U.S. patent application number 11/352546 was filed with the patent office on 2006-06-15 for fabric care composition.
This patent application is currently assigned to Unilever Home & Personal Care USA, Division of Conopco., Inc.. Invention is credited to Robert John Carswell, James Bernard Cooper, Ezat Khoshdel, Euan Stuart Reid, Keith Leslie Rutherford.
Application Number | 20060123559 11/352546 |
Document ID | / |
Family ID | 9934210 |
Filed Date | 2006-06-15 |
United States Patent
Application |
20060123559 |
Kind Code |
A1 |
Carswell; Robert John ; et
al. |
June 15, 2006 |
Fabric care composition
Abstract
This invention relates to a fabric care composition comprising a
thermoplastic elastomer and a textile compatible carrier, a method
of treating fabric with such a composition as part of a laundering
process and the use of a thermoplastic elastomer or a composition
comprising a thermoplastic elastomer to improve the crease recovery
properties and/or elasticity and/or shape retention of a
fabric.
Inventors: |
Carswell; Robert John;
(Merseyside, GB) ; Cooper; James Bernard;
(Merseyside, GB) ; Khoshdel; Ezat; (Merseyside,
GB) ; Reid; Euan Stuart; (Merseyside, GB) ;
Rutherford; Keith Leslie; (Chicago, IL) |
Correspondence
Address: |
UNILEVER INTELLECTUAL PROPERTY GROUP
700 SYLVAN AVENUE,
BLDG C2 SOUTH
ENGLEWOOD CLIFFS
NJ
07632-3100
US
|
Assignee: |
Unilever Home & Personal Care
USA, Division of Conopco., Inc.
|
Family ID: |
9934210 |
Appl. No.: |
11/352546 |
Filed: |
February 10, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10401454 |
Mar 28, 2003 |
7030076 |
|
|
11352546 |
Feb 10, 2006 |
|
|
|
Current U.S.
Class: |
8/115.51 ;
510/421; 510/475 |
Current CPC
Class: |
C08G 77/442 20130101;
C11D 3/3769 20130101; D06M 15/643 20130101; C11D 3/3742 20130101;
D06M 2200/20 20130101; D06M 15/285 20130101; D06M 15/21 20130101;
C11D 3/3773 20130101; D06M 15/693 20130101; D06M 15/263 20130101;
D06M 15/233 20130101; D06M 15/6436 20130101; C11D 3/3707 20130101;
C11D 3/373 20130101; C08F 293/005 20130101; C11D 3/3765
20130101 |
Class at
Publication: |
008/115.51 ;
510/421; 510/475 |
International
Class: |
C11D 3/00 20060101
C11D003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 3, 2002 |
GB |
0207742.8 |
Claims
1. A fabric care composition comprising a thermoplastic elastomer
which is a block copolymer comprising a core polymer having a
backbone comprising at least a proportion of C--C bonds and/or
Si--O bonds and two or more flanking polymers, each flanking
polymer being covalently bound to an end of the core polymer,
wherein the copolymer is soluble at a level of at least 1% by
weight in water or aqueous ethanol at 25.degree., and a textile
compatible carrier.
2. A composition as claimed in claim 1, wherein the core polymer
has a Tg of from --150.degree. C. to 50.degree. C.
3. A composition as claimed in claim 1, wherein the flanking
polymers have a Tg of from 30.degree. C. to 150.degree. C.
4. A composition as claimed in claim 1, wherein the block copolymer
is linear or star-shaped.
5. A composition as claimed in claim 1, wherein the block copolymer
is a linear ABA block copolymer.
6. A composition as claimed in claim 1, wherein the core polymer is
a polymer of a (C.sub.1-3 alkoxy)C.sub.1-6 alkyl acrylate and/or a
C.sub.2-4 alkylene glycol.
7. A composition as claimed in claim 6, wherein the core polymer is
a polymer of (2-methoxyethyl)acrylate.
8. A composition as claimed in claim 6, wherein the core polymer is
a polymer of ethylene glycol.
9. A composition as claimed in claim 1, wherein the core polymer is
a polysiloxane of the general formula
[Y(R.sup.12).sub.p--Si(R.sup.10)(R.sup.11)--O--[Si(R.sup.10)(R.sup.11)--O-
].sub.nSi(R.sup.10)(R.sup.11)--(R.sup.13).sub.qZ] in which n is an
integer from 5 to 1,000,000; R.sup.10 and R.sup.11 are
independently selected from monovalent, optionally substituted,
linear or branched C.sub.1-18 hydrocarbon radicals as described
above; R.sup.12 and R.sup.13 are independently selected from
divalent, optionally substituted, linear or branched C.sub.1-18
hydrocarbon radicals as described above; p and q are integers
having a value of 0 or 1, and Y and Z are independently selected
from hydroxyl, --NH.sub.2 and --NHR.sup.14 where R.sup.14 is a
monovalent, optionally substituted, linear or branched C.sub.1-18
hydrocarbon radical as defined above, with the proviso that,
either, but not both, of Y and Z may also be hydrogen or a
monovalent, optionally substituted, linear or branched C.sub.1-18
hydrocarbon radical as defined above, thereby giving a
mono-end-capped polysiloxane.
10. A composition as claimed in claim 9, wherein the core polymer
is poly(dimethylsiloxane).
11. A composition as claimed in claim 1, wherein the flanking
polymers are polymers of a C.sub.1-4alkyl methacrylate, glycerol
methacrylate, a di-(C.sub.1-4alkyl)amino C.sub.1-6 alkyl
methacrylate and/or a N,N-di(C.sub.1-4 alkyl)acrylamide.
12. A composition as claimed in claim 11, wherein the flanking
polymers are polymers of methyl methacrylate, glycerol
methacrylate, 2-dimethylaminoethyl methacrylate and/or N,N-dimethyl
acrylamide.
13. A composition as claimed in claim 1, wherein the copolymer is a
poly(2-dimethylaminoethyl methacrylate)-poly(ethylene
glycol)-poly(2-dimethylaminoethyl methacrylate) block copolymer, a
poly(glycerol methacrylate)-poly((2-methoxyethyl)
acrylate)-poly(glycerol methacrylate) block copolymer, a
poly(2-dimethylaminoethyl methacrylate)-poly
(dimethylsiloxane)-poly(2-dimethylaminoethyl methacrylate) block
copolymer, a poly
(N,N-dimethyl-acrylamide)-[poly(2-methoxyethyl)acrylate)-poly(tert-butyl
acrylate)]-poly(N,N-dimethyl acrylamide) block copolymer, a
[poly(N,N-dimethyl acrylamide)-poly(methyl
methacrylate)]-poly((2-methoxyethyl)acrylate)-[poly(N,N-dimethyl
acrylamide)-poly(methyl methacrylate)] block copolymer or a
poly(N,N-dimethyl acrylamide)-poly ((2-methoxyethyl)
acrylate)-poly(N,N-dimethyl acrylamide) block copolymer.
14. A composition as claimed in claim 1, which comprises from 0.1
to 20% by weight of the block copolymer.
15. A composition as claimed in claim 1, wherein the core polymer
has a weight average molecular weight of from 1 kDa to 500 kDa.
16. A composition as claimed in claim 1, wherein the flanking
polymers have a weight average molecular weight of from 200 Da to
250 kDa.
17. A composition as claimed in claim 1, wherein the molar ratio of
the core polymer to the flanking polymers is from 1:10 to 10:1.
18. A composition as claimed in claim 1, wherein the polymer has a
viscosity of less than 15 cp as determined for 5 wt % polymer in 50
vol % aqueous ethanol solution at 25.degree. C. using capillary
viscometry and assuming a viscosity for deionised water of 1
mpas.
19. A composition as claimed in claim 1, wherein the block
copolymer has an elastic modulus of less than 0.45 Gpa.
20. A composition as claimed in claim 1, which further comprises a
fragrance or perfume.
21. A composition as claimed in claim 1, which is in a form
suitable for spraying onto a fabric.
22. A method of treating fabric which comprises treating the fabric
with a fabric care composition according to claim 1 as part of a
laundering process.
23. A method as claimed in claim 22, wherein the fabric is treated
with the composition during the wash or rinse cycle.
24. A method as claimed in claim 22, wherein the composition is
applied to the fabric prior to drying and/or ironing.
25. A method of improving the crease recovery properties and/or
elasticity and/or shape retention of a fabric which comprises
treating the fabric with a thermoplastic elastomer as defined in
claim 1.
26. A method of improving the crease recovery properties and/or
elasticity and/or shape retention of a fabric which comprising
treating the fabric with a composition according to claim 1.
Description
[0001] THIS IS A CONTINUATION OF SER. NO. 10/401,454 FILED MAR. 28,
2003.
TECHNICAL FIELD
[0002] This invention relates to a fabric care composition
comprising a thermoplastic elastomer and a textile compatible
carrier, a method of treating fabric with such a composition as
part of a laundering process and the use of a thermoplastic
elastomer or a composition comprising a thermoplastic elastomer to
improve the crease recovery properties and/or elasticity and/or
shape retention of a fabric.
BACKGROUND OF THE INVENTION
[0003] The laundry process generally has several benefits for
fabric, the most common being to remove dirt and stains from the
fabric during the wash cycle and to soften the fabric during the
rinse cycle. However, there are numerous disadvantages associated
with repeated use of conventional laundry treatment compositions
and/or the actual laundry process; one of these being a fairly
harsh treatment of fabric in the laundry process causing fabric to
lose its shape.
[0004] One aspect of the present invention is therefore directed
towards maintaining the new appearance of fabric, that is to give
increased stretch to the fabric and also better return (after being
stretched) to the articles original shape (shape retention).
[0005] The creasing of fabrics is also an almost inevitable
consequence of cleaning fabrics, such as in a domestic laundering
process. Fabrics also become creased in wear. Creasing can be a
particular problem for fabrics, which contain cellulosic fibres
such as cotton, because the creasing is often difficult to remove.
Generally, the creases, which are developed in a fabric during
laundering, are removed by ironing. However, because ironing is
seen as a time consuming chore, there is an increasing trend for
fabrics to be designed such that the need for ironing is reduced
and/or the effort required for ironing is lower.
