Technical Field of the Invention
[0001] The present invention relates to fabric care compositions, such as laundry detergent
compositions and laundry rinse compositions, which comprise an oxazoline-ring functionalised
material. The invention also relates to a method of treating fabric using the compositions
of the invention and to the use of oxazoline-ring functionalised materials in the
treatment of fabric which comprises oxidised cellulose to provide a colour care benefit
to the fabric.
Background of the Invention
[0002] It is known that the laundry process is harsh to fabrics. Repeated wash and wear
cycles produce the problems of progressive colour loss and mechanical damage to laundered
fabrics.
[0003] A specific problem is oxidative damage to the fabrics, especially cotton based fabrics.
Oxidising species are present in the laundering process due to the wide-ranging inclusion
of oxidation sources (such as bleaches) in detergents, or oxidising species present
in the water supply (such as chlorine based disinfectants added as part of the water
treatment process).
[0006] Poly(2-ethyl-2-oxazoline) is known in the laundry field as a dye transfer inhibitor,
i.e. in that it will bind to dye released during the laundry process to prevent the
dye being transferred from one part of the fabric to another.
[0008] US 6,525,013 discloses fabric care and laundry detergent compositions which comprise low molecular
weight modified and unmodified amines which provide enhanced fabric care benefits.
The compositions may additionally comprise a polymer comprising poly(2-ethyl-2-oxazoline)
for use as a fabric abrasion polymer and dye transfer inhibitor.
[0009] EP 0 668 902 relates to compositions and processes useful for inhibiting the transfer of dyes,
released into laundering solution from coloured fabrics, from one fabric to another.
Poly(2-ethyl-2-oxazoline is an example of one such material.
[0010] However, these poly(2-ethyl-2-oxazoline) materials lose their oxazoline ring functionality
during polymerisation, so they do not comprise oxazoline in the form of a ring.
Brief Description of the Invention
[0011] The present invention arises from the surprising finding that treatment of fabrics
with an oxazoline material which is included in a polymer having at least two oxazoline-ring
moieties provides a colour benefit to laundered fabrics.
[0012] Accordingly, the present invention provides a laundry treatment composition comprising:
- a) an oxazoline material which is included in a polymer having at least two oxazoline-ring
moieties; and,
- b) at least one textile compatible carrier selected from the group consisting of detersive
surfactants and rinse conditioners.
[0013] In a preferred embodiment the detersive surfactant is chosen from anionic and/or
nonionic surfactants.
[0014] In another preferred embodiment the rinse conditioner is a quaternary ammonium compound.
[0015] In a preferred embodiment the polymer has a glass transition temperature of less
than 30°C. Preferably the polymer is an oxazoline ring-functionalised poly(styrene-acrylic)
polymer.
[0016] A further aspect of the present invention provides a method of treating fabric comprising:
- a) provision of a composition comprising an oxazoline material which is included in
a polymer having at least two oxazoline-ring moieties, and a textile compatible carrier
selected from the group consisting of detersive surfactants and rinse conditioners,
which composition is dissolved or dispersed in an aqueous medium;
- b) contacting fabric which comprises fibres of oxidised cellulose with the aqueous
medium of a); and,
- c) drying the treated fabric.
[0017] A yet further aspect of the invention relates to the use of an oxazoline material
which is included in a polymer having at least two oxazoline-ring moieties in the
treatment of fabric which comprises oxidised cellulose to provide a colour care benefit
to the fabric.
Detailed Description of the Invention
[0018] All percentages used herein refer to weight percentages by weight of laundry treatment
composition unless otherwise stated.
[0019] Except in the examples, or where otherwise explicitly indicated, all numbers in this
description indicating amounts of material or conditions of reaction, physical properties
of materials and/or use are to be understood as modified by the word "about".
[0020] The laundry treatment composition may take many varied forms, for example a main
wash detergent composition, or a rinse conditioner. The composition may alternatively
be in the form of a spray or a foaming product, for application before or after the
laundry process. Preferably the laundry treatment composition is a main wash composition
or a rinse conditioner composition.
