I, R is preferably p-octadecanoxyphenyl, undecyl,pentadecyl or heptadecyl, and R1 is preferably phenyl.
The most preferred compounds are the compound of formula I, wherein R is heptadecyl and Rl is phenyl, and the compound of formula II, wherein R8 and R1o are -OH and R7 and Rg are -NHCOC17H3s.
The compounds of formulae I and II can be prepared by methods analogous to knownones, for example by reacting the corresponding amino-substituted anthraquinones of formula V or VI
(V), ~B~)m(VI), O NHR~ R~5 R~4 wherein R1, 1 and m are as def1ned above, and two of R13, R14, R1s and R16 are -OH and the other two are -NH2, with an acid halide of formula VII
XCOR (VII), wherein R has the given meaning and X is halogen, such as bromo or, preferably, chloro.
The compounds of formulae V, VI and VII are known or they can be prepared in known manner. Some are also commercially available.
The reaction of the compounds of formula V or VI with the compound of formula VII is conveniently carAed out in the presence of an organic inert solvent under normal or elevated pressure, with or without a catalyst. Suitable solvents are, typically, toluene, xylene, chlorobenzene, dichlorobenzenes such as o-dichlorobenzene, and also trichloro-benzenes, nitrobenzene, or mixtures of aromatic and/or aliphatic solvents such as ~)Shellsols. The preferred solvent is chlorobenzene.
The products are isolated after their synthesis in conventional manner, for example by filtration. The filter product is washed, for example, with one of the above mentioned solvents and then, if appropriate, conveniently with methanol or water. The products are obtained in good yield and purity and can in principle be used, even without further purification, in finely particulate form for the mass coloration of plastics materials.
If the compounds of this invention are still not of optimum or sufficient purity and/or particle form and size for use as pigments, they can be further conditioned. By conditioning is meant the preparation of a fine particle size and form best suited to the application, for example by dry milling with or without salt, by solvent or aqueous milling or by salt-kneading, or by a subsequent hot solvent treatment.
Hot solvent treatments can be carried out, for example, in organic solvents, preferably those which have a boiling point above 100C. Particularly suitable solvents for this aftertreatment are halobenzenes, alkylbenzenes or nitrobenzenes, for exarnple toluene, chlorobenzene, o-dichlorobenzene, xylenes or nitrobenzene; alcohols such as isopropanol or isobutanol; and also ketones such as cyclohexanone; ethers such as ethylene glycol monomethyl or monoethyl ether; amides such as dimethyl formamide or N-methyl-pyrrolidone; as well as dimethyl sulfoxide, sulfolane or water by itself, under normal or elevated pressure. The aftertreatment can also be carried out in water in the presence of organic solvents and/or with the addition of surface-active substances or aliphatic amines, or m llquld ammoma.
Depending on the conditioning method andlor end use, it may be convenient to add speci-fic amounts of texture improvers to the compounds of formula I or II before or after the conditioning. Preferred texture improvers are, typically, fatty acids containing not less than 18 carbon atoms, for example stearic acid or behenic acid or the amides or metal salts thereof, preferably magnesium salts. The texture improvers are preferably added in amounts of 0.1-30 % by weight, most preferably of 2-15 % by weight, based on the final product.
2~5~0 Owing ~o their excellent compatibility, the compounds of formula I or II obtained in this invention can often be used for colouring plastics materials by direct incorporation therein without further conditioning.
Although the anthraquinone derivatives of this invention are especially suitable for the mass coloration of polyolefins, they can also be used advantageously for colouring other polymers, for example polyvinyl chloride, fluorinated polymers such as polyfluorethylene, polytrifluorochloroethylene or tetrafluoroethylene/hexafluoropropylene copolymer, but preferably for engineering plastics such as polycarbonates, polyacrylates, polymeth-acrylates, ABS, polyesters, especially polyalkyleneterephthalates such as polybutylene-terephthalate (PBT) or polyethyleneterephthalate (PET), polyamides, polyether ketones, polyurethanes, singly or in mixtures. They are conveniently used in a concentration of 0.01 to 10 % by weight, preferably 0.01 to 5 % by weight, based on the polymer.