[0006] Compositions for reducing the wrinkling of fabric are
described in WO 96/15309 and WO 96/15310. The compositions contain
a silicone and a film-forming polymer and it appears that it is the
lubricating effect of the silicone, which is responsible for their
anti-wrinkle properties. This conclusion is supported by the fact
that a wide variety of polymers is mentioned as being suitable for
use in the compositions.
[0007] Industrial treatments of fabrics to reduce their tendency to
crease are known. JP-A-04-50234 describes a textile treatment in
which the crease resistance of a plain weave cotton fabric is
increased by applying a so-called "shape memory resin" to the
fabric. However, this document teaches that the resin is applied to
the fabric at a relatively high amount of 10% by weight on weight
of fabric and it is not clear how this level of resin affects other
properties of the fabric. Furthermore, treatment of the fabric with
the resins is followed by a step of drying at 80.degree. C. and the
shape memory function is described as being heat-sensitive, with
deformations at normal temperatures being restored to the original
shape on heating at a specific temperature.
[0008] A relationship between polymer elastic properties and the
ability to impart improved wrinkle recovery to cotton fabric is
described by Rawls et al in Journal of Applied Polymer Science,
vol. 15, pages 341-349 (1971). A variety of different elastomers
was applied to fabric and, particularly in the few cases where
thermoplastic elastomers were used, the polymers were applied to
the fabric at the relatively high levels of 4% and above. There is
no indication that any benefit would be obtained in applying
polymers to the fabric at lower levels and no suggestion as to
practical applications of the technique.
[0009] The treatment of fabrics with cross-linking agents in order
to impart antiwrinkle properties is known. Compounds such as
formaldehyde-based polymers, DMDHEU (dimethylol dihydroxy ethylene
urea) and BTCA (butyl-1,2,3,4-tetracarboxylic acid) may be used as
the cross-linking agent. However, these treatments have the
disadvantage of reducing the tensile strength of the fabrics.
[0010] International publications nos. WO 00/71606 and WO 00/71607
describe polysiloxane block copolymers which are built up from
units of the formula [A] and [B] in which A is a polymeric block
built up from radically polymerisable monomer and B is a
polysiloxane block. These block copolymers may be used in cosmetic
and personal care compositions. However, there is no suggestion
that such block copolymers may exhibit fabric care benefits in a
laundry composition.
[0011] The present invention aims to reduce the tendency for
fabrics to become wrinkled or creased.
[0012] The invention further aims to reduce the deleterious effects
on elasticity and tensile strength of fabrics, which some
conventional anti-wrinkle treatments impart. The invention may also
provide a degree of shape retention in the fabric.
SUMMARY OF THE INVENTION
[0013] In a first aspect, the present invention provides a fabric
care composition comprising a thermoplastic elastomer which is a
block copolymer comprising a core polymer having a backbone
comprising at least a proportion of C--C bonds and/or Si--O bonds
and two or more flanking polymers, each flanking polymer being
covalently bound to an end of the core polymer, wherein the
copolymer is soluble at a level of at least 1% by weight in water
or aqueous ethanol at 25.degree., and a textile compatible
carrier.
[0014] In a second aspect, the invention provides a method of
treating fabric which comprises treating the fabric with a fabric
care composition comprising a thermoplastic elastomer as defined
above.
[0015] In a third aspect, the invention provides the use of a
thermoplastic elastomer as defined above or a composition as
defined above to improve the crease recovery properties and/or
elasticity and/or shape retention of a fabric.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The present invention involves the development of polymers
for use in compositions for fabric care applications. The
compositions comprise a thermoplastic elastomer. The thermoplastic
elastomer is a block copolymer comprising a core polymer having a
backbone comprising at least a proportion of C--C (ie,
carbon-carbon) bonds and/or Si--O (ie. silicon-oxygen) bonds and
two or more flanking polymers. The linkages in the backbone of the
core polymer may comprise greater than 30%, preferably greater than
50%, more preferably greater than 75%, most preferably greater then
95%, such as, for example, at least 99% (these percentages being by
number) C--C and/or Si--O bonds. In some cases, the backbone may
contain 100% (by number) C--C and/or Si--O bonds. Other bonds which
may be present in the backbone of the core polymer, in addition to
the C--C and/or Si--O bonds, include, for example, C--O bonds. The
flanking polymers are bound to an end of the core polymer.
Preferably, the flanking polymers comprise at least a proportion of
C--C (ie, carbon-carbon) bonds. The linkages in the backbone of the
flanking polymer preferably comprise greater than 50%, more
preferably greater than 75%, most preferably greater then 95%, such
as, for example, at least 99% (these percentages being by number)
C--C bonds. In some cases, the backbone of the flanking polymer may
contain 100% (by number) C--C bonds. Other bonds which may be
present in the backbone of the flanking polymer, in addition to the
C--C bonds, include, for example, C--O or C--N bonds.
[0017] The core polymer can take a number of different forms. For
example, the core polymer may be linear, branched, radial or
star-shaped (the latter polymers also being termed "aerial").
Star-shaped polymers may have three or more arms. When the core
polymer is linear, a flanking polymer is bound to each end of the
core polymer and the resulting block copolymer is an ABA block
copolymer; this is a preferred embodiment of the present invention.
When the core polymer is star-shaped, a flanking polymer is bound
to each end of the core polymer and the block copolymer therefore
contains as many flanking polymers as there are points or free ends
in the star shaped polymer. For example, if the star shaped core
polymer has four ends the block copolymer will comprise four
flanking polymer groups.
[0018] The block copolymer may therefore have the structure
(AB).sub.n-Core, where A and B are polymeric blocks, n is 2 or more
(preferably 2, or 4, 6, 8 or 12) and Core is a non-polymeric
linking core. For ABA block copolymers, there may or may not be a
non-polymeric core in the B block, depending on how polymerisation
is carried out. In one preferred embodiment of the invention, the A
and B blocks are each derived from a single monomer.
[0019] Usually, the flanking polymer (such as component A in an ABA
block polymer) comprises or consists of a material that is hard at
room temperature (ie, it has a high Tg) but becomes soft and fluid
upon heating. Such materials are known in the art as shard" blocks.
The core polymer (such as component B in an ABA block copolymer)
comprises or consists of a material that is soft at room
temperature (ie, it has a low Tg). Materials of this latter type
are known in the art as "soft blocks".
[0020] The glass transition temperature (Tg) of the flanking
polymer (eg, in the case of an ABA block copolymer, the A blocks)
is typically from 0 to 300.degree. C., preferably from 25 to
175.degree. C., more preferably from 30 to 1 50.degree. C. The
glass transition temperature of the core polymer (eg, in the case
of an ABA block copolymer, the B blocks) is typically from -200 to
150.degree. C., preferably from -150 to 75.degree. C., more
preferably from -150 to 50.degree. C. (such as from -150 to less
than 30.degree. C.). Those skilled in the art will appreciate that
the particular Tg values in any given case will depend on the
overall nature of the polymer and the identity of the particular
core and flanking polymers. The main requirement is that the
flanking polymers will constitute hard blocks, whilst the core
polymer will be a soft block. Typically, this means that the Tg of
the flanking polymers will be higher than that of the core
polymer.
[0021] Tg or glass transition is a well-known term in polymer
science that is used to describe the temperature at which a polymer
or a segment thereof undergoes a transition from a solid or brittle
material to a liquid or rubber-like material. The glass transition
temperature can be measured by a variety of standard techniques
that are well known in polymer science. A common technique for the
determination of glass transition temperature is differential
scanning calorimetry, commonly known as DSC. The glass transition
phenomenon in polymers is described in polymer textbooks and
encyclopaedias, for example "Principles of Polymer Chemistry", A
Ravve, Plenum Press, New York and London 1995, ISBN
0-30644873-4.
[0022] The core and flanking polymer segments are generally
thermodynamically incompatible and they will therefore phase
separate into multiphase compositions in which the phases are
intimately dispersed.
[0023] The flanking and core polymers are typically selected in a
manner so as to produce a block copolymer with balanced
hydrophilic/hydrophobic character. The copolymer may be, for
example, soluble in water, ethanol or mixtures thereof or soluble
in other textile acceptable diluents or carriers.
[0024] The copolymer is soluble in water or aqueous ethanol at a
level of at least 1 % by weight (more preferably at least 5% by
weight, eg, 1 to 25% by weight or 5 to 25% by weight) at 25.degree.
C. By soluble, it is meant that the copolymer forms stable micelles
that do not phase separate (for example over a period of at least 2
hours, more preferably at least 24 hours) for a 1% (or other
specified value) by weight solution in distilled water or aqueous
ethanol at 25.degree. C.
[0025] The core polymer typically has a number average molecular
weight of from 100 to 10,000,000 Da (preferably from 1,000 to
200,000 Da, more preferably from 1,000 to 100,000 Da) and a weight
average molecular weight of from 100 to 20,000,000 Da (preferably
from 1,000 to 500,000 Da, more preferably from 1,000 to 450,000 Da,
even more preferably from 1,000 to 400,000 Da). The flanking
polymers preferably have a number average molecular weight of from
80 to 500,000 Da (preferably from 100 to 100,000 Da) and a weight
average molecular weight of from 80 to 700,000 Da (preferably from
100 to 250,000 Da, more preferably from 200 to 250,000 Da). The
molar ratio of the core polymer to the flanking polymers is
typically from 1:10 to 10:1.
[0026] The viscosity of the polymer is preferably less than 15 mPas
(centipoise; cp), more preferably less than 12 mpas, such as for
example in the range from 3 to 12 mPas (cp), as estimated for 5 wt
% polymer in 50 vol % aqueous ethanol solution at 25.degree. C.
using capillary viscometry and assuming a viscosity for deionised
water of 1 mPas.
[0027] The block copolymers also preferably have an elastic modulus
of less than 0.45 GPa, as determined by the method described herein
in the examples in the section under the heading "Method for
determining elastic modulus". Preferably, the polymer has an
elastic modulus in the range of from 0.01 to 0.45 GPa, more
preferably 0.05 to 0.45 GPa, most preferably 0.1 to 0.45 GPa.
[0028] Preferably, the polymer consists essentially of (ie,
contains at least 95% and preferably substantially 100%) atoms
selected from carbon, hydrogen, silicon, oxygen and nitrogen.
[0029] Each of the flanking polymers may, independently, comprise
the same or different monomers. Hence, the copolymers used in the
invention include, for example, ABA and ABC block copolymers.