[0021] The oxazoline material is included in a polymer having at least two oxazoline-ring
moieties.
[0022] The oxazoline material may be copolymerised as part of a polymer chain. For example
a long chain polymer comprising side chains which in turn comprise oxazoline rings.
Therefore the oxazoline material still bears at least two oxazoline-ring moieties,
and preferably more. Examples of these materials are oxazoline ring-functionalised
poly(styrene-acrylic) polymers, available from Nippon Shokubai as EPOCROS(Trademark).
[0023] For the avoidance of doubt, oxazoline polymers which do not contain any oxazoline
ring moieties are outside the scope of this invention.
[0024] Preferably, the material is a polymer having at least two oxazoline groups with a
glass transition temperature of below 30°C, examples being Epocros
™ K-2020E and Epocros
™ K-2010E.
[0025] The compositions of the invention, when applied to fabric, can be cured at ambient
temperature (full curing taking between 1 and 14 days) or at elevated temperature,
for example a tumble dryer (curing taking between 30 minutes and 4 hours) or by ironing
(curing taking between 1 and 10 minutes) or a combination of these methods.
[0026] The level of oxazoline material present in the laundry treatment composition is from
0.1 to 30 wt.%. The inclusion levels are based on actual oxazoline comprising material
actives, as the material can be provided as an emulsion, or dispersion of solids in
a liquid. The laundry compositions may be in concentrated form, whereby the aforementioned
inclusion levels are appropriate, or it may take a dilute form, whereby preferred
inclusion levels of the oxazoline material are 0.01 to 10 wt.%.
[0027] The oxazoline ring moiety is believed to function as a reactive agent for oxidised
cellulose, by ring-opening reaction of the oxazoline ring with a carboxylic acid (or
carboxylate) present in oxidised cellulose. The reaction forms an amide ester link
between the oxidised cellulose and the oxazoline material.
[0028] This reaction reduces the amount of oxidised cellulose present in the fabric, so
reducing the amount of associated oxidative damage to the fabric and thus reducing
the colour negative. By reacting at the carboxylic acid group, the site of the damage
is effectively masked from further chemical processes. The reaction also removes any
propensity for the site to bind transition metals such as iron(III), thus reducing
yellowing.
[0029] The oxazoline material has two or more oxazoline moieties and can be used to crosslink
oxidised cellulose.
[0030] The fabric treated may be any cellulose-fibre containing fabric. These encompass
cotton, cotton-rich fabrics and polyester-cotton fabric mixes. Preferably the fabric
comprises at least 50% cellulosic fibres.
[0031] The method of treating fabric comprises the following steps:
- a) provision of a composition comprising an oxazoline material which is included in
a polymer having at least two oxazoline-ring moieties, and a textile compatible carrier
selected from the group consisting of detersive surfactants and rinse conditioners,
which composition is dissolved or dispersed in an aqueous medium;
- b) contacting fabric which comprises fibres of oxidised cellulose with the aqueous
medium of a); and,
- c) drying the treated fabric.
[0032] The drying step of the method starts the curing process of the polymer.
[0033] The fabrics can be cured at ambient temperature (full curing taking between 1 and
14 days) or at elevated temperature, for example a tumble dryer (curing taking between
30 minutes and 4 hours) or by ironing (curing taking between 1 and 10 minutes) or
a combination of these methods.
[0034] The curing process occurs such that the oxazoline groups react with the carboxylate
groups present on the oxidatively-damaged cellulose of the fabric.
[0035] Preferably the aqueous medium provided in part a) of the method is a main wash or
rinse liquor from a laundering process.
[0036] Laundering process used herein refers solely to the wash and rinse process. This
process may be done by machine (automatic, semi-automatic or manual), or by hand.
[0037] The compositions of the invention may be used outside this defined laundry process
(either by a pre- or post treatment in reference to the main wash and rinse), but
preferably the composition is applied as part of the laundry process as defined.