Exemplary of polyolefins which can be coloured with the compounds of formula I or II are high and low density polyethylene (HD-PE, LD-PE and LLD-PE), polypropylene and polyisobutylene, and also copolymers of polyolefins with, for example, polyethers, poly-ether ketones or polyurethanes. Polypropylene is preferred.
Coloration is effected by conventional methods, for example by blending a compound of formula I or II, or with a mixture of such compounds, with the plastics material in granular or powder form without first having to incorporate it in a preparation, and then extruding the blend to fibres, sheets or granular formulations. These last mentioned formulations can then be shaped to objects by injection moulding.
The blue to violet colourations obtained are of great clarity and excellent saturation and have good transparency as well as good fastness properties, especially heat stability and lightfastness. It must be particularly emphasised that the anthraquinone derivatives of this invention exhibit very good migration resistance and lightfastness in spite of their excellent dispersibility and the transparency of the colourations obtained with them. A
particular advantage of the polyethylene objects coloured with the compounds of formula I
or II is that - especially in the case of high density polyethylene - they exhibit no increased tendency to warping and deforrnation.
2~5;~70q~
The fibres, especially the polypropylene fibres, coloured with the compounds of formulae I and II are brilliant and have excellent textile properties such as lightfastness and fastness to washing and solvents. The use of compounds of formula I or II is also associated with a number of technical advantages, for example very easy dispersibility, few fibre ruptures, insignificant clogging of the spinnerets, and reduced filtration dmes.
The invention is illustrated by the following Examples.
Example 1: 25.6 g of R-COCI are added to a suspension of 6.8 g of 1,5-diamino-4,8-dihy-droxyanthraquinone in 200 ml of chlorobenzene. The suspension is heated to 125C, stirred for 16 hours at this temperature, allowed to cool, and filtered. The filter product is washed with methanol. The dry filter product is then extracted with dichloromethane for 2 1/2 days in a Soxhlet extractor. The residue in the jacket is slurried in methanol and the slurry is filtered. The filter product is washed with a small amount of dichloromethane and then with methanol and dried in a vacuum drier, giving 13.9 g (55 % of theory) of the compound of formula H O
OH O N--C--R
¢X~ R= ~3O-C~8H37 R--C--N O OH
Il I
O H
as a violet product.
Analysis for C64H90N28 C H N
calcd: 75.7 8.93 2.76 found: 75.5 9.08 2.67 205~70~
Examples 2 and 3: The procedure of Example 1 is repeated, except that the acid chloride of formula R-COCI is replaced with the equivalent amount of an acid chloride of formula Y-COCI, where Y has the meaning given in the following Table. Corresponding compounds of the formula given below are obtained by boiling the moist filter cake in methanol instead of using the Soxhlet method.
The results are summarised in the Table.
.
o OH O HN--C--Y
Y-C~CI~
Il o ~x~mple Y Yield ShadoAnalysis 5to calcd:74.77 9.79 3.49 2 C17H3s - 89 % violet found: 74.99 10.03 3.38 calcd: 71.89 8.57 4.41 3 CIIH7~- 88 % iiole~ found: 72.16 8.91 4.21 ExamDle 4: 24.5 g of R-COCI are added to a suspension of 12.6 g of 1-amino-4-anilinoanthraquinone in 150 ml of chlorobenzene. The suspension is heated to 125C, stirred for 17 hours at this temperature, allowed to cool and filtered. The filter product is washed briefly with cold chlorobenzene and dissolved in dichloromethane.
After addition of methanol (precipitation), the batch is refluxed for 1 hour, cooled and ltered. The filter product is washed once more with methanol and dried in a vacuum drier, giving 21 g (76 % of theory) of the compound of formula 2C~5;~7~qL
H O
O N--C--R
R ' ~}O-C~3H37 O N~
H \=/
as a violet product.