[0030] The flanking polymers in each thermoplastic elastomer are
preferably substantially identical in terms of their composition
and molecular weight. However, the flanking polymers may,
alternatively, be different from each other in terms of their
composition and/or molecular weight.
[0031] Preferably, the flanking polymer and/or the core polymer,
more preferably both the core polymer and the flanking polymer,
comprise backbones which are obtainable by free radical
polymerisation of vinylic monomers. Suitable vinylic monomers
include those based on acrylate/methacrylate, acrylamide and/or
styrenic systems. However, other block copolymeric systems such as
those derived by, for example, addition polymerisation mechanisms
such as polycondensation can also be utilised, provided that the
flanking and core polymers are derived from hard and soft segments,
respectively.
[0032] The block copolymers of the present invention can be
produced by standard polymerisation techniques such as anionic or
living free radical polymerisation methodologies. Suitable methods
for preparing the polymers will be known to those skilled in the
art.
[0033] Free radically polymerisable monomers suitable for use in
polymerisation methods to produce polymers suitable for use in the
present invention are preferably ethylenically unsaturated
monomers. The living free radical polymerisation route is preferred
due to its versatility and commercial viability. By "polymerisable"
is preferably meant monomers that can be polymerised in accordance
with a living radical polymerisation.
[0034] By "ethylenically unsaturated" is meant monomers that
contain at least one polymerisable carbon-carbon double bond (which
can be mono-, di-, tri- or tetra-substituted). Either a single
monomer or a combination of two or more monomers can be utilised.
In either case, the monomers are selected to meet the physical and
chemical requirements of the final block copolymer.
[0035] Suitable ethylenically unsaturated monomers useful herein
include protected or non-protected acrylic acid and methacrylic
acid and salts, esters, anhydrides and amides thereof.
[0036] The acrylic acid and methacrylic acid salts can be derived
from any of the common non-toxic metal, ammonium, or substituted
ammonium counter ions.
[0037] The acrylic acid and methacrylic acid esters can be derived
from C.sub.1-40 straight chain, C.sub.3-40 branched chain, or
C.sub.3-40 carbocyclic alcohols, from polyhydric alcohols having
from about 2 to about 8 carbon atoms and from about 2 to about 8
hydroxyl groups (non-limiting examples of which include ethylene
glycol, propylene glycol, butylene glycol, hexylene glycol,
glycerin, and 1,2,6-hexanetriol); from amino alcohols (non-limiting
examples of which include aminoethanol, dimethylaminoethanol and
diethylaminoethanol and their quaternised derivatives); or from
alcohol ethers (non-limiting examples of which include
methoxyethanol and ethoxyethanol).
[0038] The acrylic acid and methacrylic acid amides can be
unsubstituted, N-alkyl or N-alkylamino mono-substituted, or
N,N-dialkyl, or N,N-dialkylamino disubstituted, wherein the alkyl
or alkylamino groups can be derived from C.sub.1-40 (preferably
C.sub.1-10) straight chain, C.sub.3-40 branched chain, or
C.sub.3-40 carbocyclic moieties. In addition, the alkylamino groups
can be quaternised.
[0039] Also useful as monomers are protected and unprotected
acrylic or/and methacrylic acids, salts, esters and amides thereof,
wherein the substituents are on the two and/or three carbon
position of the acrylic and/or methacrylic acids, and are
independently selected from C.sub.1-4 alkyl, hydroxyl, halide
(--Cl, --Br, --F, --I), --CN, and --CO.sub.2H, for example
methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid and
3-cyano acrylic acid. The salts, esters, and amides of these
substituted acrylic and methacrylic acids can be defined as
described above for the acrylic/methacrylic acid salts, esters and
amides.
[0040] Other useful monomers include vinyl and allyl esters of
C.sub.1-40 straight chain, C.sub.3-40 branched chain, or C.sub.3-40
carbocyclic carboxylic acids, vinyl and allyl halides (eg, vinyl
chloride, allyl chloride), (eg, vinyl pyridine, allyl pyridine);
vinylidene chloride; and hydrocarbons having at least one
unsaturated carbon-carbon double bond (eg, styrene,
alpha-methylstyrene, t-butylstyrene, butadiene, isoprene,
cyclohexadiene, ethylene, propylene, 1-butene, 2-butene,
isobutylene, p-methylstyrene); and mixtures thereof. Preferred
ethylenically unsaturated monomers have the following general
formula: H(R.sup.1)C.dbd.C(R.sup.2)(C(O)G) in which R.sup.1 and
R.sup.2 are independently selected from hydrogen, C.sub.1-C.sub.10
straight or branched chain alkyl (the term alkyl, when used herein,
refers to straight chain and branched groups), methoxy, ethoxy,
2-hydroxyethoxy, 2-methoxyethyl and 2-ethoxyethyl groups;
[0041] G is selected from hydroxyl, --O(M).sub.1/v, --OR.sup.3,
--NH.sub.2, --NHR.sup.3 and --N(R.sup.3)(R.sup.4);
[0042] where M is a counter-ion of valency v selected from metal
ions such as alkali metal ions and alkaline earth metal ions,
ammonium ions and substituted ammonium ions such as mono-, di-,
tri- and tetraalkylammonium ions, and each R.sup.3 and R.sup.4 is
independently selected from hydrogen, C.sub.1-C.sub.8 straight or
branched chain alkyl, glycerol, N,N-dimethylaminoethyl,
2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl.
[0043] More preferred specific monomers useful herein include those
selected from protected and unprotected acrylic acid, methacrylic
acid, ethacrylic acid, methyl acrylate, ethyl acrylate, V-butyl
acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl
acrylate, decyl acrylate, octyl acrylate, methyl methacrylate,
ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate,
t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl
methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl
ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate,
2-ethylhexyl ethacrylate, decyl ethacrylate, 2,3-dihydroxypropyl
acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate,
glyceryl monoacrylate, glyceryl monoethacrylate, glycidyl
methacrylate, glycidyl acrylate, glycerol methacrylate, acrylamide,
methacrylamide, ethacrylamide, N-methyl acrylamide, N,N-dimethyl
acrylamide, N,N-dimethyl methacrylamide, N-ethyl acrylamide,
N-isopropyl acrylamide, N-butyl acrylamide, N-t-butyl acrylamide,
N,N-di-n-butyl acrylamide, N,N-diethylacrylamide, N-octyl
acrylamide, N-octadecyl acrylamide, N,N-diethylacrylamide, N-phenyl
acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide,
N-dodecyl methacrylamide, N,N-dimethylaminoethyl acrylamide,
quaternised N,N-dimethylaminoethyl acrylamide,
N,N-dimethylaminoethyl methacrylamide, quaternised
N,N-dimethylaminoethyl methacrylamide, N,N-dimethylaminoethyl
acrylate, N,N-dimethylaminoethyl methacrylate (i.e.
2-dimethylaminoethyl methacrylate) quaternised
N,N-dimethyl-aminoethyl acrylate, quaternised
N,N-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, glyceryl
acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate,
2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl
methacrylate, 2-ethoxyethyl ethacrylate, maleic acid, maleic
anhydride and its half esters, fumaric acid, itaconic acid,
itaconic anhydride and its half esters, crotonic acid, angelic
acid, diallyidimethyl ammonium chloride, vinyl pyrrolidone, vinyl
imidazole, methyl vinyl ether, methyl vinyl ketone, maleimide,
vinyl pyridine, vinyl pyridine-N-oxide, vinyl furan, styrene
sulphonic acid and its salts, allyl alcohol, allyl citrate, allyl
tartrate, vinyl acetate, vinyl alcohol, vinyl caprolactam, vinyl
acetamide, vinyl formamide and mixtures thereof.
[0044] Even more preferred monomers are those selected from methyl
acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate,
ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate, t-butyl
acrylate, n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl
acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate,
N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl
acrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl
methacrylate, glycerol methacrylate, acrylic acid, methacrylic
acid, N-t-butylacrylamide, N-sec-butylacrylamide,
N,N-dimethylacrylamide, N,N-dibutylacrylamide,
N,N-dihydroxyethylacrylamide, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, benzyl acrylate,
4-butoxycarbonylphenyl acrylate, butyl acrylate, 4-cyanobutyl
acrylate, cyclohexyl acrylate, dodecyl acrylate, 2-ethylhexyl
acrylate, heptyl acrylate, iso-butyl acrylate, 3-methoxybutyl
acrylate, 3-methoxypropyl acrylate, methyl acrylate, N-butyl
acrylamide, N,N-dibutyl acrylamide, ethyl acrylate, methoxyethyl
acrylate, hydroxyethyl acrylate, diethyleneglycolethyl acrylate and
mixtures thereof.
[0045] Particularly preferred for the flanking polymers are
polymers or copolymers of an acrylamide eg, N,N-dialkylacrylamides,
preferably N,N-dimethylacrylamide. Copolymers include, for example,
random copolymers of an acrylamide with one or more other vinylic
monomers eg, another acrylamide or an acrylate ester, as described
hereinbefore. Representative examples of particularly preferred
monomers for the flanking polymers therefore include, but are not
restricted to: acrylamide, methacrylamide, N-tert-butylacrylamide,
N-sec-butylacrylamide, N,N-dimethylacrylamide,
N,N-dibutylacrylamide, N,N-dihydroxyethylacrylamide, acrylic and
methacrylic acids and their sodium, potassium, ammonium salts,
styrene, styrenesulphonic acid, N,N-dialkylaminoethyl acrylate,
N,N-dialkylaminoethyl methacrylate, glycerol methacrylate,
N,N-dialkylaminoethyl acrylamide, vinylformamide, tert-butyl
acrylate, tert-butyl methacrylate, and, where the flanking polymer
is a copolymer, mixtures thereof. N,N-dialkylacrylamides and
N-alkylacrylamides, wherein the alkyl groups are C.sub.1-C.sub.8
straight or branched chain alkyl (particularly
N,N-dimethylacrylamide), are the most preferred class of monomers
for the flanking polymer, and are preferably used as copolymers
with C1-C6 alkyl acrylate or methacrylate esters (such as methyl
methacrylate) or acrylic acid when one or both of the flanking
polymers is a copolymer.
[0046] It is preferred that the core polymer is a polymer or
copolymer of an acrylate ester. Copolymers may, for example, be
random copolymers of two or more (preferably two) different
acrylate esters. Preferred acrylate esters are esters of acrylic
acid and C.sub.1-C.sub.8 straight or branched chain alcohols.
