U.S. patent application number 11/711229 was filed with the patent office on 2007-08-30 for wax composition and its use.
This patent application is currently assigned to Clariant International Ltd. Invention is credited to Franz-Leo Heinrichs.
Application Number | 20070203272 11/711229 |
Document ID | / |
Family ID | 38001721 |
Filed Date | 2007-08-30 |
United States Patent
Application |
20070203272 |
Kind Code |
A1 |
Heinrichs; Franz-Leo |
August 30, 2007 |
Wax composition and its use
Abstract
A wax composition comprises at least three amide waxes A, B, and
C, where amide wax A is the reaction product of alkylenediamine
with linear fatty acids or with mixtures composed of fatty acids,
amide wax B is the reaction product of alkylenediamine with
12-hydroxystearic acid, and amide wax C is the reaction product of
alkylenediamine with 12-hydroxystearic acid and with linear fatty
acids. The wax composition is suitable as a processing aid in
engineering thermoplastics or for the preparation of solvent-based
wax pastes or the preparation of wax micronizates for coatings or
for the preparation of aqueous dispersions.
Inventors: |
Heinrichs; Franz-Leo;
(Gablingen, DE) |
Correspondence
Address: |
CLARIANT CORPORATION;INTELLECTUAL PROPERTY DEPARTMENT
4000 MONROE ROAD
CHARLOTTE
NC
28205
US
|
Assignee: |
Clariant International Ltd
|
Family ID: |
38001721 |
Appl. No.: |
11/711229 |
Filed: |
February 27, 2007 |
Current U.S.
Class: |
524/210 ;
106/270; 106/271; 106/272 |
Current CPC
Class: |
C08K 5/20 20130101; C08K
2201/014 20130101; C11C 5/002 20130101 |
Class at
Publication: |
524/210 ;
106/270; 106/271; 106/272 |
International
Class: |
C08L 91/06 20060101
C08L091/06; C08K 5/00 20060101 C08K005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 28, 2006 |
DE |
10 2006 009 097.7 |
Claims
1. A wax composition comprising at least three amide waxes A, B,
and C, wherein amide wax A is the reaction product of
alkylenediamine with linear fatty acids or with mixtures of fatty
acids, amide wax B is the reaction product of alkylenediamine with
12-hydroxystearic acid, and amide wax C is the reaction product of
alkylenediamine with 12-hydroxystearic acid and with linear fatty
acids.
2. The wax composition as claimed in claim 1, wherein amide wax A
is the reaction product of ethylenediamine with linear fatty acids
or with mixtures of fatty acids without additional functional
groups, having the structure
CH.sub.3--(CH.sub.2).sub.n--CO--NH--CH.sub.2CH.sub.2--NH--CO--(CH.sub.2).-
sub.n--CH.sub.3 where n=from 6 to 20.
3. The wax composition as claimed in claim 1, wherein amide wax B
is the reaction product of ethylenediamine with 12-hydroxystearic
acid, having the structure
CH.sub.3--(CH.sub.2).sub.5--CHOH--(CH.sub.2).sub.10CO--NH--CH.sub.2CH.sub-
.2--NH--CO--(CH.sub.2).sub.10--CHOH--(CH.sub.2).sub.5--CH.sub.3
4. The wax composition as claimed in claim 1, wherein amide wax C
is the reaction product of ethylenediamine with 12-hydroxystearic
acid and with linear fatty acids, having the structure
CH.sub.3--(CH.sub.2).sub.5--CHOH--(CH.sub.2).sub.10CO--NH--CH.sub.2CH.sub-
.2--NH--CO--(CH.sub.2).sub.n--CH.sub.3 where n=from 6 to 20.
5. The wax composition as claimed in claim 1, having from 1 to 85%
by weight of amide wax A, from 1 to 85% by weight of amide wax B,
and from 1 to 50% by weight of amide wax C, based in each case on
the total weight of the wax composition.
6. The wax composition as claimed in claim 1, having from 5 to 75%
by weight of amide wax A, from 5 to 75% by weight of amide wax B,
and from 1 to 40% by weight of amide wax C, based in each case on
the total weight of the wax composition.
7. A processing aid for a thermoplastic comprising a wax
composition as claimed in claim 1.