Analysis for C4sHs4N2o4 C H N
calcd: 78.68 7.92 4.08 found: 78.75 7.91 3.82 Examples 5-7: The procedure of Example 4 is repeated, except that the acid chloride of formula R-COCI is replaced with the equivalent amount of an acid chloride of formula Y-COCI, where Y has the meaning given in the following Table. In addition, the reaction mixture is concentrated to dryness, the residue is taken up in methanol and the batch is refluxed and only then is the product isolated by filtration. Recrystallisation as in Example 1 gives corresponding compounds of the formula below. The results are summarised in the Table.
O HN--C--Y
~3 O NHPh ;21D5~
Exatttple Yield ShadeAnalysis qo calcd: 77.39 7.31 5.64 CllH23 60 % violetfound: 77.22 7.04 5.62 calcd: 78.22 8.02 5.07 6 C1sH31 77 % violetfound: 78.10 7.93 4.81 calcd: 78.58 8.33 4.82 7 Cl7H3s 46% violetfound: 79.02 8.05 4.92 Example 8: 1 g of the pigment of Example 7 and 1000 g of polyethyl~ne terephthalate (PET, ~Melinor B90, ex ICI) are mixed for 15 minutes and the mixture is pred~ied for 4 hours at 90C. The mixture is extruded twice at 270C, then granulated and dried once more for 4 hours at 90C. The coloured granular formulation so obtained is injection moulded to sheets at 270C, 280C and 290C after 5 minutes dwell time at these temperatures to give violet colourations of good resistance to heat and light.
Example 9: 400 g of polypropylene granules ((~)DAPLEN PT-55, ex Chemie LINZ) and4 g of the pigment obtained in Example 1 are thoroughly mixed in a mixing drum. The granular formulation so obtained is melt spun at 260-280C to violet coloured filaments of very good textile properties such as light- and wetfastness.
Example 10: 4.16 g of stearyl chloride in 5 ml of xylene are added dropwise at 100C over 10 minutes to a suspension of 1.25 g of 1,5-diamino-bromo-4,8-dihydroxyanthraquinone in 15 ml of xylene. The suspension is heated to 125C, stirred for 16 hours at this temperature, cooled and filtered. The residue is washed with methanol and dried. The solid is then dissolved in chloroform at room temperature and crystallised by addition of methanol and by cooling. The solid is isolated by filtration and dried, giving 2.3 g (82 %) of the compound -11- 2~5~
Ho o H~C00~7H3s C,7H3sCONH O OH
as a violet powder.
Rc (III) wherein R4 is a radical -NHR2, -N(R2~2, -OR2 or -SR2, Rs and R6 are each independently of the other H, Cl-C4alkyl, Cl-C4alkoxy, halogen or nitro, and n is 0, 1 or 2, Rl is Cl-Csalkyl or a radical of formula IV
~CH2 ~ (IV), and wherein, in formula II, two of R7, R8, R9 and Rlo are -OH and the other two are -NHCOR, R is as defined for formula I and l and m are each independently of the other 0, 1 or 2.
Individual further anthraquinones which also contain, inter alia, long-chain acylamino substituents have also been disclosed, but they are used exclusively for other utilities.
Thus DE-OS 3 240 036 discloses 1,4-bis(acylamino)anthraquinones and the use thereof as liquid crystals. In US 4 614 804 there are disclosed 8-amino-1-acylamino-4,5-dihydroxy-anthraquinones which are used in dyebaths for dyeing cellulosic fabrics. Specific 1-amino-4-alkylaminoanthraquinones (containing 1-6 carbon atoms in the alkyl moiety) which contain branched and in some cases long-chain substituents in 2-position, and the use thereof as dyes for dyeing synthetic fibres with dye solutions, are disclosed in US 3 963 763.
Specific anthraquinone derivatives of formula I above (compounds wherein R = Cl-Cl7alkyl), are disclosed in GB 1 271 040, where it is said that they are suitable for use as dyes in a process for the continuous dyeing of synthetic fibre materials by impregnating said materials with dye solutions in water-immiscible organic solvents. The synthetic fibre materials may be used in the form of woven and knitted fabrics, especially 2~5;~7 polyesters, polyamides, polyurethanes or polyolefins.