Representative examples of monomers for the core polymer include,
but are not restricted to: benzyl acrylate, 4-butoxycarbonylphenyl
acrylate, butyl acrylate, 4-cyanobutyl acrylate, cyclohexyl
acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate,
iso-butyl acrylate, 3-methoxybutyl acrylate, 3-methoxypropyl
acrylate, methyl acrylate, neopentyl acrylate, nonyl acrylate,
octyl acrylate, phenethyl acrylate, propyl acrylate, N-butyl
acrylamide, N,N-dibutyl acrylamide, ethyl acrylate, methoxyethyl
acrylate, hydroxyethyl acrylate, diethyleneglycolethyl acrylate.
More preferred are polymers or copolymers of a (C1-C3 alkoxy)C1-C6
alkyl acrylate. Particularly preferred core polymers are polymers
or copolymers of (2-methoxyethyl)acrylate. The copolymers may be
copolymers of (2-methoxyethyl)acrylate with C.sub.1 to C.sub.6
alkyl acrylate esters such as, for example, t-butyl acrylate.
[0047] Other preferred core polymers include polymers or copolymers
of C.sub.2-4 alkylene glycols, especially poly(ethylene
glycol).
[0048] Alternatively, preferred core polymers may include
polysiloxanes having nucleophilic end-groups which may be linear,
branched or hyperbranched, provided they have at least one
nucleophilic end-group as described above. Typically, such an
end-group is one capable of nucleophilic attack via its O, N or S
atom.
[0049] Examples of preferred polysiloxanes have the formula
[Y(R.sup.12).sub.p--Si(R.sup.10)(R.sup.11)--O--[Si(R.sup.10)(R.sup.11)--O-
].sub.nSi(R.sup.10)(R.sup.11)--(R.sup.13).sub.qZ] in which n is an
integer from 5 to 1,000,000;
[0050] R.sup.10 and R.sup.11 are independently selected from
monovalent, optionally substituted, linear or branched C-.sub.1-18
hydrocarbon radicals as described above;
[0051] R.sup.12 and R.sup.13 are independently selected from
divalent, optionally substituted, linear or branched C.sub.1-18
hydrocarbon radicals as described above;
[0052] p and q are integers having a value of 0 or 1, and
[0053] Y and Z are independently selected from hydroxyl, --NH.sub.2
and --NHR.sup.14 where R.sup.14 is a monovalent, optionally
substituted, linear or branched C.sub.1-18 hydrocarbon radical as
defined above, with the proviso that, either, but not both, of Y
and Z may also be hydrogen or a monovalent, optionally substituted,
linear or branched C-.sub.1-18 hydrocarbon radical as defined
above, thereby giving a mono-end-capped polysiloxane.
[0054] Particularly preferred polysiloxanes corresponding to the
above general formula have: n=5 to 1,000,000, preferably 5 to 500;
R.sup.10 and R.sup.11=methyl, p and q=0 and Y and Z=hydroxyl; or p
and q=1, R.sup.12 and R.sup.13=(CH.sub.2).sub.3 and Y and
Z=NH.sub.2.
[0055] Polydimethylsiloxane is particularly preferred as a core
polymer.
[0056] Preferably, the block copolymer of the invention contains up
to 85% by weight of the flanking polymers, based on flanking and
core polymers. More preferably, the block copolymer contains from
20% to 85% by weight of the flanking polymers.
[0057] In the block copolymers of the invention, each of the core
and flanking polymers is preferably derived from a single
monomer.
[0058] The core polymer is preferably a polymer of (2-methoxyethyl)
acrylate or ethylene glycol or is polydimethylsiloxane.
(2-Methoxyethyl)acrylate polymers are especially preferred.
Preferably, the flanking polymers are polymers of glycerol
methacrylate, 2-dimethylaminoethyl methacrylate or, especially
N,N-dimethyl acrylamide. More preferably, the copolymer is a
poly(2-dimethylaminoethyl methacrylate)-poly(ethylene
glycol)-poly(2-dimethylaminoethyl methacrylate) block copolymer, a
poly(glycerol methacrylate)-poly((2-methoxyethyl)
acrylate)-poly(glycerol methacrylate) block copolymer, a
poly(2-dimethylaminoethyl methacrylate)-poly
(dimethylsiloxane)-poly(2-dimethylaminoethyl methacrylate) block
copolymer, a poly
(N,N-dimethyl-acrylamide)-[poly(2-methoxyethyl)acrylate)-poly(tert-butyl
acrylate)]-poly(N,N-dimethyl acrylamide) block copolymer, a
[poly(N,N-dimethyl acrylamide)-poly(methyl
methacrylate)]-poly((2-methoxyethyl)acrylate)-[poly(N, N-dimethyl
acrylamide)-poly(methyl methacrylate)] block copolymer or a
poly(N,N-dimethyl acrylamide)-poly ((2-methoxyethyl)
acrylate)-poly(N,N-dimethyl acrylamide) block copolymer.
[0059] The block copolymers of the invention may have further
polymer chains grafted onto the core polymer and/or one or more (or
all) of the flanking polymers. Suitable polymer chains for grafting
onto the block copolymers include, for example, silicones, and
polymers derived from monomers such as acrylate and methacrylate
esters (eg, esters of acrylic or methacrylic acid with
C.sub.1-C.sub.8 straight or branched chain alcohols), styrene
(optionally substituted with one or more C.sub.1-C.sub.12 straight
or branched chain alkyl groups) and mixtures thereof. Other
suitable polymer chains include polyalkyleneglycols, such as
polyethyleneglycol or polypropyleneglycol. The polymer chains which
may be grafted onto the block copolymers may be hydrophobic or
hydrophilic or mixtures of hydrophobic and hydrophilic chains may
be grafted onto the block copolymers. Suitable hydrophobic and
hydrophilic macromers for the grafts are described in WO
95/06078.
ABA Block Copolymers
[0060] The preferred polymers for use in the present invention are
ABA block copolymers. As used herein, "A-B-A block copolymer"
refers to a polymer comprising at least three segments having at
least two differing compositions and also having any one of a
number of different architectures, where the monomers are not
incorporated into the polymer architecture in a solely statistical
or uncontrolled manner. The transition from each A block to B block
may be sharply defined or may be tapered (ie, there may be a
gradual compositional change from A to B blocks). Although there
may be two, three, four or more monomers in a single block-type
polymer architecture, it will still be referred to herein as a
block copolymer. In some embodiments, the block copolymers of this
invention include one or more blocks of random copolymer (referred
to herein as an "R" block) together with one or more blocks of
single monomers. Thus, the polymer architecture may be A-R-A,
R-B-R, R-B-A, R-R'-R, A-R-B-A or A-R-B-R-A, where R and R' are
random blocks of monomers A and B or of monomers B and C or more
monomers. Moreover, the random block can vary in composition or
size with respect to the overall block copolymer. In some
embodiments, for example, the random block will account for between
5 and 80% by weight of the mass of the block copolymer. In other
embodiments, the random block R will account for more or less of
the mass of the block copolymer, depending on the application.
Furthermore, the random block may have a compositional gradient of
one monomer to the other (e.g., A:B) that varies across the random
block in an algorithmic fashion, with such algorithm being either
linear having a desired slope, exponential having a desired
exponent (such as a number from 0.1-5) or logarithmic. The random
block may be subject to the same kinetic effects, such as
composition drift, that would be present in any other radical
copolymerization and its composition, and size may be affected by
such kinetics, such as Markov kinetics. Any of the monomers listed
elsewhere in this specification may be used in the block copolymers
of this invention.
[0061] A "block" within the scope of the block copolymers of this
invention typically comprises about 5 or more monomers of a single
type (with the random blocks being defined by composition and/or
weight percent, as described above). In preferred embodiments, the
number of monomers within a single block may be about 10 or more,
about 15 or more, about 20 or more or about 50 or more. Each block
may have a desired architecture and thus, each block may be linear,
branched (with short or long chain branches), star (with 3 or more
arms), etc. Other architectures will be apparent to those of skill
in the art upon review of this specification.
[0062] In one embodiment, block copolymers are assembled by the
sequential addition of different monomers or monomer mixtures to
living polymerization reactions. In another embodiment, the
addition of a pre-assembled functionalized block (such as a
telechelic oligomer or polymer) to a free radical polymerization
mixture yields a block copolymer (e.g., the polymerization mixture
may be controlled or "living"). Ideally, the growth of each block
occurs with high conversion. Conversions are determined by NMR via
integration of polymer to monomer signals. Conversions may also be
determined by size exclusion chromatography (SEC) via integration
of polymer to monomer peak. For UV detection, the polymer response
factor must be determined for each polymer/monomer polymerization
mixture. Typical conversions can be 50% to 100 % for each block,
more specifically in the range of from about 60% to about 90%).
Intermediate conversion can lead to block copolymers with a random
copolymer block separating the two or more homopolymer blocks,
depending on the relative rates of polymerization and monomer
addition. At high conversion, the size of this random block is
sufficiently small such that it is less likely to affect polymer
properties such as phase separation, thermal behaviour and
mechanical modulus. This fact can be intentionally exploited to
improve polymerization times for many applications without
measurably affecting the performance characteristics of the
resulting polymer. This is achieved by intentionally "killing" or
terminating the living nature of the polymerization when a desired
level of conversion (e.g., >80%) is reached by, e.g., cooling
the polymerization to room temperature or by neutralizing the
control agent, for example by introducing acids, bases, oxidizing
agents, reducing agents, radical sources, scavengers, etc. In the
absence of a radical control agent, the polymerization continues
uncontrolled (typically at much higher reaction rates) until the
remaining monomer is consumed.
[0063] When the block copolymer contains a polysiloxane, it may be
formed in the presence of an atom transfer radical initiator via a
nucleophilic displacement reaction between the nucleophilic
end-groups on the polysiloxane and leaving groups on the other
polymers respectively. The nucleophilic displacement reaction of
the second reaction step may be carried out under conventional
reaction conditions. This process is described in more detail in
International publications nos. WO 00/71606 and WO 00/71607.
