VAN BOHEMEN ROEDOLPH (NL)
PIRRUNG FRANK OLIVER HEINRICH (DE)
ENGELBRECHT LOTHAR ALEXANDER (NL)
VAN BOHEMEN ROEDOLPH (NL)
PIRRUNG FRANK OLIVER HEINRICH (DE)
| US2449956A | 1948-09-21 | |||
| US20010000253A1 | 2001-04-12 | |||
| US5952402A | 1999-09-14 | |||
| US4775729A | 1988-10-04 |
Claims:
1. Pigmented tinting concentrates comprising a) stabilized pigments; b) humectant compounds obtainable by effecting a Diels Alder reaction at a temperature of 150-260 0 C between a polyunsaturated compound and a co-reactant having the formula R 1 XOC-CH=CH-COXR 2 or CH 2 =CH-COXR 3 or CH 2 =CH(CH 3 )-COXR 3 wherein X is oxygen or -NH- and wherein at least one of Ri and R 2 is a polyether moiety and any other of Riand R 2 is a polyether moiety or hydrogen and R 3 is a polyether moiety.
2. Pigmented tinting concentrates according to claim 1 , wherein the polyunsaturated compound is sorbic acid (2,4 hexadiene acid), β-lonone (2,6,6, trimethylcyclohexenyl-buten- 2-one), myrcene (7-methyl-3-methylen-1,6-octadien).
3. Pigmented tinting concentrates according to claim 1 , wherein the polyunsaturated compound is a polyunsaturated oil or a transesterificated oil obtained therefrom.
4. Pigmented tinting concentrates according to claim 3, wherein the polyunsaturated oil is tung oil or oiticica oil or transesterificated tung oil or oiticica oil.
5. Pigmented tinting concentrates according to claim 1, wherein the humectant compound is a compound of the formula I
Y is -CH 2 -, when a, b and c are 1 ; and
Y is CrC 2O alkyl or a polyether moiety when a is 1 and b and c are zero; R 4 is
X is oxygen or -NH-;
R 5 and R 6 are hydrogen or R 4 or polyunsaturated fatty acid moieties; at least one of Ri and R 2 is a polyether moiety and any other of Riand R 2 is a polyether moiety or hydrogen;
R 3 is a polyether moiety,
R 7 is hydrogen or methyl;
W -(CH 2 V or -(CH 2 ) p -CO-(CH 2 ) q -; n is O to 20, preferably 4 to 10; m is (2n-2) to 2n; p is 1 to 20, preferably 4 to 10; p' is 1 to 20; preferably 2 to 4; q is 1 to 20, preferably 4 to 10.
6. The use as humectant of a compound obtainable as described in claim 1 by effecting a Diels Alder reaction at a temperature of 150-260 0 C between a polyunsaturated compound and a co-reactant having the formula RiXOC-CH=CH-COXR 2 or CH 2 =CH-COXR 3 or CH 2 =CH(CH 3 )-COXR 3 wherein X is oxygen or -NH- and wherein at least one of Ri and R 2 is a polyether moiety and any other of Riand R 2 is a polyether moiety or hydrogen and R 3 is a polyether moiety.
7. The use of a compound of the formula I as defined in claim 5 as humectant. |
New humectant
The invention relates to humectants for aqueous based pigmented tinting concentrates.
Aqueous based pigmented tinting concentrates are used in a variety of industrial applications such as the manufacture of printing ink, paint, pulp and paper, coatings, and textiles to provide coloration.
Aqueous based pigmented tinting concentrates contain humectants to reduce or eliminate nozzle clogging due to drying at the front end of nozzles. However, humectants significantly reduce the drying rate of paints tinted with the pigment concentrates.
Current commercially available aqueous tinting concentrates contain ethylene glycol as humectant which performs well as a humectant in aqueous tinter concentrates, but it is moderately volatile having a vapour pressure substantially above 1.3Pa at 25°C. Like all volatile organic liquids, ethylene glycol now attracts environmental disapproval.
Furthermore, ethylene glycol humectants have negative effects on gloss levels in humid atmosphere.
An object of the present invention is therefore to provide Volatile Organic Compound (VOC) free organic and inorganic pigmented tinting concentrates which have no negative effects on gloss levels.
It has been found that polyethers functionalized with Diels Alder reaction products provide a VOC-free humectants.