8. The processing aid as claimed in claim 7, wherein the
thermoplastic is selected from the group consisting of PVC,
polystyrene, polyamide, polycarbonate, polyalkylene terephthalate,
polyoxymethylene, polyphenylene oxide, and thermoplastic
polyurethane,
9. A preparation aid for solvent-based wax pastes comprising a wax
composition as claimed in claim 1.
10. A wax micronizate comprising a wax composition as claimed in
claim 1.
11. An aqueous dispersion comprising a wax composition as claimed
in claim 1.
12. A thermoplastic comprising at least one thermoplastic and a wax
composition according to claim 1, and wherein the wax composition
is present from 0.1 to 10% by weight, preferably from 0.2 to 5% by
weight, particularly preferably from 0.2 to 2% by weight, based on
the total weight of plastic and wax composition.
13. The thermoplastic as claimed in claim 12, wherein the wax
composition is present from 0.2 to 5% by weight.
14. The thermoplastic as claimed in claim 12, wherein the wax
composition is present from 0.2 to 2% by weight.
15. A paint comprising the preparation aid as claimed in claim
9.
16. The micronizate as claimed in claim 10, further comprising at
least one millable wax.
17. A coating comprising a wax micronizate as claimed in claim
10.
18. A coating comprising a wax micronizate as claimed in claim 16.
Description
[0001] The present invention is described in the German priority
application No. 10 2006 009 097.7, filed 28. Feb. 2006, which is
hereby incorporated by reference as in fully disclosed herein.
[0002] The invention relates to a wax composition composed of at
least three components and to its use as additive in plastics
processing, as matting agent, as rheological agent, as slip
additive, or for the preparation of dispersions. The components
present in the wax composition have been selected from the amide
waxes group.
[0003] Conventional plastics, such as PVC or styrene, and also
engineering thermoplastics, such as polyamide, polycarbonate,
polyalkylene terephthalate, polyoxymethylene, polyphenylene oxide,
or thermoplastic polyurethane are widely processed by the
injection-molding technique. Process optimization therefore places
particular importance on what is known as mold-release behavior and
flow behavior of the relevant plastics. Small amounts of external
processing aids are added to the plastics in order to adjust these
features. Important factors with these processing aids are both
their internal action and their external action.
[0004] For internal action, such as control of rheological
properties of the melt, reduction of friction, dispersion of
additives and of colorants, substances with good compatibility with
the polymer are needed. In contrast, for external action, e.g. in
the form of lubricants and release agents, substances having some
degree of incompatibility with the polymer are needed. Another
factor that has to be considered is that the chemical structure of
engineering thermoplastics makes them especially susceptible to
hydrolysis, and that acidic or basic additives therefore lead to
uncontrolled side-reactions in these thermoplastics and simply for
this reason are not suitable as processing aids.
[0005] These varied, complex, and often contradictory requirements
placed upon ideal processing aids are satisfied by only a very
small group of substances. Among these are fatty acid derivatives,
waxes, and, with some restrictions, metal soaps, polyesters, or
amides. However, even these substances continually give rise in
particular cases to disadvantages, which have to be accepted in the
absence of a better alternative.
[0006] Although fatty acids are excellent processing aids, they
promote polymer degradation and at the, often high, processing
temperatures reached by plastics during injection molding they are
volatile and escape in the form of fume. Soaps can easily decompose
in the presence of acidic constituents and then behave in exactly
the same way as fatty acids. Fatty acid esters are often
excessively polar and in polar plastics exhibit only internal
action, whereas in nonpolar plastics a marked tendency toward
migration is observed. The behavior of the amides of stearic acid,
erucic acid, or oleic acid is similar to that of the fatty acid
esters.
[0007] For improvement of formulations for injection molding, the
preferred trend is therefore in the direction of longer-chain
compounds, for example those derivable from montan wax acid and
from its derivatives, or toward reaction products of long-chain
fatty acids with diamines. The prior art uses reaction products of
stearic acid or of palmitic acid with ethylenediamine. However, the
ideal balance has not yet been found between internal action and
external action.
[0008] It was therefore an object to find a suitable processing aid
intended for plastics during injection molding and which on the one
hand provides adequate internal action but at the same time also
exhibits good lubricant action and release action at the surface of
the plastic, without at the same time inhibiting or preventing
further treatment of the surface of the plastic via excessive
migration.
[0009] Surprisingly, it has been found that this object can be
achieved via the use of a specific combination of amide waxes as
components of a wax composition. The expression "amide waxes" is
intended to be defined as a collective term for a product group
which is the result of reaction of a long-chain carboxylic acid
with a mono- or polyfunctional amine or with ammonia.