The compounds of forrnula I of this invention in which R is Cl8-C35alkyl or Cl8-C3s-alkenyl, or in which R has the same meaning as R3, and the compounds of formula II, are novel. The invention therefore further relates to anthraquinones containing long-chain acylamino groups of formula Ia or II
~COR11 (B~Br)m(II), O NHRl Rg R8 wherein Rll is a radical Rl2 or has the meaning of R3, and Rl2 is Cl8-C3salkyl or Cl8-C3s-alkenyl, and R1, R3, R7 to R1o and I and m are as de~lned above.
Where R is a radical R2, the C10-C3salkyl or C1O-C35alkenyl radicals may be straight-chain or branched. Typical suitable alkyl or alkenyl radicals are n-decyl, n-undecyl, n-dodecyl, n-tridecyl, iso~idecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, l-methylpentadecyl, n-octadecyl, n-icosyl, n-tetracosyl, n-hexacosyl, n-triacontyl, 8-heptadecenyl and 8-pentadecenyl. The same applies to the R2 groups of the substituents R4 of the radicals of formula III.
R2 is preferably straight chain. A preferred meaning of R2 is C1O-C20alkyl, most preferably Cll-Cl8alkyl.
Where R is a radical R3 of formula III, n is preferably 0, R4 is preferably a radical -OR2, and Rs and R6 are each independently of the other preferably fluoro, chloro or bromo, Cl-C3alkyl such as methyl, ethyl, propyl or isopropyl, Cl-C3alkoxy and, preferably, H.
Particularly preferred are radicals of formula III, wherein R5 and R6 are ~I and the substituent R4 is in para-position.
Cl-CsAlkyl radicals Rl may be straight-chain or branched and are, typically, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl or isopentyl. R1 is preferably methyl or ethyl or, preferably, a radical of formula IV, wherein n is O and Rs and R6 are - 4 - 205~
each independently of the other fluoro, chloro or bromo, Cl-C3alkyl, Cl-C3alkoxy and, preferably, H.
Among the compounds of formula II, those compounds are especially preferred wherein R8 and Rto are -OH and R7 and Rg are -NHCOR, and particularly those wherein R is p-decanoxyphenyl, heptadecyl or undecyl. The sum of 1~ m is preferably not greater than 2, and is more particularly 1 or, most preferably, 0.
Among the compounds of formula I, R is preferably p-octadecanoxyphenyl, undecyl,pentadecyl or heptadecyl, and R1 is preferably phenyl.
The most preferred compounds are the compound of formula I, wherein R is heptadecyl and Rl is phenyl, and the compound of formula II, wherein R8 and R1o are -OH and R7 and Rg are -NHCOC17H3s.
The compounds of formulae I and II can be prepared by methods analogous to knownones, for example by reacting the corresponding amino-substituted anthraquinones of formula V or VI
(V), ~B~)m(VI), O NHR~ R~5 R~4 wherein R1, 1 and m are as def1ned above, and two of R13, R14, R1s and R16 are -OH and the other two are -NH2, with an acid halide of formula VII
XCOR (VII), wherein R has the given meaning and X is halogen, such as bromo or, preferably, chloro.
The compounds of formulae V, VI and VII are known or they can be prepared in known manner. Some are also commercially available.
The reaction of the compounds of formula V or VI with the compound of formula VII is conveniently carAed out in the presence of an organic inert solvent under normal or elevated pressure, with or without a catalyst. Suitable solvents are, typically, toluene, xylene, chlorobenzene, dichlorobenzenes such as o-dichlorobenzene, and also trichloro-benzenes, nitrobenzene, or mixtures of aromatic and/or aliphatic solvents such as ~)Shellsols. The preferred solvent is chlorobenzene.
The products are isolated after their synthesis in conventional manner, for example by filtration. The filter product is washed, for example, with one of the above mentioned solvents and then, if appropriate, conveniently with methanol or water. The products are obtained in good yield and purity and can in principle be used, even without further purification, in finely particulate form for the mass coloration of plastics materials.
If the compounds of this invention are still not of optimum or sufficient purity and/or particle form and size for use as pigments, they can be further conditioned. By conditioning is meant the preparation of a fine particle size and form best suited to the application, for example by dry milling with or without salt, by solvent or aqueous milling or by salt-kneading, or by a subsequent hot solvent treatment.