Thus, the invention relates to pigmented tinting concentrates comprising a) stabilized pigments; b) humectant compounds obtainable by effecting a Diels Alder reaction at a temperature of 150-260°C between a polyunsaturated compound and a co-reactant having the formula R 1 XOC-CH=CH-COXR 2 or CH 2 =CH-COXR 3 or CH 2 =CH(CH 3 )-COXR 3 wherein X is oxygen or -NH- and wherein at least one of Ri and R 2 is a polyether moiety and any other of Riand R 2 is a polyether moiety or hydrogen and R 3 is a polyether moiety.
Compounds of the formula R 1 XOC-CH=CH-COXR 2 may be prepared by opening maleic acid anhydride a hydroxy-functional polyether.
Polyunsaturated compounds are, for example, sorbic acid (2,4 hexadiene acid), β-lonone (2,6,6, trimethylcyclohexenyl-buten-2-one), myrcene (7-methyl-3-methylen-1 ,6-octadien) or preferably polyunsaturated oils.
Polyunsaturated oils are preferably drying oils including, for example, tung oil, oiticica oil, de- hydrated castor oil, perilla oil, linseed oil, polymerized linseed oil soybean oil, sunflower oil, safflower oil, cotton seed oil, tall oil, fish oil and so forth as well as transesterificated oils obtained therefrom.
Transesterification is preferably carried out using a CrC 2 oalkyl alcohol, preferably methanol or a polyether or a polyether amine (jeffamine).
The drying oils from which the above adducts are derived contain fatty acids such as, e.g., 9,11,13 octadecatriene acid (eleostearic acid) or 4-oxo-9, 11 , 13 octadecatriene acid (licanic acid, oiticica oil) or esters thereof.
Fatty acids having more than 2 double bonds are preferred.
Thus, preferred are humectant compounds of the formula I
Y is -CH 2 -, when a, b and c are 1 ; and
Y is CrC 2O alkyl or a polyether moiety when a is 1 and b and c are zero; R 4 is
C Vni MHmm--OCUH
X is oxygen or -NH-;
R 5 and R 6 are hydrogen or R 4 or polyunsaturated fatty acid moieties; at least one of Ri and R 2 is a polyether moiety and any other of Riand R 2 is a polyether moiety or hydrogen;
R 3 is a polyether moiety, R 7 is hydrogen or methyl; W -(CH 2 V or -(CH 2 ) p -CO-(CH 2 ) q -; n is 0 to 20, preferably 4 to 10; m is (2n-2) to 2n; p is 1 to 20, preferably 4 to 10; p' is 1 to 20; preferably 2 to 4; q is 1 to 20, preferably 4 to 10.
The term polyether moiety denotes a moiety derived from the transesterification of the polyunsaturated oil using a polyether or a polyether amine.
The term polyether denotes a macromolecule containing a plurality of ether groups and having a hydroxy end group, for example HO-CH 2 CH 2 -(O-CH 2 CH 2 )y-OR or HO-CH 2 CH 2 CH 2 -(O-CH 2 CH 2 CH 2 )y-OR or HO-CH 2 CH(CH 3 )-(O-CH 2 CH(CH 3 ))y-OR or mixed EO/PO-polyethers; wherein y is generally 0 to 22, preferably 3 to 22, most preferably 3 to 13, and R is alkyl, preferably CrC 6 alkyl; most preferably methyl or ethyl.
The term polyether amine denotes a macromolecule containing a plurality of ether groups and having an amine end group, for example H 2 N-CH 2 CH 2 -(O-CH 2 CH 2 )y-OR or H 2 N-CH 2 CH 2 CH 2 -(O-CH 2 CH 2 CH 2 )y-OR or H 2 N-CH 2 CH(CH 3 )-(O-CH 2 CH(CH 3 ))yOR or mixed EO/PO-polyether amines wherein y is generally 0 to 22, preferably 3 to 22, most preferably 3 to 13, and R is alkyl, preferably d-C 6 alkyl; most preferably methyl or ethyl.
The pigment may be both organic and inorganic pigments such as phthalocyanines, azo- pigments, quinacridones or carbon blacks, titanium dioxides and iron oxides. The weight percentage of pigment in a tinter for example varies from 10 to 75 wt% depending on the strength of tinter required. Where a tinter is deliberately required to have a low strength (for
example where only slightly off-white shades are wanted) there may be an insufficient number of pigment particles to enable the dispersing agent to generate enough structure. In such circumstances, it is usual to add extra neutral solid particles to the tinter and these neutral particles are often referred to as "extender" particles. For the purposes of this invention, any necessary extender particles will be considered to be pigment particles. Typical extenders include clays, chalks, talcs, barytes and silicas.