[0064] A typical polysiloxane block copolymer obtainable by the
process described above is built up from units of the general
formula [A]L[B], in which A is a polymeric block built up from
radically polymerisable monomer, B is a polysiloxane block and L is
a divalent linker group which links the A and B blocks via O--Si,
N--Si or S--Si bonds to the B block. Preferably L is selected from:
[0065] --R.sup.15--C(O)--O--; [0066] --R.sup.15--O--C(O)--O--;
[0067] --R.sup.15--C(O)--N(R.sup.16)--; [0068]
--R.sup.15--O--C(O)--N(R.sup.16)--, or [0069]
--R.sup.15--N(R.sup.16)--C(O)--N(R.sup.17)--; in which R.sup.15 is
a divalent, optionally substituted, linear or branched C.sub.1-18
hydrocarbon radical as described above, and
[0070] R.sup.16 and R.sup.17 are independently selected from
monovalent, optionally substituted, linear or branched C-.sub.1-18
hydrocarbon radicals as described above.
[0071] The overall molecular architecture of the silicone block
copolymers of the invention can be described by the formulas A-L-B,
A-L-B-L-A, -(A-L-B)n-, wherein n is an integer of 2 or greater, or
[A-L-][A-L-]B[-L-A][-L-A], wherein A-L-B represents a diblock
structure, A-L-B-L-A represents a triblock structure, -(A-L-B),-
represents a multiblock structure, and [A-L-][A-L-]B[-L-A][-L-A]
represents a dendritic structure.
[0072] The existence of a block copolymer according to this
invention is determined by methods known to those of skill in the
art. For example, those of skill in the art may consider nuclear
magnetic resonance (NMR) studies of the block copolymer. Those of
skill in the art would also consider the measured increase of
molecular weight upon addition of a second monomer to chain-extend
a living polymerization of a first monomer. Block copolymer
structure can be suggested by observation microphase separation,
including long range order (determined by X-ray diffraction),
microscopy and/or birefringence measurements. Other methods of
determining the presence of a block copolymer include mechanical
property measurements, (e.g., elasticity of soft/hard/soft block
copolymers), thermal analysis and chromatography (e.g., absence of
homopolymer).
[0073] Measurement of optical properties, such as absorbance (color
and clarity), provides information about the phase morphology and
microstructure of the polymer emulsions. Thus, for example,
birefringence measurements may indicate the presence of optical
anisotropy resulting from microphase separation in hard/soft block
copolymers. Likewise, sharp color delineations in optical
micrographs of annealed polymer films can indicate the presence of
ordered, microphase-separated block copolymer structure.
[0074] Block copolymers of sufficiently high molecular weight phase
separate on a microscopic scale, to form periodically arranged
microdomains which typically comprise predominantly one or the
other polymer. These may take the form of lamellae, cylinders,
spheres, and other more complex morphologies, and the domain sizes
and periods are typically in the range 10-100 nm. Such microphase
separation can be detected obtained in a variety of ways, including
electron microscopy, x-ray or neutron scattering or reflectivity,
measurement of optical anisotropy, and Theological measurements.
The absence of a periodic microstructure is not necessarily
evidence against having synthesized a block copolymer, as such
absence may be due to low molecular weight, broad molecular weight
distribution of the individual blocks, weak intermolecular
interactions, or inadequate time and slow kinetics for microphase
separation. However, the presence of a periodic microstructure on
the 10-100 nm scale is considered extremely compelling evidence for
block copolymer formation in accord with this invention. A periodic
microstructure is not, however, an essential feature of the
copolymers which may be used in the compositions of this
invention.
[0075] Block copolymers are well-known to form terraced films,
where the film thickness is restricted to integer or half-integer
multiples of the microstructure period. This occurs because
preferential interactions of one or the other block with the
substrate and/or free surface cause a layering of the microdomains
parallel to the film surface (see for example G. Coulon, D.
Ausserre, and T. P. Russell, J. Phys. (Paris) 51, 777 (1990); and
T. P. Russell, G. Coulon, V. R. Deline, and D. C. Miller,
Macromolecules 22, 4600-6 (1989)). When observed in a reflection
microscope (on a reflecting substrate such as a silicon wafer), the
terracing manifests itself as a series of discrete, well-defined
colors with sharp boundaries between them. The colors are a result
of interference between light reflected from the top and bottom
surfaces of the film, and depend on the local film thickness
("Newton's rings"). If terracing does not occur, the colors blend
continuously from one into the other.
[0076] The presence of chemically homogeneous sequences within
block copolymers leads to a phase transition known as microphase
separation. Energetically unfavorable interactions between
chemically distinct monomers drive the blocks to separate into
spatially distinct domains. Since the blocks are covalently bound
together, these domains are comparable in size to the dimensions of
the polymers themselves. The presence of these domains alters the
physical properties of the materials, giving the resulting
composite many of the chemical and physical characteristics of each
block.
Polymerisation Process
[0077] Although any conventional method can be used for the
synthesis of the block copolymers of the invention, living free
radical polymerisation is a preferred polymerisation process. Such
polymerisations are described in the literature, for example:
Tailored polymers by free radical processes, E Rizzardo et al,
Macromol. Symp. 1999, 143 (World Polymer Congress, 37.sup.th
International Symposium on Macromolecules, 1998), 291-307, ISSN:
102-1360: also Atom transfer radical polymerisation and controlled
radical polymerisation, Z Zhang, et al, Gaofenzi Tongabo, 1999, (3)
138-144; K Matyjazewski, Classification and comparison of various
controlled/"living" radical polymerisations, Book of Abstracts,
218.sup.th ACS National Meeting, New Orleans, Aug. 22-26 (1999),
Poly-042.
[0078] In principle, any "living" free radical polymerisation
techniques such as nitroxide radical controlled, atom transfer
radical polymerisation (ATRP), reversible addition fragmentation
chain transfer (RAFT) and catalytic chain transfer (CCT) could be
used. Some of the preferred polymerisation routes for the block
copolymers used in this invention are nitroxide mediated processes.
Thus, a bis-nitroxide initiator may be employed to produce
well-defined ABA block copolymers. The process comprises two steps.
In the first step, a core polymer of a defined length is
synthesised with the bis-nitroxide initiator at the "centre" of the
core polymer. This involves the living polymerisation of the
monomer or monomers with a bis-nitroxide initiator. After this
first stage is complete, the core polymer is optionally purified or
used without purification. The second step involves the
introduction of the flanking polymer monomer or monomers using the
same technique of living polymerisation. The polymerisation process
can be closely monitored by gel permeation chromatography (GPC),
NMR and viscosity measurements. The polymerisation process is
preferably stopped when high conversions are achieved.
[0079] Other preferred polymerisation routes for the block
copolymers used in this invention involve the preparation of a
macroinitiator of the core polymer and the subsequent formation of
the desired block copolymer in an atom transfer radical
polymerisation reaction.
[0080] Living free radical polymerisation techniques suitable for
use in the preparation of polymers for use in the invention
include, for example, those described in Hawker et al.,
"Development of a Universal Alkoxyamine for `Living` Free Radical
Polymerizations," J. Am. Chem. Soc., 1999, 121(16), pp. 3904-3920
for a nitroxide mediated processes and in U.S. patent application
Ser. No. 09/520,583, filed Mar. 8, 2000 and corresponding
international application PCT/US00/06176, which process is
particularly preferred, and both of these applications are
incorporated herein by reference.
[0081] Suitable polymerisation reactions include, for example, the
following ratios of starting materials, temperature, pressure,
atmosphere and reaction time. Temperatures for polymerization are
typically in the range of from about 0.degree. C. to about
130.degree. C., more preferably in the range of from about
20.degree. C. to about 130.degree. C. and even more preferably in
the range of from about 25.degree. C. to about 130.degree. C. The
atmosphere may be controlled, with an inert atmosphere being
preferred, such as nitrogen or argon. The molecular weight of the
polymer can be controlled via controlled free radical
polymerization techniques or by controlling the ratio of monomer to
initiator. Generally, the ratio of monomer to initiator is in the
range of from about 200 to about 800. In a nitroxide radical
controlled polymerization the ratio of control agent to initiator
can be in the range of from about 1 mol % to about 10 mol % and
this is preferred. The polymerization may be carried out in bulk or
in a suitable solvent such as diglyme. Polymerization reaction time
may be in the range of from about 0.5 hours to about 72 hours,
preferably from about 1 hour to about 24 hours and more preferably
from about 2 hours to about 12 hours.
[0082] The polymers used in the present invention are preferably
produced by the living free radical process.
Compositions of the Invention
[0083] Compositions of the present invention are preferably
formulated into fabric care compositions comprising a solution,
dispersion or emulsion comprising a thermoplastic elastomer and a
textile compatible carrier for use in part of a laundering process.
The laundering process may be a large scale or small-scale (e.g.
domestic) process. When the laundering process is a domestic
process, the composition may be packaged and labelled for this
use.
[0084] The polymer composition comprises a thermoplastic elastomer
as described above. The composition may contain other components,
for example other polymers which impart benefits to a fabric.
Preferably, the composition comprises from 0.1 to 20% by weight of
the thermoplastic elastomer.
[0085] Conveniently, the thermoplastic polymers have a molecular
weight of from 1,000 to 2,000,000, preferably from 2,000 to
1,000,000 and most preferably from 3,000 to 500,000.
[0086] In the present invention, the thermoplastic elastomer is
applied to a fabric such that from 0.01% to 2% by weight on weight
of fabric of the thermoplastic elastomer is coated onto the fabric.
Advantageously, lower levels of thermoplastic elastomer can be
applied eg, from 0.01% to 1.5% preferably 0.01% to 1%, more
preferably 0.1% to 1%. Generally, the thermoplastic elastomer will
at least partially coat individual fibres. At these levels of
application, the physical properties of the fabric which make it
suitable for use in a garment are retained (ie, the overall feel
and appearance of the fabric remains substantially unchanged) but,
unexpectedly, the fabric has improved crease recovery properties
and/or elasticity and/or shape retention.
[0087] The crease recovery properties of a fabric treated according
to the present invention are improved relative to fabric not so
treated. Treatment of the fabric typically reduces the tendency of
the fabric to remain creased. Thus, following treatment according
to the invention, the crease recovery angle, which is a measure of
the degree to which a fabric returns to its original shape
following creasing, increases. The fabric may still require a
degree of treatment (eg, by ironing) to reduce its creasing after
washing and drying in a conventional domestic laundering process.
However, the amount of crease reduction by ironing required for
fabric treated according to the invention will typically be less
than that required by untreated fabric. It will be appreciated that
any reduction in the amount of crease reduction, such as ironing,
which is required, is beneficial.
[0088] The method of the invention preferably comprises the step of
applying a composition of the thermoplastic elastomer to a fabric.
The solution may be applied to the fabric by conventional methods
such as dipping, spraying or soaking, for example.
[0089] The fabric care composition of the invention comprises a
solution, dispersion or emulsion comprising a thermoplastic
elastomer and a textile compatible carrier. The textile compatible
carrier facilitates contact between the fabric and the
thermoplastic elastomer. The textile compatible carrier may be
water, low molecular weight polyols or alcohols (e.g. ethanol,
isopropanol or glycol) or a surfactant. However, when it is water,
it is preferred that a perfume is present. In a composition that is
used during the washing or rinse cycles of a washing machine, it is
highly preferable if the textile compatible carrier is a cationic
surfactant, more preferably a cationic softening agent.
[0090] If the fabric care composition of the invention is in the
form of a dispersion or emulsion of the thermoplastic elastomer or
if, in the method of the invention, a dispersion or emulsion of the
thermoplastic elastomer is used, the fabric treated with the
composition may need to be heated to a temperature above the Tg of
the hard blocks of the elastomer in order to obtain the advantages
of the invention. The heating of the treated fabric can be carried
out as a separate heating step or may form part of the laundering
process eg taking place during drying of the fabric (for example in
a tumble dryer) or, more preferably, during ironing of the fabric.
Alternatively, a plasticiser or coalescing agent may be used to
lower the Tg of the thermoplastic elastomer in order to avoid the
need for heating or to reduce the temperature of the heating step
required to obtain the advantages of the invention.
[0091] The method of the invention may be carried out as a
treatment of the fabric before or after it has been made into
garments, as part of an industrial textile treatment process.
Alternatively, it may be provided as a spray composition eg, for
domestic (or industrial) application to fabric in a treatment
separate from a conventional domestic laundering process.
[0092] Alternatively, in the method of the invention, the treatment
is carried out as part of a laundering process. Suitable laundering
processes include large scale and small-scale (eg domestic)
processes. Such a process may involve the use of a fabric care
composition of the invention, for example. The fabric care
composition of the invention may be a main wash detergent
composition, in which case the textile compatible carrier may be a
detergent and the composition may contain other additives, which
are conventional in main wash detergent compositions.
Alternatively, the fabric care composition may be adapted for use
in the rinse cycle of a domestic laundering process, such as a
fabric conditioning composition or an adjunct, and the textile
compatible carrier may be a fabric conditioning compound (such as a
quaternary alkylammonium compound) or simply water, and
conventional additives such as perfume may be present in the
composition.
[0093] It is advantageous in compositions for use in a domestic
setting to further comprise a plasticiser. In the context of this
invention, a plasticiser is any material that can modify the flow
properties of the thermoplastic elastomer. Suitable plasticisers
include C.sub.12-C.sub.20 alcohols, glycol ethers, phthalates and
automatic hydrocarbons. It is also highly advantageous, if the
compositions comprise a perfume.
Detergent Active Compounds
[0094] If the fabric care composition of the present invention is
in the form of a detergent composition, the textile compatible
carrier may be chosen from soap and non-soap anionic, cationic,
nonionic, amphoteric and zwilterionic detergent active compounds,
and mixtures thereof.
[0095] Many suitable detergent active compounds are available and
are fully described in the literature, for example, in
"Surface-Active Agents and Detergents", Volumes I and II, by
Schwartz, Perry and Berch.
[0096] The preferred textile compatible carriers that can be used
are soaps and synthetic non-soap anionic and nonionic
compounds.
[0097] Anionic surfactants are well known to those skilled in the
art. Examples include alkylbenzene sulphonates, particularly linear
alkylbenzene sulphonates having an alkyl chain length of
C.sub.8-C.sub.15; primary and secondary alkylsulphates,
particularly C.sub.8-C.sub.15 primary alkyl sulphates; alkyl ether
sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl
sulphosuccinates; and fatty acid ester sulphonates. Sodium salts
are generally preferred.
[0098] Nonionic surfactants that may be used include the primary
and secondary alcohol ethoxylates, especially the C.sub.8-C.sub.20
aliphatic alcohols ethoxylated with an average of from 1 to 20
moles of ethylene oxide per mole of alcohol, and more especially
the C.sub.10-C.sub.15 primary and secondary aliphatic alcohols
ethoxylated with an average of from 1 to 10 moles of ethylene oxide
per mole of alcohol. Non-ethoxylated nonionic surfactants include
alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides
(glucamide).
[0099] Cationic surfactants that may be used include quaternary
ammonium salts of the general formula
R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+ X.sup.- wherein the R groups
are independently hydrocarbyl chains of C.sub.1-C.sub.22 length,
typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is
a solubilising cation (for example, compounds in which R.sub.1 is a
C.sub.8-C.sub.22 alkyl group, preferably a C.sub.8-C.sub.10 or
C.sub.12-C.sub.14 alkyl group, R.sub.2 is a methyl group, and
R.sub.3 and R.sub.4, which may be the same or different, are methyl
or hydroxyethyl groups); and cationic esters (for example, choline
esters) and pyridinium salts.
[0100] The total quantity of detergent surfactant in the
composition is suitably from 0.1 to 60 wt % e.g. 0.5-55 wt %, such
as 5-50wt %.
[0101] Preferably, the quantity of anionic surfactant (when
present) is in the range of from 1 to 50% by weight of the total
composition. More preferably, the quantity of anionic surfactant is
in the range of from 3 to 35% by weight, e.g. 5 to 30% by
weight.
[0102] Preferably, the quantity of nonionic surfactant when present
is in the range of from 2 to 25% by weight, more preferably from 5
to 20% by weight.
[0103] Amphoteric surfactants may also be used, for example amine
oxides or betaines.
[0104] The compositions may suitably contain from 10 to 70%,
preferably from 15 to 70% by weight, of detergency builder.
Preferably, the quantity of builder is in the range of from 15 to
50% by weight.
[0105] The detergent composition may contain as builder a
crystalline aluminosilicate, preferably an alkali metal
aluminosilicate, more preferably a sodium aluminosilicate.
[0106] The aluminosilicate may generally be incorporated in amounts
of from 10 to 70% by weight (anhydrous basis), preferably from 25
to 50%. Aluminosilicates are materials having the general formula:
0.8-1.5 M.sub.2O. Al.sub.2O.sub.3. 0.8-6 SiO.sub.2 where M is a
monovalent cation, preferably sodium. These materials contain some
bound water and are required to have a calcium ion exchange
capacity of at least 50 mg CaO/g. The preferred sodium
aluminosilicates contain 1.5-3.5 SiO.sub.2 units in the formula
above. They can be prepared readily by reaction between sodium
silicate and sodium aluminate, as amply described in the
literature. Fabric Softening and/or Conditioner Compounds
[0107] If the fabric care composition of the present invention is
in the form of a fabric conditioner composition, the textile
compatible carrier will be a fabric softening and/or conditioning
compound (hereinafter referred to as "fabric softening compound"),
which may be a cationic or nonionic compound.
[0108] The softening and/or conditioning compounds may be water
insoluble quaternary ammonium compounds. The compounds may be
present in amounts of up to 8% by weight (based on the total amount
of the composition) in which case the compositions are considered
dilute, or at levels from 8% to about 50% by weight, in which case
the compositions are considered concentrates.
[0109] Compositions suitable for delivery during the rinse cycle
may also be delivered to the fabric in the tumble dryer if used in
a suitable form. Thus, another product form is a composition (for
example, a paste) suitable for coating onto, and delivery from, a
substrate e.g. a flexible sheet or sponge or a suitable dispenser
during a tumble dryer cycle.
[0110] Suitable cationic fabric softening compounds are
substantially water-insoluble quaternary ammonium materials
comprising a single alkyl or alkenyl long chain having an average
chain length greater than or equal to C.sub.20 or, more preferably,
compounds comprising a polar head group and two alkyl or alkenyl
chains having an average chain length greater than or equal to
C.sub.14. Preferably the fabric softening compounds have two long
chain alkyl or alkenyl chains each having an average chain length
greater than or equal to C.sub.16. Most preferably at least 50% of
the long chain alkyl or alkenyl groups have a chain length of
C.sub.18 or above. It is preferred if the long chain alkyl or
alkenyl groups of the fabric-softening compound are predominantly
linear.
[0111] Quaternary ammonium compounds having two long-chain
aliphatic groups, for example, distearyldimethyl ammonium chloride
and di(hardened tallow alkyl) dimethyl ammonium chloride, are
widely used in commercially available rinse conditioner
compositions. Other examples of these cationic compounds are to be
found in "Surface-Active Agents and Detergents", Volumes I and II,
by Schwartz, Perry and Berch. Any of the conventional types of such
compounds may be used in the compositions of the present
invention.
[0112] The fabric softening compounds are preferably compounds that
provide excellent softening, and are characterised by a chain
melting Lo to La transition temperature greater than 25.degree. C.,
preferably greater than 35.degree. C., most preferably greater than
45.degree. C. This L.beta. to L.alpha. transition can be measured
by DSC as defined in "Handbook of Lipid Bilayers", D Marsh, CRC
Press, Boca Raton, Fla., 1990 (pages 137 and 337).
[0113] Substantially water-insoluble fabric softening compounds are
defined as fabric softening compounds having a solubility of less
than 1.times.10.sup.-3 wt % in demineralised water at 20.degree. C.
Preferably the fabric softening compounds have a solubility of less
than 1.times.10.sup.-4 wt %, more preferably less than
1.times.10.sup.-8to 1.times.10.sup.-6 wt %.
[0114] Especially preferred are cationic fabric softening compounds
that are water-insoluble quaternary ammonium materials having two
C.sub.12-22 alkyl or alkenyl groups connected to the molecule via
at least one ester link, preferably two ester links. An especially
preferred ester-linked quaternary ammonium material can be
represented by the formula II: ##STR1## wherein each R.sub.1 group
is independently selected from C.sub.1-4 alkyl or hydroxyalkyl
groups or C.sub.2-4 alkenyl groups; each R.sub.2 group is
independently selected from C.sub.8-28 alkyl or alkenyl groups; and
wherein R.sub.3 is a linear or branched alkylene group of 1 to 5
carbon atoms, T is ##STR2## and p is 0 or is an integer from 1 to
5.