Hot solvent treatments can be carried out, for example, in organic solvents, preferably those which have a boiling point above 100C. Particularly suitable solvents for this aftertreatment are halobenzenes, alkylbenzenes or nitrobenzenes, for exarnple toluene, chlorobenzene, o-dichlorobenzene, xylenes or nitrobenzene; alcohols such as isopropanol or isobutanol; and also ketones such as cyclohexanone; ethers such as ethylene glycol monomethyl or monoethyl ether; amides such as dimethyl formamide or N-methyl-pyrrolidone; as well as dimethyl sulfoxide, sulfolane or water by itself, under normal or elevated pressure. The aftertreatment can also be carried out in water in the presence of organic solvents and/or with the addition of surface-active substances or aliphatic amines, or m llquld ammoma.
Depending on the conditioning method andlor end use, it may be convenient to add speci-fic amounts of texture improvers to the compounds of formula I or II before or after the conditioning. Preferred texture improvers are, typically, fatty acids containing not less than 18 carbon atoms, for example stearic acid or behenic acid or the amides or metal salts thereof, preferably magnesium salts. The texture improvers are preferably added in amounts of 0.1-30 % by weight, most preferably of 2-15 % by weight, based on the final product.
2~5~0 Owing ~o their excellent compatibility, the compounds of formula I or II obtained in this invention can often be used for colouring plastics materials by direct incorporation therein without further conditioning.
Although the anthraquinone derivatives of this invention are especially suitable for the mass coloration of polyolefins, they can also be used advantageously for colouring other polymers, for example polyvinyl chloride, fluorinated polymers such as polyfluorethylene, polytrifluorochloroethylene or tetrafluoroethylene/hexafluoropropylene copolymer, but preferably for engineering plastics such as polycarbonates, polyacrylates, polymeth-acrylates, ABS, polyesters, especially polyalkyleneterephthalates such as polybutylene-terephthalate (PBT) or polyethyleneterephthalate (PET), polyamides, polyether ketones, polyurethanes, singly or in mixtures. They are conveniently used in a concentration of 0.01 to 10 % by weight, preferably 0.01 to 5 % by weight, based on the polymer.
Exemplary of polyolefins which can be coloured with the compounds of formula I or II are high and low density polyethylene (HD-PE, LD-PE and LLD-PE), polypropylene and polyisobutylene, and also copolymers of polyolefins with, for example, polyethers, poly-ether ketones or polyurethanes. Polypropylene is preferred.
Coloration is effected by conventional methods, for example by blending a compound of formula I or II, or with a mixture of such compounds, with the plastics material in granular or powder form without first having to incorporate it in a preparation, and then extruding the blend to fibres, sheets or granular formulations. These last mentioned formulations can then be shaped to objects by injection moulding.
The blue to violet colourations obtained are of great clarity and excellent saturation and have good transparency as well as good fastness properties, especially heat stability and lightfastness. It must be particularly emphasised that the anthraquinone derivatives of this invention exhibit very good migration resistance and lightfastness in spite of their excellent dispersibility and the transparency of the colourations obtained with them. A
particular advantage of the polyethylene objects coloured with the compounds of formula I
or II is that - especially in the case of high density polyethylene - they exhibit no increased tendency to warping and deforrnation.
2~5;~70q~
The fibres, especially the polypropylene fibres, coloured with the compounds of formulae I and II are brilliant and have excellent textile properties such as lightfastness and fastness to washing and solvents. The use of compounds of formula I or II is also associated with a number of technical advantages, for example very easy dispersibility, few fibre ruptures, insignificant clogging of the spinnerets, and reduced filtration dmes.
The invention is illustrated by the following Examples.