The pigment is stabilized using for example fatty acid modified emulsifiers such as, for example, EFKA 6225, EFKA 6220 or EFKA 6230 or dispersants such as EFKA 5071 , EFKA 4550, EFKA 4570, EFKA 4580 and the like.
The humectants according to the invention are particularly suitable for the production of pigment concentrates. For this purpose, the compounds according to the invention are introduced into water, and the pigments to be dispersed are added with stirring. In addition, these pigment concentrates may contain binder vehicles and/or other adjuvant substances. These pigment concentrates can be incorporated in various binder vehicles, such as alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins for example.
The humectants according to the invention are also suitable for the production of ink jet inks.
Examples
The invention is further illustrated by the following Examples.
General procedure for intermediates A and B: Intermediate A:
1 part of caustic potash is dissolved in 15 parts of methanol. 75 parts of Oiticica oil is added. The mixture is vigorously stirred at ambient temperature for about 1 hour under nitrogen atmosphere. After a resting time of about 1 day the lower phase is discarded as chemical waste. The upper phase mainly consisting of the methyl esters of the corresponding fatty acids can be used in the succeeding experiments without additional purification.
In the same way intermediate B based on tung oil was synthesized.
General procedure for humectant syntheses Nl: Maleic acid anhydride and a hydroxy-fu notional polyether were placed in a three-necked flask under nitrogen atmosphere and heated to 120 0 C. At this temperature an unsaturated raw material (reactive as a diene in terms of a Diels-Alder reaction) was added. The reaction mixture was heated up to 180-190 °C for about 5 h. For detailed mol ratios see Table 1.
General procedure for humectant syntheses Till:
A mixture of an unsaturated raw material (reactive as a diene in terms of a Diels-Alder reaction) and a (meth)acrylic-functional polyether was placed in a three-necked flask under nitrogen atmosphere and heated to 180-190 0 C for about 5 h. For detailed mol ratios see Table 2.
General procedure for humectant syntheses TIMl:
A mixture of intermediate A (B resp.), a mono-OH functional polyether and 0,5 weight-% of p- toluenesulfonic acid was placed in a three-necked flask under nitrogen atmosphere and heated to 180-190 0 C for about 5 h. After cooling to 120 0 C maleic anhydride is added. This mixture is heated to 180-190 °C for about 3 h more. For detailed mol ratios see Table 3.
The obtained products showed an excellent performance as humectants. The performance could be enhanced by addition of siccatives and/or ionization of the acidic groups. Fatty acid amine condensates were in particular suitable as ionizing agents.
Legend to chemical composition of used raw materials: PEG-200: Polyethylene glycol; M w ~ 200 g/mol PEG-600: Polyethylene glycol; M w ~ 600 g/mol MPPG-200 Polypropylene glycol monomethyl ether; M w ~ 200 g/mol MPEG-350: Polyethylene glycol monomethyl ether; M w ~ 350 g/mol MPEG-500: Polyethylene glycol monomethyl ether; M w ~ 500 g/mol MPEG-750: Polyethylene glycol monomethyl ether; M w ~ 750 g/mol MPEG-1000: Polyethylene glycol monomethyl ether; M w ~ 1000 g/mol PLURAFAC LF 401 : Nonionic surfactants from BASF PLURAFAC LF 600: Nonionic surfactants from BASF
BISOMER MPEG 350 MA: Monomethyl polyethylene glycol methacrylic ester; Average mol weight: 350 g/mol
BISOMER MPEG 550 MA: Monomethyl polyethylene glycol methacrylic ester; Average mol weight: 550 g/mol BISOMER MPEG 1000 MA: Monomethyl polyethylene glycol methacrylic ester; Average mol weight: 1000 g/mol
Mn siccative: Nuodex WEB Manganese 9 from Elementis Ce siccative: Valirex Ce 10 % D60 Co siccative: Cobalt naphthenate from Aldrich Ionizing agent: Fatty acid amine condensates and similar compounds.