[0115] Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or its
hardened tallow analogue is especially preferred of the compounds
of formula (II).
[0116] A second preferred type of quaternary ammonium material can
be represented by the formula (III): ##STR3## wherein R.sub.1, p
and R.sub.2 are as defined above.
[0117] It is advantageous if the quaternary ammonium material is
biologically biodegradable. Preferred materials of this class such
as 1,2-bis(hardened tallowoyloxy)-3-trimethylammonium propane
chloride and their methods of preparation are, for example,
described in U.S. Pat. No. 4,137,180 (Lever Brothers Co).
Preferably these materials comprise small amounts of the
corresponding monoester as described in U.S. Pat. No. 4,137,180,
for example, 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammonium
propane chloride.
[0118] Other useful cationic softening agents are alkyl pyridinium
salts and substituted imidazoline species. Also useful are primary,
secondary and tertiary amines and the condensation products of
fatty acids with alkylpolyamines.
[0119] The compositions may alternatively or additionally contain
water-soluble cationic fabric softeners, as described in GB 2 039
556B (Unilever).
[0120] The compositions may comprise a cationic fabric softening
compound and an oil, for example as disclosed in EP-A-0829531.
[0121] The compositions may alternatively or additionally contain
nonionic fabric softening agents such as lanolin and derivatives
thereof.
[0122] Lecithins are also suitable softening compounds.
[0123] Nonionic softeners include Lp phase forming sugar esters (as
described in M Hato et al Langmuir 12, 1659, 1666, (1996)) and
related materials such as glycerol monostearate or sorbitan esters.
Often these materials are used in conjunction with cationic
materials to assist deposition (see, for example, GB 2 202 244).
Silicones are used in a similar way as a co-softener with a
cationic softener in rinse treatments (see, for example, GB 1 549
180).
[0124] The compositions may also suitably contain a nonionic
stabilising agent. Suitable nonionic stabilising agents are linear
C.sub.8 to C.sub.22 alcohols alkoxylated with 10 to 20 moles of
alkylene oxide, C.sub.10 to C.sub.20 alcohols, or mixtures
thereof.
[0125] Advantageously the nonionic stabilising agent is a linear
C.sub.8 to C.sub.22 alcohol alkoxylated with 10 to 20 moles of
alkylene oxide. Preferably, the level of nonionic stabiliser is
within the range from 0.1 to 10% by weight, more preferably from
0.5 to 5% by weight, most preferably from 1 to 4% by weight. The
mole ratio of the quaternary ammonium compound and/or other
cationic softening agent to the nonionic stabilising agent is
suitably within the range from 40:1 to about 1:1, preferably within
the range from 18:1 to about 3:1.
[0126] The composition can also contain fatty acids, for example,
C.sub.8 to C.sub.24 alkyl or alkenyl monocarboxylic acids or
polymers thereof. Preferably saturated fatty acids are used, in
particular, hardened tallow C.sub.16 to C.sub.18 fatty acids.
Preferably the fatty acid is non-saponified, more preferably the
fatty acid is free, for example oleic acid, lauric acid or tallow
fatty acid. The level of fatty acid material is preferably more
than 0.1% by weight, more preferably more than 0.2% by weight.
Concentrated compositions may comprise from 0.5 to 20% by weight of
fatty acid, more preferably 1% to 10% by weight. The weight ratio
of quaternary ammonium material or other cationic softening agent
to fatty acid material is preferably from 10:1 to 1:10.
[0127] The fabric conditioning compositions may include silicones,
such as predominately linear polydialkylsiloxanes, e.g.
polydimethylsiloxanes or aminosilicones containing
amine-functionalised side chains; soil release polymers such as
block copolymers of polyethylene oxide and terephthalate;
amphoteric surfactants; smectite type inorganic clays; zwitterionic
quaternary ammonium compounds; and nonionic surfactants.
[0128] The fabric conditioning compositions may also include an
agent, which produces a pearlescent appearance, e.g. an organic
pearlising compound such as ethylene glycol distearate, or
inorganic pearlising pigments such as microfine mica or titanium
dioxide (TiO.sub.2) coated mica.
[0129] The fabric conditioning compositions may be in the form of
emulsions or emulsion precursors thereof.
[0130] Other optional ingredients include emulsifiers, electrolytes
(for example, sodium chloride or calcium chloride) preferably in
the range from 0.01 to 5% by weight, pH buffering agents, and
perfumes (preferably from 0.1 to 5% by weight).
[0131] Further optional ingredients include non-aqueous solvents,
perfume carriers, fluorescers, colourants, hydrotropes, antifoaming
agents, antiredeposition agents, enzymes, optical brightening
agents, opacifiers, dye transfer inhibitors, anti-shrinking agents,
anti-wrinkle agents, anti-spotting agents, germicides, fungicides,
anti-oxidants, UV absorbers (sunscreens), heavy metal sequestrants,
chlorine scavengers, dye fixatives, anti-corrosion agents, drape
imparting agents, antistatic agents and ironing aids. This list is
not intended to be exhaustive.
Fabric Treatment Products
[0132] The fabric care composition of the invention may be in the
form of a liquid, solid (e.g. powder or tablet), a gel or paste,
spray, stick or a foam or mousse. Examples including a soaking
product, a rinse treatment (e.g. conditioner or finisher) or a
mainwash product. The composition may also be applied to a
substrate e.g. a flexible sheet or used in a dispenser which can be
used in the wash cycle, rinse cycle or during the dryer cycle.
[0133] The present invention has the advantage not only of
increasing the crease recovery angle and/or elasticity and/or shape
retention of a fabric but also of improving the tensile strength of
the fabric. The tensile strength of fabrics has in the past been
increased by, for example, including fibres of a thermoplastic
elastomer, such as Lycra (trade mark) yarns, in the fabric itself.
It was unexpected that coating the fibres with a thermoplastic
elastomer, according to the invention, could provide improved
crease resistance, elasticity and/or shape retention and increased
tensile strength. The effect was particularly surprising because a
number of conventional treatments for improving the crease
resistance of fabrics can have the opposite effect of reducing the
tensile strength of the fabric, particularly where the treatment
involves cross-linking of the fabric.
[0134] It is preferable if after application of compositions
according to the invention a curing process takes place such as
ironing or tumble drying.
[0135] The following non-limiting examples illustrate the
invention.
EXAMPLES
[0136] Synthesis and Characterisation
[0137] The synthesis and characterisation of the polymers was
carried out according to the following general procedures.
[0138] In the following examples, the following abbreviations are
used: [0139] PEG=poly(ethylene glycol) [0140] MMA=methyl
methacrylate [0141] MEA=(2-methoxyethyl)acrylate [0142]
GMA=Glycerol methacrylate [0143] DMAEMA=2-dimethylaminoethyl
methacrylate [0144] tBu=tert.-butyl acrylate [0145]
DMA=N,N-dimethylacrylamide [0146] PDMS=polydimethylsiloxane
[0147] Synthesis:
Example 1
[0148] Synthesis of P(DMA)-P(MEA)-P(DMA) copolymer
[0149] Synthesis 1. bis-initiator ##STR4## 2. free nitroxide
##STR5## 3. monomer for midblock (B block) 2-methoxyethyl acrylate
(MEA) ##STR6## 4. monomer for endblock (A block) ##STR7##
N,N-dimethylacrylamide (DMA) 5. Preparation of midblock (B
block)
[0150] Bis-initiator (0.5557 g, 0.6147 mmol), MEA (40.00 g, 307.36
mmol) and free nitroxide (2.70 mg, 0.0123 mmol) were mixed in a 200
mL flask under argon, and heated at 125.degree. C. with vigorous
stirring for 5 hrs, then cooled to room temperature. The conversion
was 77% as measured by .sup.1H-NMR. The reaction mixture was
dissolved in acetone (60 mL), and precipitated into hexane (600
mL). The polymer was collected and dried under vacuum at 45.degree.
C., affording a clear viscous liquid (30.08 g).
[0151] 6. Preparation of triblock copolymer (ABA)
[0152] Midblock polymer (30.08 g), diglyme (30 g) DMA (38.20 g) and
free nitroxide (2.70 mL, 2.0 mg/mL solution in diglyme) were mixed
in a 250 mL flask under argon. The mixture was stirred and heated
at 125.degree. C. for 4 hrs, then cooled to room temperature. The
mixture was dissolved in acetone (100 mL), and precipitated into
hexane (600 mL). The precipitation process was repeated once. The
triblock copolymer was collected and dried under vacuum (50 g).
[0153] From these polymerisation methods, it will be evident to
those of skill in the art that linking atoms may exist between the
A and B blocks. These linking atoms are typically artefacts of the
particular polymerisation mechanism employed. The presence of the
linking atoms does not necessarily affect the properties of the
block copolymers of the invention and polymers containing linking
atoms are not intended to be excluded from the definition of the
block copolymers no matter which formula is used, such as A-B-A,
A-R-A, etc.
Example 2
[0154] Synthesis of PDMAEMA-PEG-PDMAEMA
[0155] (a) Preparation of poly(ethylene glycol) macroinitiator
[0156] Poly(ethylene glycol), MW=1000, ex Polysciences Inc. (20 g,
0.02 moles) was dissolved in anhydrous toluene (100 ml) in a
2-necked round bottom flask fitted with a suba seal and calcium
chloride guard tube. 4-(Dimethylamino)pyridine (0.054 g,
4.4.times.10.sup.-4 moles), triethylamine (4.45 g, 0.044 moles) and
a magnetic stirrer bar were added to the PEG solution.
2-Bromoisobutyryl bromide (10.12 g, 0.044 moles) was added dropwise
via a syringe through the suba seal, which caused the initially
clear solution to turn to a milky suspension. After stirring at
ambient overnight, the toluene was removed by evaporation using a
rotary evaporator and the remaining brown liquid was dissolved in
dichloromethane (200 ml). This solution was added to a separating
funnel and washed successively with saturated sodium bicarbonate
solution (100 ml), 1 M hydrochloric acid (100 ml) and brine (100
ml). The dichloromethane layer was then dried over magnesium
sulfate, filtered and the solvent evaporated. After drying
overnight under vacuo the product was obtained as a brown oil
(19.25 g, 73.1% yield). ##STR8##
[0157] Characterisation:
[0158] IR: 1734 cm.sup.-1 (s, saturated ester carbonyl)
[0159] NMR (.sup.1H-CDCl.sub.3): 1.94 (d, ester CH.sub.3,12H); 3.64
(s, PEG CH.sub.2, 80H); 3.73 (t, CH.sub.2--O, 4H); 4.33 (t,
CH.sub.2--O, 4H).
[0160] (b) Preparation of PDMAEMA-PEG-PDMAEMA block copolymers
2-(Dimethylamino)ethyl methacrylate (ex Aldrich) (15.41 g, 0.098
moles, the amount required to give a theoretical molecular weight
of 5000) and the PEG-macroinitiator (2 g, 1.54.times.10.sup.-3
moles) were dissolved in demineralised water (20 ml) and added to a
3-necked 50 ml round bottom flask fitted with a magnetic stirrer
bar, a thermometer, a N.sub.2 inlet and a suba seal fitted with a
gas outlet. Dry N.sub.2 gas was bubbled through the solution for 45
minutes. Copper(I)bromide (0.221 g, 1.54.times.10.sup.-3 moles) and
2,2'-dipyridyl (0.4866 g, 3.08.times.10.sup.-1 moles) were weighed
into a glass vial, mixed and added to the reaction mixture by
lifting the thermometer from the flask's socket, replacing the
thermometer immediately after addition of the solids. The reaction
mixture turned to a brown colour on mixing the solids into
solution, also an increase in viscosity was noted. A reaction
exotherm of 28.degree. C. was recorded over a time period of 6
minutes. After mixing for 2 hours under a N.sub.2 blanket, the
contents of the flask were poured into a beaker and diluted with
water (100 ml). This solution was then poured through a bed of
silica to remove the copper metal, which resulted in the initially
dark green solution to become clear and almost water-white.
[0161] This aqueous solution was freeze-dried over the weekend
yielding 15 g of slightly pink material. ##STR9##
[0162] Characterisation:
[0163] IR: 1723 cm.sup.-1 (s, saturated ester carbonyl)
[0164] NMR (.sup.1H-CDCl.sub.3): 2.3 (m, N--CH.sub.3, 6H); 2.6 (s,
N--CH.sub.2, 2H); 3.65(s, O--CH.sub.2--CH.sub.2--O, 4H); 4.08 (s,
CH.sub.2--O, 2H).
[0165] GPC (eluent=THF; PMMA standards): Mn=9000; Mw=11900;
Pdi=1.35
Example 3
[0166] Synthesis of PDMAEMA-PDMS-PDMAEMA
[0167] (a) Preparation Method:
[0168] Cu(I)Br (0.2732 g, 1.905 mmol) along with a magnetic stirrer
bar was placed in a dry Schlenk flask which was then evacuated and
flushed with nitrogen three times. 2-dimethylaminoethyl
methacrylate (3.9 mL, 0.023 moles), toluene (7.2 mL) and the PDMS
initiator (1) (2 g, 0.952 mmol) were added to the Schlenk using
degassed syringes. The solution was then deoxygenated by three
freeze--pump--thaw cycles. Finally, once the flask had reached the
desired reaction temperature of 900C the
n-propyl-2-pyridinalmethanimine ligand (2) (0.54 mL, 3.809 mmol)
was added with stirring. The reaction mixture immediately turned
dark brown in colour on addition of the ligand. ##STR10##
[0169] Target molecular weight of DMAEMA blocks=4000, molecular
weight of initiator=2000 (total=6000). The ratio of
[monomer]:[initiator] determines molecular weight of end polymer.
In the described ATRP the required ratio of --[monomer]:
[initiator]=25: 1. The ratios for the other listed reagents are as
follows; [Cu(I)Br]: [Initiator]=1:2, [LigandI: [Cu(I)Br]=2:1 and
solvent volume: monomer volume 2:1.
[0170] The monomer was purified by passing down a basic alumina
column prior to use and purged with nitrogen for at least one hour.
Toluene, which was used as a solvent for all polymerisations, was
also degassed in this manner. Cu(l)Br was purified before use
according to a published procedure.
[0171] 1) Keller, R. N.; Wycoff, H. D. -Inorganic Synthesis, 1947,
2,1.
[0172] (b) Purification of Polymer
[0173] The resultant dark brown solution was passed down an alumina
column several times using a conventional solvent such as
dichloromethane or tetrahydrofuran. When the solution appeared
colourless the solvent was removed under vacuum to yield a pale
yellow solid.
Examples 4 to 10
[0174] The following polymers were also prepared according to
methods analagous to the synthesis methods described in Examples 1
to 3 above.
Example 4
PDMAEMA-PEG-PDMAEMA
Example 5
P(GMA)-P(MEA)-(GMA)
Example 6
PDMAEMA-PDMS-PDMAEMA
Example 7
P(DMA)-[P(MEA)-P(tBu)]-P(DMA)
Example 8
{P(DMA)P(MMA}-P(MEA)-{P(DMA)P(MMA)}
Example 9
P(DMA)-P(MEA)-P(DMA)
Example 10
P(DMA)-P(MEA)-P(DMA)
[0175] Method for Determining Elastic Modulus
[0176] Modulus (E) was determined at 10 Hz, 1% strain, 25.degree.
C. in a simple tension geometry after two days of equilibration at
50% relative humidity, 25.degree. C. Samples of polymer were molded
at 120.degree. C. into sheets 1.24 mm thick. This sheet was trimmed
into a bar measuring 9.5.times.10 mm and mounted in the single
cantilever test fixture of a Rheometric Scientific DMTA-IV dynamic
mechanical thermal analyzer.
[0177] Method For Determining Viscosity
[0178] Viscosity (0) was estimated for 5 wt % polymer in 50 vol %
aqueous ethanol solution at 25.degree. C. using capillary
viscometry and assuming a viscosity for deionized water of 1
cp.
[0179] Method For Determining Molecular Weights
[0180] Number average molecular weights (Mn) for midblock polymers
are calculated from the monomer-to-initiator ratios, and the
conversion of monomer as measured by NMR (generally about 80%),
assuming the polymerization process is living. Mn for endblock
polymers are calculated from monomer mole fractions and Mn values
of midblock polymers. Monomer mole fractions are determined by
NMR.
[0181] Molecular Weights of Polymers TABLE-US-00001 Polymer MWt A
Block MWt B Block Total Mwt Comments Ex 7 19K 52K 90K B block
contains .about.10% .sup.tBu Ex 8 25K 49K 81K A block contains
.about.10% MMA Ex 9 17K 30K 62K Ex 10 21K 44K 86K
Polydispersity of all polymers ca. 1.1-1.35
Example 11
[0182] Assessment of Shape Retention Benefits (Elasticitv)
[0183] Each of the elastomers was applied to prewashed woven
sheeting by pad application from an aqueous or aqueous ethanol
solution at a level of 1% on weight of fabric. The dried sheets
were ironed and then conditioned at 65% relative humidity and
20.degree. C. for at least 24hrs
[0184] The fabric extension parameters defined below were measured
using a Testometric tester when a sample is stretched and
relaxed.
[0185] Sample size: 150 mm.times.50 mm cut on the bias
[0186] Area of stretching: 100 mm.times.25 mm
[0187] Elongation Rate: 100 mm/min
[0188] Measurement: Extend the fabric by 20 mm and return to 0 mm
measuring the force Ability to Recover from Deformation (ARfD) is
related to the force exerted by the fabric during recovery and is
defined as the force exerted after recovering by 10 mm (RF10)
normalised to that for untreated fabric (RF10.sub.o).
[0189] ARfD=RF10 RF10.sub.o
[0190] Values greater than 1 show increased ability to recover from
deformation compared to untreated fabric. The examples listed in
Table 1 all displayed ArfD values greater than 1 TABLE-US-00002
TABLE 1 Ex. No. Name ARfD 4 1% pdmaema-peg-pdmeama 1.45 5 1%
p(GMA)-P(MEA)-P(GMA) 1.60 6 1% PDMAEMA-PDMS-PDMAEMA 2.39 7 1%
P(DMA)-[P(MEA)-P(tBu)]-P(DMA) 2.36 8 1% {P(DMA)P(MMA)}-P(MEA)- 2.63
{P(DMA)P(MMA)} 9 1% P(DMA)-P(MEA)-P(DMA) 2.85 10 1%
P(DMA)-P(MEA)-P(DMA) 3.22
[0191] The Residual Extension (RE) is defined as the extension
during the recovery cycle at which the measured force drops below
0.006 kgf. All the examples listed in Table 2 showed a reduced
residual extension (RE) relative to untreated fabric TABLE-US-00003
TABLE 2 Ex. No. Name RE Untreated Fabric 8.82 4 1%
pdmaema-peg-pdmeama 8.48 5 1% p(GMA)-P(MEA)-P(GMA) 8.42 6 1%
PDMAEMA-PDMS-PDMAEMA 7.23 7 1% P(DMA)-[P(MEA)-P(tBu)]-P(DMA) 6.89 8
1% {P(DMA)P(MMA)}-P(MEA)- 6.95 {P(DMA)P(MMA)} 9 1%
P(DMA)-P(MEA)-P(DMA) 6.87 10 1% P(DMA)-P(MEA)-P(DMA) 6.69
Example 12
[0192] Assessment of Wrinkle Recovery Benefits
[0193] The fabrics were prepared as described in Example 11 above,
conditioned at 20.degree. C., 65% relative humidity then the crease
recovery angle (CRA) measured (using a modified method based on
BS1553086). A sample of fabric (25 mm.times.50 mm) is folded in
half forming a sharp crease and held under a weight of 1 kg for 1
minute. On releasing the sample the crease opens up to a certain
degree. After 1 minute relaxation time the angle is measured. The
fabric is tested in the warp direction only (hence maximum CRA is
180.degree.). Higher CRAs correspond to less wrinkled fabrics.
TABLE-US-00004 Ex. No. Sample Control CRA Sample CRA 5
P(GMA)-P(MEA)-P(GMA) 55 71 6 P(DMAEMA)-PDMS-P(DMAEMA) 55 78 8
{P(DMA)P(MMA)}-P(MEA)- 55 73 {P(DMA)P(MMA)} 9 P(DMA)-P(MEA)-P(DMA)
66 79 10 P(DMA)-P(MEA)-P(DMA) 55 82.5
* * * * *