Example 1: 25.6 g of R-COCI are added to a suspension of 6.8 g of 1,5-diamino-4,8-dihy-droxyanthraquinone in 200 ml of chlorobenzene. The suspension is heated to 125C, stirred for 16 hours at this temperature, allowed to cool, and filtered. The filter product is washed with methanol. The dry filter product is then extracted with dichloromethane for 2 1/2 days in a Soxhlet extractor. The residue in the jacket is slurried in methanol and the slurry is filtered. The filter product is washed with a small amount of dichloromethane and then with methanol and dried in a vacuum drier, giving 13.9 g (55 % of theory) of the compound of formula H O
OH O N--C--R
¢X~ R= ~3O-C~8H37 R--C--N O OH
Il I
O H
as a violet product.
Analysis for C64H90N28 C H N
calcd: 75.7 8.93 2.76 found: 75.5 9.08 2.67 205~70~
Examples 2 and 3: The procedure of Example 1 is repeated, except that the acid chloride of formula R-COCI is replaced with the equivalent amount of an acid chloride of formula Y-COCI, where Y has the meaning given in the following Table. Corresponding compounds of the formula given below are obtained by boiling the moist filter cake in methanol instead of using the Soxhlet method.
The results are summarised in the Table.
.
o OH O HN--C--Y
Y-C~CI~
Il o ~x~mple Y Yield ShadoAnalysis 5to calcd:74.77 9.79 3.49 2 C17H3s - 89 % violet found: 74.99 10.03 3.38 calcd: 71.89 8.57 4.41 3 CIIH7~- 88 % iiole~ found: 72.16 8.91 4.21 ExamDle 4: 24.5 g of R-COCI are added to a suspension of 12.6 g of 1-amino-4-anilinoanthraquinone in 150 ml of chlorobenzene. The suspension is heated to 125C, stirred for 17 hours at this temperature, allowed to cool and filtered. The filter product is washed briefly with cold chlorobenzene and dissolved in dichloromethane.
After addition of methanol (precipitation), the batch is refluxed for 1 hour, cooled and ltered. The filter product is washed once more with methanol and dried in a vacuum drier, giving 21 g (76 % of theory) of the compound of formula 2C~5;~7~qL
H O
O N--C--R
R ' ~}O-C~3H37 O N~
H \=/
as a violet product.
Analysis for C4sHs4N2o4 C H N
calcd: 78.68 7.92 4.08 found: 78.75 7.91 3.82 Examples 5-7: The procedure of Example 4 is repeated, except that the acid chloride of formula R-COCI is replaced with the equivalent amount of an acid chloride of formula Y-COCI, where Y has the meaning given in the following Table. In addition, the reaction mixture is concentrated to dryness, the residue is taken up in methanol and the batch is refluxed and only then is the product isolated by filtration. Recrystallisation as in Example 1 gives corresponding compounds of the formula below. The results are summarised in the Table.
O HN--C--Y
~3 O NHPh ;21D5~
Exatttple Yield ShadeAnalysis qo calcd: 77.39 7.31 5.64 CllH23 60 % violetfound: 77.22 7.04 5.62 calcd: 78.22 8.02 5.07 6 C1sH31 77 % violetfound: 78.10 7.93 4.81 calcd: 78.58 8.33 4.82 7 Cl7H3s 46% violetfound: 79.02 8.05 4.92 Example 8: 1 g of the pigment of Example 7 and 1000 g of polyethyl~ne terephthalate (PET, ~Melinor B90, ex ICI) are mixed for 15 minutes and the mixture is pred~ied for 4 hours at 90C. The mixture is extruded twice at 270C, then granulated and dried once more for 4 hours at 90C. The coloured granular formulation so obtained is injection moulded to sheets at 270C, 280C and 290C after 5 minutes dwell time at these temperatures to give violet colourations of good resistance to heat and light.
Example 9: 400 g of polypropylene granules ((~)DAPLEN PT-55, ex Chemie LINZ) and4 g of the pigment obtained in Example 1 are thoroughly mixed in a mixing drum. The granular formulation so obtained is melt spun at 260-280C to violet coloured filaments of very good textile properties such as light- and wetfastness.