Tab. 1 : General procedure for humectant syntheses I
Example maleic anhydride Polyether Polyunsaturated compound
1 7.5 g 15.Og PEG-200 37.5g tung oil
2 7.5 g 26.3g MPEG-350 37.5g tung oil
3 7.5 g 37.5g MPEG-500 37.5g tung oil
4 7.5 g 15.Og PEG-200 37.5g oiticica oil
5 7.5 g 26.3g MPEG-350 37.5g oiticica oil
6 7.5 g 37.5g MPEG-500 37.5g oiticica oil
7 7.5 g 18.4g MPEG-500 37.5g tung oil
8 7.5 g 37.5g MPEG-500 39.4g intermediate B
9 7.5 g 37.5g MPEG-500 39.4g intermediate A
10 7.5 g 37.5g MPEG-500 23.3g intermediate B
11 7.5 g 37.5g MPEG-500 23.3g intermediate A
12 7.5 g 46.7g Plurafac LF 401 37.5g tung oil
13 7.5 g 46.7g Plurafac LF 401 37.5g oiticica oil
14 7.5 g 29.9g Plurafac LF 600 37.5g oiticica oil
15 10.0 g 20.Og PEG-200 31.2g intermediate A
16 10.0 g 20.Og PEG-200 31.2g intermediate B
17 2.5 g 24.Og Plurafac LF 600 39.4g intermediate A
18 2.5 g 37.5g Plurafac LF 401 7.3g intermediate B
19 3.O g 18.4g PEG-600 30.Og tung oil
20 3.O g 18.4g PEG-600 30.Og oiticica oil
21 2-7 g 27.5g MPEG-1000 40.5g tung oil
22 2-7 g 27.5g MPEG-1000 40.5g oiticica oil
23 7.5 g 26.3g MPEG-350 23.3g intermediate A
24 7.5 g 26.3g MPEG-350 23.3g intermediate B
25 7.5 g 75.Og MPEG-1000 23.3g intermediate B
26 7.5 g 75.Og MPEG-1000 23.3g intermediate A
TI 7.5 g 56.3g MPEG-750 23.3g intermediate B
28 7.5g 56.3g MPEG-750 23.3g intermediate A
Tab. 2 General procedure for humectant syntheses
Sorbic acid = 2,4 hexadiene acid β-lonone = 2,6,6, trimethylcyclohexenyl-buten^-one. Myrcene = 7-methyl-3-methylen-1 ,6-octadien.
Preparation of pigmented tinting concentrates:
The pigment concentrates based on a universal colourant guide formulation (see comparative Example 2).
The ratio between solid carrier (humectant), pigment and dispersant is equal to the guide formulation.
Additional demi-water was used to bring the concentrates on the right grinding-viscosity and ground them for 1 hour with glass beads in a Scandex (paint shaker).
The commercial products "Nuosperse 2000" and "Humectant GRB2" were used in the comparative examples 3 and 4 as reference aside from a pure Long Oil Alkyd [concentrate] (see comparative example 1) which is "the ideal standard", and comparative example 2 as the existing guide-formulation for this application.
Humidity test with these concentrates:
The concentrates were mixed out in Long Oil Alkyd transparent let down:
Long Oil Alkyd 70 solid 81.7
White spirit 14.6
Ca 10% dryer 1.2
Co 10% dryer 0.4
Zr 18% dryer 1.7
Anti skinning agent 0.4
Addition of PY 74 - concentrates was calculated on 4g dry pigment into 100g of L.O. Alkyd transparent.
By using this calculation the amount of carrier and dispersant etc. was the same between all the mixtures, only the amount of water was different.
PY 42 - concentrates were mixed out based on 10g of dry pigment on 100g of L.O. Alkyd transparent paint.
PV 23 - concentrates were mixed out based on 1.3g of dry pigment on 100g of L.O. Alkyd transparent paint.
The mixtures were stirred-in by hand and draw-downs were made with a 75 micron wire-bar on polyester foil and placed direct after application (wet) in a humidity cabinet on 40 0 C for drying during one night. After drying the gloss (60°) was measured.
Test results:
Humidity test results confirm that paint films based on the humectant of the invention show a high glossof the cured film compared to polyethylene glycol humectants (comparative Ex.2 and 4).
PY 74: monoazo from Ciba or Clariant
PV23: Dioxazine from Ciba or Clariant
Note: Pigment % = 10%PV23 + 15% china clay from Engelhard
PY42: Yellow-oxide from Bayer.
Nuosperse 2000 from Elementis
Humectant GRB2 from Avecia
Shellsol D40 from Shell,
EFKA-6225 from EFKA Additives B.V.