[0038] The use of an oxazoline material which is included in a polymer having at least two
oxazoline-ring moieties in the treatment of fabric which comprises oxidised cellulose
to provide a colour care benefit to the fabric can be achieved in various ways.
[0039] The oxazoline material which is included in a polymer having at least two oxazoline-ring
moieties can be part of a cellulosic textile substantive material, which binds to
one surface of the cellulosic textile, and allows reaction with oxidised cellulose
to take place via an oxazoline ring moiety. Having at least two oxazoline rings to
enable cellulosic crosslinking to occur via each oxazoline ring.
[0040] The colour care benefit provided to the fabric can be the reduction in colour fading
of the fabric, or dye transfer inhibition. Preferably the colour care benefit is the
reduction in colour fading of the fabric.
Textile Compatible Carrier
[0041] In the context of the present invention the term "textile compatible carrier" includes
a component which can assist in the interaction of the cellulose cross-liking agent
with a textile. The carrier is selected from a detersive surfactant or a rinse conditioner
compound.
Detersive Surfactants
[0042] If the textile compatible carrier is a detersive surfactant, then preferably it is
selected from anionic, nonionic, cationic, zwitterionic or amphoteric detersive surfactants.
[0043] More preferably the detersive surfactant is an anionic and/or nonionic surfactant.
[0044] The composition comprises between 2 to 70 wt% of a detersive surfactant, most preferably
10 to 30 wt %. The detersive surfactant may be chosen from the surfactants described
"
Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949,
Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the
current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing
Confectioners Company or in "
Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated.
[0045] Suitable nonionic detergent compounds which may be used include, in particular, the
reaction products of compounds having a hydrophobic group and a reactive hydrogen
atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene
oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic
detergent compounds are C
6 to C
22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units
of ethylene oxide per molecule, and the condensation products of aliphatic C
8 to C
18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5
to 40 EO.
[0046] Suitable anionic detergent compounds which may be used are usually water-soluble
alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing
from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl
portion of higher acyl radicals.
[0047] Examples of suitable synthetic anionic detergent compounds are sodium and potassium
alkyl sulphates, especially those obtained by sulphating higher C
8 to C
18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl
C
9 to C
20 benzene sulphonates, particularly sodium linear secondary alkyl C
10 to C
15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those
ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols
derived from petroleum. The preferred anionic detergent compounds are sodium C
11 to C
15 alkyl benzene sulphonates and sodium C
12 to C
18 alkyl sulphates. Also applicable are surfactants such as those described in
EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants
described in
EP-A-070 074, and alkyl monoglycosides.
[0048] Suitable amphoteric surfactants are amine oxides or betaines.
[0049] Preferred surfactant systems are mixtures of anionic with nonionic detergent active
materials, in particular the groups and examples of anionic and nonionic surfactants
pointed out in
EP-A-346 995 (Unilever). Especially preferred is surfactant system that is a mixture of an alkali
metal salt of a C
16 to C
18 primary alcohol sulphate together with a C
12 to C
15 primary alcohol 3 to 7 EO ethoxylate.
[0050] The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25
to 90 wt % of the surfactant system. Anionic surfactants can be present, for example,
in amounts in the range from about 5% to about 40 wt % of the surfactant system.
Rinse Conditioners
[0051] If the textile compatible carrier is a rinse conditioner compound, then preferably
the textile compatible carrier is a cationic compound.
[0052] Preferred cationic compounds are quaternary ammonium compounds.
[0053] It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound
having at least one C
12 to C
22 alkyl chain.
[0054] It is preferred if the quaternary ammonium compound has the following formula:

in which R
1 is a C
12 to C
22 alkyl or alkenyl chain; R
2, R
3 and R
4 are independently selected from C
1 to C
4 alkyl chains and X
- is a compatible anion. A preferred compound of this type is the quaternary ammonium
compound cetyl trimethyl quaternary ammonium bromide.