Example 10: 4.16 g of stearyl chloride in 5 ml of xylene are added dropwise at 100C over 10 minutes to a suspension of 1.25 g of 1,5-diamino-bromo-4,8-dihydroxyanthraquinone in 15 ml of xylene. The suspension is heated to 125C, stirred for 16 hours at this temperature, cooled and filtered. The residue is washed with methanol and dried. The solid is then dissolved in chloroform at room temperature and crystallised by addition of methanol and by cooling. The solid is isolated by filtration and dried, giving 2.3 g (82 %) of the compound -11- 2~5~
Ho o H~C00~7H3s C,7H3sCONH O OH
as a violet powder.
Claims (14)
1. A plastics material which is mass coloured with an anthraquinone which contains long-chain acylamino groups of formula I or II
(I) (II), wherein R is a radical R2 or R3, and R2 is C10-C35alkyl or C10-C35alkenyl, and R3 is a radical of formula III
(III) wherein R4 is a radical -NHR2, -N(R2)2, -OR2 or -SR2, R5 and R6 are each independently of the other H, C1-C4alkyl, C1-C4alkoxy, halogen or nitro, and n is 0, 1 or 2, R1 is C1-C5alkyl or a radical of formula IV
(IV), and wherein, in forrnula II, two of R7, R8, R9 and R10 are -OH and the other two are -NHCOR, R is as defined for formula I and l and m are each independently of the other 0, 1 or 2.
(I) (II), wherein R is a radical R2 or R3, and R2 is C10-C35alkyl or C10-C35alkenyl, and R3 is a radical of formula III
(III) wherein R4 is a radical -NHR2, -N(R2)2, -OR2 or -SR2, R5 and R6 are each independently of the other H, C1-C4alkyl, C1-C4alkoxy, halogen or nitro, and n is 0, 1 or 2, R1 is C1-C5alkyl or a radical of formula IV
(IV), and wherein, in forrnula II, two of R7, R8, R9 and R10 are -OH and the other two are -NHCOR, R is as defined for formula I and l and m are each independently of the other 0, 1 or 2.
2. A plastics material according to claim 1, wherein R2 is C10-C20alkyl.
3. A plastics material according to claim 1, wherein R2 is C11-C18-alkyl.
4. A plastics material according to claim 1, wherein R3 is a radical of formula III in which n is 0, R4 is -OR2, and Rs and R6 are each independently of the other fluoro, chloro or bromo, C1-C3alkyl, C1-C3alkoxy or H.
5. A plastics material according to claim 4, wherein R5 and R6 are H.
6. A plastics material according to claim 1, wherein R1 is ethyl, methyl or, preferably, a radical of formula IV, wherein n is 0 and R5 and R6 are each independently of the other fluoro, chloro or bromo, C1-C3alkyl, C1-C3alkoxy or H.
7. A plastics material according to claim 6, wherein R5 and R6 are H.
8. A plastics material according to claim 1, wherein, in the radical of formula III, R5 and R6 are H and the substituent R4 is in para-position.
9. A plastics material according to claim 1, wherein R8 and R10 are -OH and R7 and R9 are -NHCOR.
10. A plastics material according to claim 1 containing the compound of formula I, wherein R is heptadecyl and R1 is phenyl, or the compound of formula II, wherein R8 and R10 are -OH and R7 and R9 are -NHCOC17H35.
11. A plastics material according to claim 1 which is a polyolefin.
12. A plastics material according to claim 11 which is polypropylene.
13. A plastics material according to claim 1 containing 0.01 to 10 % by weight, based on the polymer, of a compound of formula I or II.
14. An anthraquinone containing long-chain acylamino groups of formula Ia or II
(Ia), (II), wherein R11 is a radical R12 or has the meaning of R3, and R12 is C18-C35alkyl or C18-C35-alkenyl, and R1, R3, R7 to R10 and 1 and m are as defined in claim 1.
FD 4.3/SZ/cw*
(Ia), (II), wherein R11 is a radical R12 or has the meaning of R3, and R12 is C18-C35alkyl or C18-C35-alkenyl, and R1, R3, R7 to R10 and 1 and m are as defined in claim 1.