[0010] The invention achieves the object via a wax composition of
the type mentioned at the outset which comprises a combination
composed of at least three amide waxes A, B, and C, and the
characterizing feature of which is that [0011] amide wax A is the
reaction product of alkylenediamine with linear fatty acids or with
mixtures composed of fatty acids, [0012] amide wax B is the
reaction product of alkylenediamine with 12-hydroxystearic acid,
and [0013] amide wax C is the reaction product of alkylenediamine
with 12-hydroxystearic acid and with linear fatty acids.
[0014] Reaction products of ethylenediamine and stearic acid or
palmitic acid, olamide, erucaamide, stearylamide are available
industrially.
[0015] In the case of the inventive wax composition composed of the
amide waxes A, B, and C, these being surprisingly suitable as
processing aids during the injection molding of plastics with
optimized internal and external action, in contrast, suitable
amounts of three different components A, B, and C are combined with
one another.
[0016] Amide wax A is reaction products of alkylenediamine,
preferably of ethylenediamine, with linear fatty acids or mixtures
of fatty acids, for example tallow fatty acid, coconut fatty acid,
stearic acid, palmitic acid, behenic acid, or erucic acid, having
the structure
CH.sub.3--(CH.sub.2).sub.n--CO--NH--CH.sub.2CH.sub.2--NH--CO--(CH.sub.2)-
.sub.n--CH.sub.3
where n=from 6 to 20.
[0017] Amide wax B is the reaction product of alkylenediamine,
preferably of ethylenediamine, with 12-hydroxystearic acid,
preferably having the following composition:
CH.sub.3--(CH.sub.2).sub.5--CHOH--(CH.sub.2).sub.10CO--NH--CH.sub.2CH.su-
b.2--NH--CO--(CH.sub.2).sub.10--CHOH--(CH.sub.2).sub.5--CH.sub.3
[0018] Amide wax C is the reaction product of alkylenediamine,
preferably of ethylenediamine, with 12-hydroxystearic acid and with
linear fatty acids, preferably having the structure:
CH.sub.3--(CH.sub.2).sub.5--CHOH--(CH.sub.2).sub.10CO--NH--CH.sub.2CH.su-
b.2--NH--CO--(CH.sub.2).sub.n--CH.sub.3
where n=from 6 to 20.
[0019] The inventive wax composition preferably comprises an amount
in the range from 1 to 85% by weight of amide wax A, an amount in
the range from 1 to 85% by weight of amide wax B, and an amount in
the range from 1 to 50% by weight of amide wax C, based in each
case on the total weight of the wax composition.
[0020] In one particularly preferred embodiment of the invention,
the wax composition comprises an amount in the range from 5 to 75%
by weight of amide wax A, an amount in the range from 5 to 75% by
weight of amide wax B, and an amount in the range from 1 to 40% by
weight of amide wax C, again based in each case on the total weight
of the wax composition.
[0021] The reaction of the starting materials with alkylenediamine,
preferably with ethylenediamine, for preparation of the amide waxes
takes place at temperatures above 100.degree. C. In particular, the
fatty acid mixtures are placed in a reactor where they are melted
under an inert gas. At temperatures around 140.degree. C.,
ethylenediamine is metered, with stirring, into the resultant melt.
After feed of the stoichiometrically prescribed amount of
ethylenediamine, the temperature is further increased to
190.degree. C., and stirring is continued, with removal of the
water of reaction by distillation, until both the acid number AcN
and the alkali number AIN have fallen below the value 6. The acid
number AcN is determined to DIN EN ISO 3682 to monitor the progress
of the reaction, the alkali number AIN being determined to DGF
method H III 2a (92).
[0022] The inventive wax compositions are then prepared from the
amide waxes A, B, and C of the preparation examples via mixing. The
precise composition of the wax compositions is analyzed by gas
chromatography.
[0023] Surprisingly, it has been found that the inventive wax
compositions comprising at least the amide waxes A, B, and C have
particular suitability as processing aids for the injection molding
of conventional plastics, such as PVC or styrene, or of engineering
thermoplastics, such as polyamide, polycarbonate, polyalkylene
terephthalate, polyoxymethylene, polyphenylene oxide, or for
thermoplastic polyurethane. The amounts of the wax composition
inventively added as processing aid to the plastics are in the
range from 0.1 to 10% by weight, preferably from 0.2 to 5% by
weight, particularly preferably from 0.2 to 2% by weight, based in
each case on the total weight of plastic plus processing aid.
[0024] The inventive wax compositions can be employed as pure
substances or can be mixed with known prior-art mixture components,
such as polyethylene waxes, polypropylene waxes, amide waxes,
Fischer-Tropsch waxes, and then can be micronized. The particle
size here is advantageously adjusted within the range from 10 to 20
.mu.m.
[0025] The inventive wax compositions can moreover also be
dissolved in solvents at an elevated temperature and be
precipitated via cooling. Pastes thus prepared can be used in print
applications for control of viscosity and of slip behavior.
[0026] The invention will be further clarified for the person
skilled in the art via the inventive examples below. All of the
amounts stated in mixtures here are % by weight amounts unless
otherwise stated. The following amide waxes were first prepared
here:
Preparation example 1 for amide wax C,
[0027] 1.5 mol of 12-hydroxystearic acid 0.5 mol of tallow fatty
acid (35/65) 1.0 mol of ethylenediamine
AIN: 4.3/AcN: 4.7
Preparation example 2 for amide wax C,
[0028] 1.0 mol of 12-hydroxystearic acid 1.0 mol of tallow fatty
acid (35/65) 1.0 mol of ethylenediamine
AIN: 4.9, AcN: 4.9
Preparation example 3 for amide wax C,
[0029] 1.5 mol of 12-hydroxystearic acid 0.5 mol of tallow fatty
acid (45/55) 1.0 mol of ethylenediamine
AIN: 4.8/AcN: 4.3
Preparation example 4 for amide wax A:
[0030] 0.5 mol of stearic acid 1.5 mol of tallow fatty acid (30/70)
1.0 mol of ethylenediamine
AIN: 4.1/AcN: 4.5
Preparation example 5 for amide wax B:
[0031] 2.0 mol of 12-hydroxystearic acid 1.0 mol of
ethylenediamine
AIN: 4.3/AcN: 4.7
Comparative example of the prior art, c1:
[0032] 2.0 mol of tallow fatty acid (30/70) 1.0 mol of
ethylenediamine
AIN: 5.1/AcN 4.8
Comparative example of the prior art, c2:
[0033] 2.0 mol of pure stearic acid 1.0 mol of ethylenediamine
AIN: 5.3 AcN 4.9
[0034] The wax compositions are then prepared from the amide waxes
A, B, and C of preparation examples 1 to 5. The exact composition
of the inventive wax compositions is analyzed by means of GC. The
composition by weight of the inventive wax compositions WC1 to WC4
and of the comparative mixture c1 and c2 of the prior art have been
listed in the table below. These were then tested as processing aid
in engineering plastics and in micronized form as additives in the
coating.
TABLE-US-00001 WC WC2 WC3 WC4 c1 c2 C.sub.16-EDA-C.sub.16 7 3 11.5
7 9 C.sub.16-EDA-C.sub.18 25 11.5 28 31 42
C.sub.16-EDA-C.sub.18--OH 13 17.5 17 C.sub.18-EDA-C.sub.18 24 10.5
17 37 49 100 C.sub.18-EDA-C.sub.18--OH 24 32.5 20.5
C.sub.18--OH-EDA-C.sub.18--OH 7 25 6 25 Total 100 100 100 100 100
100
Thermoplastic Polyurethane
[0035] An amount of 0.4% by weight of the wax compositions, based
on the weight of the mixture composed of esterdiol and wax
composition, was inserted into the esterdiol component during the
preparation of thermoplastic polyurethane (TPU).
[0036] This mixture was reacted with diisocyanates to give the
polyurethane. Injection moldings were then produced from the
resultant polymers, Mold release and migration behavior at room
temperature, at 60 and at 80.degree. C. were evaluated and graded
(low-number grades here indicating best performance).
[0037] Tests were carried out on the inventive products comprising
wax compositions WC1 to WC4, the mixture 1, and pure EBS c2, and
also on a commercially available derivative of montan wax acid. The
data showed that the inventive products can significantly improve
migration behavior at an adequate level of demolding force.
Performance in Thermoplastic Polyurethane
TABLE-US-00002 [0038] Montan wax WC1 WC2 WC3 WC4 c1 c2 derivative
Demolding 1.6 1.9 1.5 1.8 1.5 2.9 3 Migration 23.degree. C. 2.5 1.5
2.5 3.5 3 1.5 Migration 60.degree. C. 3 1.5 2.5 3 2.5 3 1.5
Migration 80.degree. C. 3 4 3 3 6 6 1.5
Use in Polystyrene
[0039] Injection-molding behavior of polystyrene in combination
with the inventive wax compositions was tested in a ratio of 95/5,
90/10, and 85/15. For comparison, pure polystyrene was tested, as
were the combinations with the substances of the prior art. The
measurements made were the separation force in newtons, the flow
path within the test spiral in cm, color, transparency, exudation
and lubricant action, these being evaluated against the standard by
giving grades (low-number grades indicating best performance).
[0040] Commercially available products were used as comparison. c1
is Hostalub FA 1 and c3 is Hostalub FA 5. The experiments showed
that the inventive wax compositions improved flow behavior and
migration behavior at identical demolding force. The inventive
products remain within the matrix and do not exude even when the
amounts added are relatively high.
Performance Test in Polystyrene, 95/05
TABLE-US-00003 [0041] Styrene c1 c3 WC1 WC2 Unit Exudation -- 3 3 2
2 -- Color 1 2 4 2 2 -- Flow behavior 63 63 63 64 64 cm Lubricant
action -- 2 2 2 2 -- Mixture 85/15 3 4 2 2 Mixture 90/10 3 3 2 2
Mixture 95/05 2 2 2 2 Transparency 1 2 3 2 3 2 3 -- Release action
1772 1585 1605 1557 1592 N
Use in PVC
[0042] The inventive mixtures were also tested in PVC against
standard amide waxes and montan wax derivatives.
[0043] The following mixture was used as test formulation: 100
parts of Vinnolit S 3160, PVC from Vinnolit, 1.5 parts of Mark 17
MOK, 5 parts of Kane ABE-58A, 1 part of Paraloid K 120 N, 0.3 part
of Loxiol G 16, 0.4 part of test product or comparative
product.
[0044] c1=Hostalub FA1 amide wax, c3=Hostalub FA 5 amide wax
[0045] The behavior of the inventive products was the same as that
of the standard in terms of release action and lubricant action,
and when compared with the prior-art products they were poorer in
terms of color but better in terms of exudation behavior.
Performance Test in PVC
TABLE-US-00004 [0046] c1 c3 WC1 WC2 Release action 3 3 3 3 Color 1
2 4 3 Transparency 90.0% 90.0% 90.0% 90.0% Exudation 3 3 2 2
Lubricant action 3 3 3 3
[0047] Use in Polycarbonate
[0048] Action was tested in a test formulation composed of 100
parts of Makrolon 3108, 0.5 part of wax composition/comparative
product. The mixtures WC1 and WC2 were tested against Licolub FA1
and Licolub FA 5. Color, transparency, release action and melt
index were tested.
[0049] Experiment results on polycarbonate:
[0050] Results from wax compositions composed of amide waxes in
polycarbonate
TABLE-US-00005 Makrolon Amount Demolding MVR Polycarbonate M 3108
[% by force 275.degree. C./5 kg Yellowness Transparency VN Wax wt.]
[N] [cm.sup.3/10 min] index [%] 91463 -- 1800 12.5 2.33 88.8 91464
Licolub 1 1700 17.4 2.15 88.9 FA 1 91465 Licolub 1 1700 13 2.45
88.9 FA 5 91466 FHG 514 1 1600 16.3 2.47 88.9 91467 FHG 515 1 1600
15 2.46 88.9 91468 Licolub 1.5 1300 24.6 1.92 89.3 FA 1 91469
Licolub 1.5 1500 15.1 2.38 88.9 FA 5 91470 FHG 514 1.5 1600 23.4
2.08 89.2 91471 FHG 515 1.5 1600 20.6 1.76 89.4 FA 5 = Reaction
product of hydroxystearic acid and tallow amine, FA 1 = Reaction
product of stearic acid and ethylenediamine, FHG 515 = Mixture 2 (=
WC2) of the examples FHG 514 = Mixture 1 (= WC1) of the
examples
[0051] The table shows that the inventive wax compositions have
good compatibility with polycarbonate and remain within the matrix
even when the amounts added are relatively high. In terms of
external action, no increase occurs in demolding force.
* * * * *