[0055] A second class of materials for use with the present invention are the quaternary
ammonium of the above structure in which R
1 and R
2 are independently selected from C
12 to C
22 alkyl or alkenyl chain; R
3 and R
4 are independently selected from C
1 to C
4 alkyl chains and X
- is a compatible anion.
[0056] Other suitable quaternary ammonium compounds are disclosed in
EP 0 239 910 (Proctor and Gamble).
[0057] The cationic compound may be present from 1.5 wt % to 50 wt % of the total weight
of the composition. Preferably the cationic compound may be present from 2 wt % to
25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.
[0058] Compositions suitable for delivery during the rinse cycle may also be delivered to
the textile 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.
Builders or Complexing Agents
[0059] The composition may comprise one or more builders. Such materials may suitably be
aluminosilicates, silicates, carbonates, citrates, polycarboxylates, complexing agents,
and phosphates.
[0060] Where builder is present, the compositions may suitably contain from 10 to 70 wt.%
of detergency builder. Preferably the total level of builder is less than 20 wt.%.
[0061] Examples of suitable zeolites are: zeolite A, zeolite B (also known as zeolite P),
zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in
EP-A-0,384,070.
[0062] The composition may also comprise a complexing agent such as: ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic
acid, or, mixtures thereof.
[0063] Alternatively, or additionally to the aluminosilicate builders, phosphate builders
may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate,
and phosphonate species. Other forms of builder include silicates, such as soluble
silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
[0064] For low cost formulations carbonate (including bicarbonate and sesquicarbonate) and/or
citrate may be employed as builders.
Polymers
[0065] The composition may comprise one or more polymers. Examples are: carboxymethylcellulose,
poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), polycarboxylates
(such as polyacrylates, maleic/ acrylic acid copolymers and lauryl methacrylate/acrylic
acid copolymers), and mixtures thereof. The composition may additionally comprise
soil release polymers such as block copolymers of polyethylene oxide and terephthalate.
[0066] The composition may additionally comprise a dye transfer inhibition agent. These
prevent migration of dyes, especially during long soak times. Such agents are preferably
selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl
imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI), and copolymers
thereof, and/or mixtures thereof.
[0067] The amount of dye transfer inhibition agent if present, in the composition will be
from 0.01 to 10 %, preferably from 0.02 to 5 %, more preferably from 0.03 to 2 %,
by weight of the composition.
Enzymes
[0068] Additional colour benefits can be obtained by the incorporation of enzymes. Enzymes
contemplated for use in laundry detergent compositions include proteases, alpha-amylases,
cellulases, lipases, peroxidases/oxidases, pectate lyases, mannanases, or mixtures
thereof.
Optional Colour Care Benefit Agents
[0069] The compositions of the invention may also contain optional colour care benefit agents.
Preferred colour care benefit agents are polysaccharides. Typically, the wash/rinse
liquor will comprise around 0.01 g/L of a polysaccharide colour care benefit agent.
[0070] Preferably the polysaccharide is a beta 1-4 polysaccharide; more preferably a cellulose
derivative, such as a hydroxy C2-C4 alkyl derivative. More preferably the hydroxy
C2-C4 alkyl derivative is a hydroxy ethyl derivative.
[0071] Preferably the degree of substitution (DS) of the polysaccharide is 1.5-2.25. Preferably
the molecular weight of the polysaccharide is 100,000 to 500,000 Dalton.
Other Detergent Ingredients
[0072] The composition may also contain other conventional detergent ingredients such as
e.g. fabric conditioners including clays or silicones, foam boosters, anti-corrosion
agents, soil-suspending agents, anti-soil redeposition agents, dyes, anti-abrasion
agents, anti-microbials, stabilisers, tarnish inhibitors, or perfumes.
[0073] Further optional ingredients include non-aqueous solvents, perfume carriers, fluorescers,
colourants, hydrotropes, antifoaming agents and opacifiers.
[0074] In addition, compositions may comprise one or more of anti-shrinking agents, anti-wrinkle
agents, anti-spotting agents, germicides, fungicides, anti-oxidants, UV absorbers
(sunscreens), heavy metal sequestrants, chlorine scavengers, dye fixatives, anti-abrasion
agents, anti-corrosion agents, drape imparting agents, antistatic agents and ironing
aids. The lists of optional components are not intended to be exhaustive.
[0075] In order that the invention may be further understood and carried forth into practice
it will be described below with reference to non-limiting examples.
Examples
Example 1
[0076] Indanthrene, Remazol and Procion refer to the various dyes used in the examples:-
Indanthrene Blue RS (Vat Blue 4)
Remazol Brilliant Orange 3R (Reactive Orange 16)
Procion Yellow H-EXL (Reactive Yellow 138:1)
Procion Crimson H-EXL (Reactive Red 231)
Procion Navy H-EXL
Remazol Brilliant Yellow RNL (Reactive Orange 107)
Remazol Red RB (Reactive Red 198)
Remazol Blue BB (Reactive Blue 220)
Remazol Brilliant Yellow RNL (Reactive Orange 107)
Remazol Red RB (Reactive Red 198)
Remazol Black B (Reactive Black 5)
[0077] A load comprising 4 panels of each of the following were washed 10 times in a front
loading washing machine (Whirlpool Electronic AWM6100-6K, 40°C cotton cycle) using
Prenton water and 100g Persil Performance to generate damage on the cloth. The fabrics
were tumble dried (Miele Novotronic T430) after every wash.
Cotton interlock knitted fabric:
| 1. |
BP1-K |
2% Indanthrene Blue RS |
| 2. |
BP2-K |
4% Remazol Brilliant Orange 3R |
| 3. |
BP3-K |
3.85% Procion Yellow H-EXL 1.35% Procion Crimson H-EXL 2.41% Procion Navy H-EXL |
| 4. |
BP4-K |
1.6% Remazol Brilliant Yellow RNL 1.2% Remazol Red RB 1.2% Remazol Blue BB |
| 5. |
BP5-K |
2.2% Remazol Brilliant Yellow RNL 1.3% Remazol Red RB 1.3% Remazol Black B |
On woven cotton sheeting:
| 1. |
BP3-W |
3.85% Procion Yellow H-EXL 1.35% Procion Crimson H-EXL 2.41% Procion Navy H-EXL |
| 2. |
BP4-W |
1.6% Remazol Brilliant Yellow RNL 1.2% Remazol Red RB 1.2% Remazol Blue BB |
| 3. |
BP5-W |
2.2% Remazol Brilliant Yellow RNL 1.3% Remazol Red RB 1.3% Remazol Black B |
[0078] The fabrics were cut into 100 x 50cm pieces, folded into 50 x 50cm double panels
and overlocked around the three remaining edges. Four pieces of each cloth were used
(total 32 pieces, weight 2.1kg).
[0079] After the washes were complete, four new loads were prepared containing:
1 piece of each of the washed fabrics detailed above,
1 new piece of each of the fabrics detailed above, and,
900g of non-fluorescent woven cotton sheeting.
[0080] Total load weight was 2.0kg. Standard colour measurements (CIELAB coordinates, reflectance
and K/S spectra, UV excluded, 400nm cut-off) were taken of all the coloured fabrics
using a Datacolor Spectraflash SF600+ spectrometer.
[0081] The loads were then washed in the same Whirlpool machine using the same wash program
using the following products:

[0082] The fabrics were tumble dried (Miele Novotronic T430) after each wash cycle. The
fabrics were measured after the 9
tn wash using the Spectraflash spectrometer using the same conditions as before.
[0083] The parameter ΔΔL* (Delta Delta L*) is measured on a reflectance spectrophotometer.
After calibrating the machine using the standard black trap and white tile, the colour
coordinates of the white tile are measured and used as the reference standard. The
coloured fabrics used in the test are then measured against this standard. The measurements
are known as the CIELAB space coordinate system based around the theory of the three
opponent pairs of colour vision:
L* = lightness (0 = black, 100 = white)
a* = red-green (-a = green, +a = red)
b* = blue-yellow (-b = blue, +b = yellow)
[0084] For each fabric, an average of these values is then calculated. After washing, the
measurements are repeated. The changes in these values can thus be calculated. Given
that the dyes used are stable and no bleach is present in the system, the largest
change occurs in the lightness parameter - the actual shade of the fabric remains
relatively constant but the fabric becomes lighter.
[0085] Analysis of the data showed that the major changes were in the lightness (L*), as
the reactive dyes used are known for their light/oxidative stability and thus no major
changes in shade (which would be evident in the a and b colour coordinates). Thus,
a small ΔΔL* shows that the fabric has become only slightly lighter while a negative
ΔΔL shows that the fabric has actually become darker.
[0086] 9 wash Delta Delta L* (ΔΔL*) measurements (95% confidence limits in brackets):-
K = Knitted fabric, W = Woven fabric,
washed = fabric already washed 10 times, new = new fabric
| |
|
ΔΔL*-Control |
ΔΔL*-Comfort |
ΔΔL*-K-2010E |
ΔΔL*-Combo |
| BP1-K |
Washed |
1.471 (0.261) |
1.288 (0.228) |
0.740 (0.281) |
0.171 (0.272) |
| BP2-K |
Washed |
1.406 (0.145) |
1.715 (0.161) |
1.323 (0.130) |
0.985 (0.125) |
| BP3-K |
Washed |
0.177 (0.173) |
-0.087 (0.250) |
-0.489 (0.284) |
-1.248 (0.201) |
| BP4-K |
Washed |
1.248 (0.146) |
1.130 (0.218) |
0.786 (0.179) |
0.250 (0.269) |
| BP5-K |
Washed |
2.720 (0.181) |
2.638 (0.299) |
1.916 (0.321) |
1.465 (0.165) |
| BP3-W |
Washed |
0.889 (0.173) |
0.490 (0.222) |
0.414 (0.183) |
-0.015 (0.143) |
| BP4-W |
Washed |
1.126 (0.313) |
0.846 (0.237) |
0.740 (0.259) |
0.155 (0.202) |
| BP5-W |
Washed |
2.571 (0.210) |
2.263 (0.247) |
1.955 (0.381) |
1.564 (0.202) |
| BP1-K |
New |
1.303 (0.228) |
0.964 (0.184) |
0.429 (0.190) |
-0.569 (0.208) |
| BP2-K |
New |
1.183 (0.097) |
1.151 (0.189) |
0.984 (0.104) |
0.583 (0.196) |
| BP3-K |
New |
2.771 (0.137) |
2.281 (0.101) |
1.588 (0.151) |
1.161 (0.139) |
| BP4-K |
New |
1.986 (0.191) |
1.779 (0.297) |
1.250 (0.199) |
0.544 (0.203) |
| BP5-K |
New |
2.226 (0.161) |
1.899 (0.152) |
1.248 (0.131) |
0.495 (0.175) |
| BP3-W |
New |
0.712 (0.154) |
0.566 (0.161) |
0.295 (0.158) |
-0.567 (0.165) |
| BP4-W |
New |
1.224 (0.315) |
1.092 (0.422) |
0.752 (0.266) |
0.190 (0.295) |
| BP5-W |
New |
1.431 (0.182) |
0.979 (0.180) |
0.931 (0.354) |
0.204 (0.220) |
[0087] In all cases, the combination of Comfort and K2010E shows the largest benefit.
[0088] In four cases the combination has actually made the fabric slightly darker (producing
a negative ΔΔL* value).
[0089] The polymer can be incorporated into main wash powders or liquids (most preferably
those based around cationic surfactants) or rinse conditioner products.