FD 4.3/SZ/cw*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH321790 | 1990-10-05 | ||
| CH3217/90-3 | 1990-10-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2052704A1 true CA2052704A1 (en) | 1992-04-06 |
Family
ID=4251183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002052704A Abandoned CA2052704A1 (en) | 1990-10-05 | 1991-10-03 | Anthraquinones containing long-chain acylamino groups and use thereof |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0479728B1 (en) |
| JP (1) | JPH04261442A (en) |
| KR (1) | KR100187312B1 (en) |
| CA (1) | CA2052704A1 (en) |
| DE (1) | DE59104677D1 (en) |
| TW (1) | TW211023B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1907783C3 (en) * | 1969-02-15 | 1978-03-02 | Bayer Ag, 5090 Leverkusen | Anthraquinone dyes and their uses |
| DE1928131C3 (en) * | 1969-06-03 | 1975-09-11 | Bayer Ag, 5090 Leverkusen | Anthraquinone dyes, their manufacture and use |
| BE757188A (en) * | 1969-10-07 | 1971-03-16 | Bayer Ag | CONTINUOUS DYEING PROCESS OF SYNTHETIC FIBROUS MATERIALS |
-
1991
- 1991-09-19 KR KR1019910016399A patent/KR100187312B1/en not_active IP Right Cessation
- 1991-09-26 EP EP91810756A patent/EP0479728B1/en not_active Expired - Lifetime
- 1991-09-26 DE DE59104677T patent/DE59104677D1/en not_active Expired - Fee Related
- 1991-10-02 TW TW080107776A patent/TW211023B/zh active
- 1991-10-03 CA CA002052704A patent/CA2052704A1/en not_active Abandoned
- 1991-10-04 JP JP3256837A patent/JPH04261442A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0479728A1 (en) | 1992-04-08 |
| KR100187312B1 (en) | 1999-05-15 |
| TW211023B (en) | 1993-08-11 |
| EP0479728B1 (en) | 1995-02-22 |
| KR920008151A (en) | 1992-05-27 |
| DE59104677D1 (en) | 1995-03-30 |
| JPH04261442A (en) | 1992-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5244476A (en) | Benzophenone ether esters, processes for their preparation, and their use for improving the light stability of polyester dyeings | |
| JPH07173406A (en) | New diketopyrrolopyrrole and colorant | |
| CA2428957A1 (en) | Process for the preparation of n,n'-disubstituted 1,4-diaminoanthraquinones | |
| CA2397894A1 (en) | Preparation of 1-amino-4-hydroxyanthraquinones | |
| US4176113A (en) | Process for dyeing polyesters in the melt | |
| CA2052704A1 (en) | Anthraquinones containing long-chain acylamino groups and use thereof | |
| US4126626A (en) | 1-nitroarylamino-5 or 8-phenoxy or phenylmercapto anthraquinone | |
| US5238984A (en) | Dianthraquinonyl compounds | |
| US4264326A (en) | New disperse dyestuffs; their preparation and their applications to the coloration of synthetic materials | |
| US4077960A (en) | Imido-quinoline dyes | |
| US4150025A (en) | Novel quinoline derivatives | |
| CA2430606C (en) | Dyeing or printing of manufactured natural polymer and synthetic hydrophobic fibre materials | |
| US4211688A (en) | Process for dyeing high-molecular organic material in the melt | |
| US3923454A (en) | Polyester and plastic dyes | |
| US3272821A (en) | Delta form of quinacridone pigment | |
| KR20030064845A (en) | Anthraquinone dyes, preparation thereof and use thereof | |
| US3992421A (en) | 6-Anilino-1,4,5-trihydroxyanthraquinones | |
| US3975410A (en) | Process for the manufacture of halogen-containing anthraquinoidal compounds, their use and new halogen-containing anthraquinoidal compounds | |
| KR0152266B1 (en) | Dianthraquinonyl compounds | |
| US4801406A (en) | Dicyanobenzanthrone compounds | |
| JPS5922749B2 (en) | New disperse dye | |
| TW575639B (en) | Preparation of styryl dyes | |
| US4750228A (en) | Disperse dyes | |
| JPH02131455A (en) | Monoazocompound containing long chain alkyl group | |
| US4082778A (en) | Arylaminoanthraquinones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |