Method for treating an animal substrate
[0001] This invention relates to an improved method for tanning an animal substrate, to
animal substrates obtained by said method and to articles comprising said tanned
substrates.
BACKGROUND
[0002] At present most of the output from the leather industry is derived from the tanning of
animal substrates (e.g. hides) using chromium III containing tanning agents to form an
intermediate leather substrate. This intermediate tanned substrate is also known as 'wet
blue'. Wet blue is typically re-tanned, dyed and finished. Chromium III is a particularly
effective tanning agent and provides leathers which perform exceptionally well, however
there is an increasing level of concern regarding the toxicology and environmental safety of
tanning agents containing chromium III compounds.
[0003] Attempts have been made to provide tanning agents and processes which are "freeof-
chromium" (FOC) and one such FOC option is referred to as "wet white". Generally, "wet
white" is a material obtained by tanning pickled hides/skins with pre-tanning agents such as
as aldehydes (e.g. glutaraldehyde), aluminium (III) based tanning products or synthetic
tanning agents (syntans).
[0004] Unfortunately, in many industrial applications, leathers derived from wet-white
processes do not perform as well as chromium III tanned (wet blue) leathers. In particular,
the hydrothermal stability, of wet white leather is substantially lower than that for chromium
III tanned leather. Generally, for wet white leather substrates, the shrinkage temperatures of
the final leathers do not exceed 90°C, and are typically in the region 70-80°C. Thus wetwhite
based leathers are not commonly used for applications where hydrothermal stability is
needed e.g. in steam forming as is often used in the manufacturing of shoes.
[0005] The performance requirements of automotive leathers can be especially stringent.
Automotive leathers can be required to have greater hydrothermal stability and resistance to
photochemical and/or thermal ageing in many demanding environments. Such requirements
are likely to become more important to the high-performance automotive leather in the
future.
[0006] It has also been observed by the present inventors that known tanning processes
tend not to provide conditions which facilitate suitably deep penetration of the tanning agents
into the substrate, especially when small amounts of fluid (e.g. water) are employed.
[0007] In view of the foregoing there is a need for a method of tanning an animal substrate
using an efficient, environmentally kind process, utilizing a chromium-free tanning agent
which provides a resulting substrate with one or more of the following desirable properties:
1. High hydrothermal stability relative to those normally obtainable with wet white
processes;
2 . High photochemical / thermal resistance relative to those normally obtainable with
wet white processes;
3 . High levels of incorporation of the tanning agent;
4 . Deep penetration of the tanning agent into the substrate.
[0008] It is also an object of the present invention to provide a method which achieves
sufficiently tanned animal substrates more rapidly.
[0009] The present invention has as its objectives the provision of a tanning process,
resulting tanned animal substrates and final articles comprising the tanned animal substrates
which addresses, at least in part, one or more of these needs.
BRIEF SUMMARY OF THE DISCLOSURE
[0010] According to a first aspect of the present invention there is provided a method for
tanning an animal substrate comprising the steps:
i) agitating the animal substrate with a chromium-free tanning agent; and
ii) agitating the animal substrate with a tanning agent having an oxazolidine group;
wherein at least some of the agitation is performed in the presence of a solid particulate
material, and wherein the solid particulate material has an average particle size of from 1 to
500mm.
[0011] Steps i) and ii) may be performed separately, simultaneously or the steps i) and ii)
overlap in time.
[0012] Preferably, the steps i) and ii) are performed in the order step i) followed by step ii).
[0013] At least some of the agitation in both steps i) and ii) is suitably performed in the
presence of the particulate solid material.
[0014] Preferably, the solid particulate material has an average particle size of from 1 to
100mm, more typically the solid particulate material has an average particle size of from 1 to
50mm.
[0015] The solid particulate material preferably has a density of from 1.0 to 5.0g/cm3.
[0016] Typically, the chromium-free tanning agent is one or more tanning agents selected
from vegetable tanning agents, synthetic tanning agents and aldehydes, more typically a
vegetable tanning agent. The chromium-free tanning agent may also be or comprise one or
more mineral tanning agents other than those containing chromium including those
containing aluminium, titanium, zirconium or iron salts or complexes or combinations thereof.
[0017] Typically, the vegetable tanning agent is a catechol-type tanning agent, more
typically the vegetable tanning agent is or comprises a catechol.
[0018] Typically, the vegetable tanning agent is or comprises an extract selected from
mimosa, birch, hemlock, quebracho, alder, fir and oak or a chemical derivative thereof, more
typically the vegetable tanning agent is or comprises an extract from mimosa or a chemical
derivative thereof.
[0019] The chromium-free tanning agent may be sulphited although preferably the
chromium-free tanning agent is not sulphited. This is especially so in the case of vegetable
tanning agents.
[0020] The chromium-free tanning agent(s) is/are preferably present in a total amount of
from 0.1 to 100wt% relative to the weight of animal substrate.
[0021] Typically the tanning agent having an oxazolidine group has one or more oxazolidine
groups of the chemical Formula (1) or (2):
Formula (1)
Formula (2),
[0022] Preferably, the tanning agent having an oxazolidine group is of the Formula (3), (4) or
(5):
Formula (4)
CHzOH
Formula (5).
[0023] The tanning agent having an oxazolidine group is preferably present in an amount of
from 0.1 to 100% by weight relative to the weight of animal substrate.
[0024] Typically, step i) is performed at a pH of no more than 5 , more typically at a pH of no
more than 4.5.
[0025] Typically, step ii) is performed at a pH of at least 5 , more typically a pH of at least 6 .
[0026] Optionally, the method according to the first aspect of the present invention
additionally comprises a tanning step A) of agitating the animal substrate with an aldehydecontaining
tanning agent, which typically is or comprises glutaraldehyde.
[0027] The tanning step A) typically precedes step i).
[0028] Preferably, the solid particulate material is or comprises a polymeric or non-polymeric
material, more typically is or comprises a polymeric material. Suitable polymeric materials
can be selected from polyalkylenes, polyesters, polyamides and polyurethanes including
mixtures and copolymers thereof.
[0029] Preferably, the weight ratio of animal substrate : solid particulate material is from 5:1
to 1:5.
[0030] Preferably, at least some of the agitation steps are performed for at least some of the
time in the presence of water.
[0031] Typically, when water is present the weight ratio of animal substrate to water is from
1:5 to 100:1 .
[0032] Preferably, the animal substrate is or comprises an animal hide, which is preferably
selected from animal hides obtained from cows, pigs, goats and sheep.
[0033] The method may comprise one or more subsequent steps selected from dyeing,
drying, coating, lacquering, polishing, cutting, shaping, forming, embossing, punching,
gluing, sewing, stapling and packaging the tanned animal substrate.
[0034] According to a second aspect of the invention there is provided an animal substrate
obtained by the method according to the first aspect of the present invention.
[0035] According to a third aspect of the present invention there is provided an article which
is or comprises an animal substrate according to the second aspect of the present invention
wherein said article is selected from one or more of: articles of apparel and personal
accessories, footwear, bags, briefcases and suitcases, covers for phones, tablets and
laptops, saddlery, furniture and upholstered articles, sporting goods and accessories, pet
collars and leashes, and vehicle interior coverings.
DETAILED DESCRIPTION
FIGURES
[0036] Figure 1 is a depiction of a thermogram obtained from a differential scanning
calorimeter. It shows how the shrinkage onset temperature is obtained.
ORDER OF METHOD STEPS
[0037] The steps in the method according to the present invention can be performed in any
order. Step ii) may be followed by step i), although more typically step i) is followed by step
ii).
[0038] The steps i) and ii) can be performed separately, simultaneously or the steps i) and ii)
overlap in time. Preferably, steps i) and ii) are performed substantially separately. The
separation of each step has been found to be particularly desirably so as to control the
conditions of the tanning processes in each step. Such conditions include temperature, time
and especially pH. Controlling the pH of steps i) and ii) has been found to be particularly
desirable to provide better tanning results.
SOLID PARTICULATE MATERIAL
[0039] The solid particulate material has an average particle size of from 1 to 500mm, more
typically from 1 to 100mm, even more typically from 1 to 50mm, especially typically from 1 to
10mm and most typically from 2 to 8mm.
[0040] In other embodiments the solid particulate material has an average particle size of
from 1.0 to 5.0 mm and in further embodiments of from 2.5 to 4.5 mm.
[0041] The average is a number average. The average is preferably performed on at least
10, more preferably at least 100 particles and especially at least 1000 particles.
[0042] The size of each particle is established by measuring the volume of particle and
then assuming it is a sphere and calculating the effective diameter corresponding to a
sphere having that volume; the effective diameter is then taken to be the particle size.
[0043] Preferably, the solid particulate material has a length of from 1 to 500 mm and in
particular from 1 to 100 mm. Typically, the solid particulate material has a length of from 1 to
25 mm, or from 1 to 15mm or from 1 to 10mm, or from 1 to 6.0 mm, or from 1.0 to 5.0 mm or
from 2.5 to 4.5 mm. The length can be defined as the maximum dimension of each threedimensional
solid particle. The average is preferably a number average. The average is
preferably performed on at least 10, more preferably at least 100 particles and especially at
least 1000 particles of the solid particulate material.
[0044] Preferably, the solid particulate material can comprise a multiplicity of polymeric
particles, a multiplicity of non-polymeric particles or a mixture of a multiplicity of polymeric
and non-polymeric particles.
[0045] The solid particulate material typically is or comprises a polymeric or non-polymeric
material.
[0046] The polymeric or non-polymeric particles can comprise or be in the form of beads.
[0047] Preferably, a polymeric particle has an average volume of from 1 to 500 mm3, more
preferably from 5 to 275 mm3.
[0048] Preferably, the polymer in the polymeric particles is or comprises polyalkenes,
polyamides, polyesters, polysiloxanes, polyurethanes or copolymers thereof.
[0049] Thus, the polymer in the polymeric particles can be or comprise polyalkenes or
polyurethanes, or copolymers thereof.
[0050] Thus, the polymer in the polymeric particles can be or comprise polyamide or
polyester or copolymers thereof.
[0051] Preferably, said polyamide is or comprises Nylon.
[0052] Preferably, the polyamide is or comprises Nylon 6 or Nylon 6,6.
[0053] Preferably, the polyester is or comprises polyethylene terephthalate or polybutylene
terephthalate.
[0054] The solid particulate material can be partially or substantially soluble. Typically,
however the solid particulate material is substantially insoluble. Preferably, the fluid in which
solubility or insolubility is determined is water, more preferably water at pH 7.0, and
especially water at a temperature of 25°C. For the purposes of this invention the solid
particulate material is determined to be insoluble if the solubility is less than 5wt%, more
typically less than 1wt% in a given fluid (typically water).
[0055] The particles of the solid particulate material can be chemically modified to include
one or more moieties selected from the group consisting of: enzymes, oxidizing agents,
catalysts, metals, reducing agents, chemical cross-linking agents and biocides.
[0056] Preferably, the non-polymer in the non-polymeric particles is or comprises ceramic
material, refractory material, igneous, sedimentary or metamorphic minerals, composites,
metal or glass.
[0057] The solid particulate material may be in the shape of cylinders, ellipsoids, spheres,
cuboids and shapes which are intermediates between these. Of these ellipsoids, spheres
and the shapes in-between are preferred.
[0058] Typically, the particulate solid material has a density of from 0.5 to 20g/cm3, more
typically from 1 to 10g/cm3, even more typically from 1 to 8g/cm3, yet more typically from 1 to
5g/cm3. Where the particulate solid material is or comprises a polymer the density is
preferably from 1 to 3g/cm3, especially from 1.2 to 2.5g/cm 3 and most especially from 1.3 to
2.0g/cm 3. Such densities are considered to provide a particularly good balance of
mechanical action and separation efficiency to aid separation of the particulate solid material
from the substrate after the tanning steps.
[0059] The agitation steps i) or ii) may be performed in the presence of the particulate solid
material, and preferably the agitation steps in both i) and ii) are performed in the presence of
the particulate solid material.
[0060] At least some of the agitation in step i) and/or step ii) is performed in the presence of
the particulate solid, more preferably at least some of the agitation in each of steps i) and ii)
is performed in the presence of the particulate solid material, and more preferably at least
some of the agitation in both of steps i) and ii) is performed in the presence of the particulate
solid material..
[0061] Preferably, the particulate solid material is present in step i) and/or step ii) for at least
50, 60, 70, 80, 90 or 95% of the time taken for the step or steps.
[0062] Preferably the agitation in steps i) and/or ii) is performed entirely in the presence of
the particulate solid material, and more preferably the agitation in steps i) and ii) is performed
entirely in the presence of the particulate solid material.
[0063] Preferably, the particulate solid material is re-used in one or more subsequent
tanning methods according to the first aspect of the present invention.
CHROMIUM FREE TANNING AGENT
[0064] At least one chromium-free tanning agent must be present in step i). A plurality of
chromium-free tanning agents can be present in step i). Preferably, no tanning agent present
in step i) is a chromium-containing tanning agent, more preferably no tanning agent present
in step i) and step ii) is a chromium-containing tanning agent, yet more preferably no tanning
agent present in any part of the tanning process is a chromium-containing tanning agent.
[0065] Suitable chromium-free tanning agents include those selected from vegetable tanning
agents, synthetic tanning agents and aldehydic tanning agents (especially aldehydes). Other
suitable chromium-free tanning agents include mineral tanning agents including, for
example, tanning agents containing aluminium, titanium, zirconium and iron. Of these
vegetable tanning agents have been found to be especially suitable for providing tanned
animal substrates having desirable hydrothermal stability.
[0066] The vegetable tanning agent preferably is or comprises a catechol. Preferably, the
vegetable tanning agent is or comprises an extract selected from mimosa, birch, hemlock,
quebracho, alder, fir and oak or a chemical derivative thereof. Of these mimosa extracts and
chemical derivatives thereof have been found to be especially suitable for hydrothermal
stability. Vegetable tanning agents are often extracts from leaves or more commonly bark.
[0067] The chromium-free tanning agent (especially the vegetable tanning agent) can be
sulphited but is more preferably not sulphited.
[0068] The chromium-free tanning agent(s) is/are present in a total amount of from 0.1 to
100wt%, more preferably from 1 to 100wt%, even more preferably from 1 to 50wt% and yet
more preferably from 1 to 20wt% relative to the weight of animal substrate. The weight refers
to the wet weight of the animal substrate. The amounts refer to the active or dry amount of
the tanning agent(s).
CONDITIONS FOR STEP i)
[0069] Preferably step i) is performed at a temperature of from 5 to 95°C, more preferably
from 5 to 80°C and especially from 5 to 60°C.
[0070] Step i) is typically performed for a period of from 10 minutes to 10 hours, more
typically from 10 minutes to 5 hours and most typically from 30 minutes to 4 hours.
[0071] Step i) can be performed at a pH of from 1 to 10, more typically from 2 to 10, even
more typically at a pH of from 2 to 8 and especially a pH of from 3 to 6 .
[0072] Step i) can be performed at a pH of no more than 7 , more typically no more than 6 ,
even more typically no more than 5 , yet more typically at a pH of no more than 4.5. The
lower limit for the pH is typically pH 1, 2 or 3 .
OXAZOLIDINE TANNING AGENT
[0073] It has been found that oxazolidine tanning agents are particularly effective when used
in conjunction with chromium-free and more especially vegetable tanning agents.
[0074] The oxazolidine group in the oxazolidine tanning agent can be a 1,2-oxazolidine (also
known as an isoxazolidine) but is preferably 1,3-oxazolidine.
[0075] Preferably, the tanning agent having an oxazolidine group has one or more
oxazolidine groups of the chemical Formula (1) or (2):
Formula (1)
Formula (2).
[0076] Especially suitable tanning agents having an oxazolidine group are those of the
Formula (3), (4) and (5):
Formula (3)
Formula (4)
CH;:OH
Formula (5).
[0077] The tanning agent of Formula (3) is 4,4-Dimethyl-1-oxa-3-aza -cyclopentane and has
a more trivial name Oxazolidine A.
[0078] The tanning agent of Formula (4) is 5-Ethyl-1-aza-3,7-dioxabyciclo [3,3,0] octane and
has a more trivial name Oxazolidine E.
[0079] The tanning agent of Formula (5) is 5-Hydroxymethyl-1- aza-3,7-dioxabyciclo [3,3,0]
octane and has a more trivial name Oxazolidine T.
[0080] Oxazolidine A, E and T have been found to be particularly effective oxazolidine
tanning agents especially in conjunction with vegetable tanning agents.
[0081] Suitable oxazolidines can be obtained from Trumpler GmbH under the Trupotan
tradename or from Angus chemicals Ltd under the Zolidine trade name.
[0082] The tanning agent containing an oxazolidine group used in step ii) of the present
invention is preferably chromium-free. Preferably, no tanning agent present in step ii) is a
chromium-containing tanning agent.
[0083] For clarification a tanning agent which is both chromium-free and which has an
oxazolidine group is preferably regarded, for the purposes of this invention, as a tanning
agent having an oxazolidine group. Accordingly, the chromium-free tanning agent in step i)
preferably has no oxazolidine groups.
[0084] Typically, the tanning agent having an oxazolidine group is present in an amount of
from 0.1 to 100%, more typically from 1 to 50wt%, especially typically from 1 to 20wt% by
weight relative to the weight of animal substrate. The weight refers to the wet weight of the
animal substrate. The amount of tanning agent is based on the active or dry amount.
CONDITIONS FOR STEP ii)
[0085] Step ii) is typically preformed for a period of from 10 minutes to 10 hours, more
typically from 30 minutes to 5 hours and most typically from 1 to 4 hours.
[0086] Step ii) is preferably performed at a temperature of from 5 to 95°C, more preferably
from 10 to 80°C and especially from 20 to 80°C and most especially from 35 to 65°C.
[0087] Typically, step ii) is performed at a pH of at least 3 , more typically at least 4 , even
more typically at least 5 , yet more typically at a pH of at least 6 . The upper limit for the pH
may be 12, 11, 10, 9 , 8 or more typically 7 . Step ii) can be performed at a pH of from 3 to 10,
more typically at a pH of from 5 to 10, especially at a pH of from 5 to 9 and most especially a
pH of from 6 to 7 .
PRE-TANNING - STEP A)
[0088] The method according to the first aspect of the present invention can additionally
comprises a tanning step A) of agitating the animal substrate with an aldehyde-containing
tanning agent.
[0089] Preferably, the aldehyde-containing tanning agent in step A) is or comprises
glutaraldehyde.
[0090] Preferably, the optional tanning step A) precedes tanning step i).
[0091] The amount of aldehyde-containing tanning agent present during step A) is typically
from 0.1 to 100wt%, more typically from 1 to 50wt% and especially from 1 to 20wt% based
on the weight of animal substrate. The weight of animal substrate is calculated based on the
wet weight.
[0092] Preferably, the agitation in step A) is performed at least partly, more preferably
entirely in the presence of the particulate solid material.
[0093] Step A) is preferably conducted at a pH of from 1 to 5 , more preferably from 2 to 4
and especially at a pH of around 2.5 to 3.5.
AGITATION
[0094] The agitation in any of the steps i) or ii) or optional steps such as A) can be of any
kind. Preferred kinds of agitation include shaking, stirring, ultrasonication and especially
rotating. Rotation so as to cause the animal substrate to tumble is especially preferred.
[0095] The agitation need not be conducted for any entire tanning time. The agitation may
be continuous or intermittent.
[0096] The agitation is preferably achieved by rotating an animal substrate in a drum. The
drum may additionally contain a fluid. The drum preferably also contains the particulate solid
material.
ANIMAL SUBSTRATE
[0097] Preferably, the animal is or comprises an animal skin or more preferably a hide.
[0098] Preferably the animal hide is selected from animal hides obtained from cows, pigs,
goats and sheep, of these cow hides are especially preferred.
FLUIDS AND WATER
[0099] Preferably, at least some of the agitation steps are performed for at least some of the
time in the presence of a fluid, which preferably is or comprises a liquid, which preferably is
or comprises water. When water is present it preferably has the pH values in steps i) and/or
ii) as previously mentioned herein.
[00100] More preferably, both of the agitation steps i) and ii) are performed for at least
some of the time in the presence of a liquid medium, which preferably is or comprises water.
Similarly, it is preferred that step A) is performed for at least some of the time in the
presence of a liquid medium, which preferably is or comprises water.
[00101] Fluids (e.g. water) may be added to the animal substrate or to the particulate
solid. The fluids (e.g. water) are typically introduced with the chromium-free and/or
oxazolidine group-containing tanning agents. Fluids (e.g. water) may be added prior to,
during or after agitation steps i) or ii)
REMOVAL OF PARTICULATE SOLID
[00102] Preferably, after completion of the tanning method according to the first
aspect of the present invention the particulate solid material is removed from the tanned
animal substrate.
[00103] The removed particulate solid material can then be stored and is preferably
re-used in subsequent tanning methods according to the first aspect of the present invention.
RATIOS
[00104] Preferably, the weight ratio of animal substrate : particulate solid material is
from 10:1 to 1:10, more preferably from 5:1 to 1:5, preferably from 3:1 to 1:3, preferably from
2:1 to 1:2. Preferably, the weight of the animal substrate for this ratio is based on the wet
weight of the animal substrate.
[00105] Preferably, the weight ratio of the animal substrate : fluid, as used herein,
refers to the weight of the fluid added prior to, during or after step i) and step ii) and, when
present, step A). The weight ratio of the animal substrate : fluid, as used herein preferably
excludes any fluid associated with the optional moistening step described herein and/or
preferably excludes any latent fluid (typically water) present within the animal substrate itself.
[001 06] Preferably, throughout this invention the dry weight of a wet substrate is from
25 to 75wt% of the wet weight, typically about 50wt%. So for example, 2kgs of wet animal
substrate comprises 1kg of dry animal substrate.
[00107] Preferably, the weight ratio of the animal substrate : fluid (especially water) is
from about 1:5 to about 100:1 , typically from about 1:2, typically from about 1:1, and typically
from about 2:1 , typically from about 3:1 and typically from about 5:1, typically no more than
about 40:1 , typically no more than about 30:1, typically no more than about 20:1 , and
typically no more than about 15:1 . Preferably the weight of the animal substrate is based on
the wet weight of the animal substrate.
[00108] Preferably, the weight ratio of the dry animal substrate : fluid is 10:1 to 1:10,
more preferably 7:1 to 1:7, even more preferably 4:1 to 1:4, yet more preferably 3:1 to 1:3
and most preferably 2:1 to 1:2 by weight.
[00109] Preferably, the ratio of the volume of the drum (in m3) : to the weight of fluid in
the drum (in metric tonnes) is from about 1:100 to about 100: 1.
[001 10] Preferably, the ratio of the volume of the drum (in m3) : to the weight of fluid in
the drum (in metric tonnes) is in order of increasing preference at least 1:4, 1:3, 1:2, 1:1, 2:1,
3:1 , 4:1 , 5:1, 10:1 , 20:1 , 25:1 , 30:1, 35:1 , 40:1, 45:1, 50:1 , 60:1 and 70:1 .
[001 11] In some cases the ratio of the volume of the drum (in m3) : to the weight of
fluid in the drum (in metric tonnes) is in order of increasing preference no more than about
75: 1, no more than 60: 1, no more than 50: 1, no more than 40: 1, no more than 30: 1, no more
than 25: 1, no more than 20: 1 and no more than 15:1.
[001 12] Thus, a preferred method for tanning an animal substrate according to the first
aspect of the present invention comprises the steps of:
A) agitating the animal substrate with an aldehyde-containing tanning agent.
i) agitating the animal substrate with a chromium-free tanning agent; and
ii) agitating the animal substrate with a tanning agent having an oxazolidine group;
wherein the steps are performed in the order of step A) followed by step i) followed by step
ii), preferably wherein the animal substrate is a moistened animal substrate;
wherein at least some of the agitation is performed in the presence of a solid particulate
material (and preferably wherein at least some of the agitation in each of steps A) and i) and
ii) is performed in the presence of the particulate solid material, and preferably wherein all of
the agitation in each of steps A) and i) and ii) is performed in the presence of the particulate
solid material);
wherein the solid particulate material has an average particle size of from 1 to 500mm;
wherein the chromium-free tanning agent is one or more tanning agents selected from
vegetable tanning agents, synthetic tanning agents and aldehydes (and is preferably a
vegetable tanning agent) and is present in a total amount of from 0.1 to 100wt% relative to
the weight of animal substrate;
wherein the tanning agent having an oxazolidine group is present in an amount of from 0.1 to
100% by weight relative to the weight of animal substrate;
wherein the weight ratio of animal substrate : solid particulate material is from 10:1 to 1: 0
(preferably from 2:1 to 1:2);
wherein at least some of the agitation steps are performed for at least some of the time in
the presence of water and wherein the weight ratio of animal substrate to water is from 1:5 to
100:1 (preferably from 1:1 to 15:1).
OPTIONAL ADDITIONAL METHOD STEPS
[001 13] The method according to the first aspect of the present invention is preferably
conducted on a moistened animal substrate. A moistened animal substrate preferably
exhibits a weight ratio of fluid : animal substrate of from about 1:1000 to about 10:1 ,
preferably from about 1:100 to about 10:1 , preferably from about 1:10 to about 10:1,
preferably from about : to about 10:1 . Preferably the fluid is or comprises water. Where
weight ratios are defined herein with reference to the "wet weight" of the animal substrate,
said "wet weight" refers to the moistened animal substrate. Thus, the method of the first
aspect of the invention is preferably preceding by the step of moistening the animal substrate
with a fluid, preferably by moistening with water, and where said method comprises a pretanning
step A) as described herein then the moistening step is preferably conducted prior to
the pre-tanning step A).
[001 14] The method according to the first aspect of the present invention may be
preceded by any one or more of the following steps including: skinning, curing, soaking,
liming, de-hairing and scudding, de-liming, bating and pickling, and where said method
comprises the pre-tanning step A) as described herein then said preceding step(s) is/are
preferably conducted prior to the pre-tanning step A). Said preceding step(s) may result in a
moistened animal substrate for use in the method of the present invention.
[001 15] The method according to the first aspect of the present invention can be
followed by any one or more of the following steps including: dyeing, drying, coating,
lacquering, polishing, cutting, shaping, forming, embossing, punching, gluing, sewing,
stapling and packaging the tanned animal substrate.
FURTHER ASPECTS OF THE INVENTION
[001 16] According to a fourth aspect of the invention, there is provided the use of a
solid particulate material in a method for tanning an animal substrate wherein said method
comprises the steps of (i) agitating the animal substrate with a chromium-free tanning agent
and (ii) agitating the animal substrate with a tanning agent having an oxazolidine group,
wherein at least some of the agitation is performed in the presence of a solid particulate
material, wherein the solid particulate material has an average particle size of from 1 to
500mm, and wherein said use is for the purpose of improving one or more properties
selected from the group consisting of:
(1) hydrothermal stability;
(2) photochemical and/or thermal resistance;
(3) the degree of incorporation of the tanning agent into said substrate; and
(4) the degree of penetration of the tanning agent into said substrate.
[001 17] According to a fifth aspect of the invention, there is provided a tanning method
for improving one or more properties of an animal substrate, wherein said properties are
selected from the group consisting of:
(1) hydrothermal stability;
(2) photochemical and/or thermal resistance;
(3) the degree of incorporation of a tanning agent into said substrate; and
(4) the degree of penetration of a tanning agent into said substrate,
wherein said method comprises the steps of (i) agitating the animal substrate with a
chromium-free tanning agent and (ii) agitating the animal substrate with a tanning agent
having an oxazolidine group, wherein at least some of the agitation is performed in the
presence of a solid particulate material, and wherein the solid particulate material has an
average particle size of from 1 to 500mm.
[001 18] In the fourth and fifth aspects of the invention, the improvement of said
properties is relative to a tanning method in which said solid particulate material is not used.
[001 19] In the fourth and fifth aspects, an improvement in hydrothermal stability is
particularly preferred, optionally in combination with improvement in one or more of the
other properties defined in the fourth and fifth aspects. Herein, hydrothermal stability is
preferably determined as the shrinkage onset temperature of a moist sample measured by
differential scanning calorimetry at 5°C/minute over a temperature range of 20 to 140°C.
Preferably, the method of the present invention provides an animal substrate which exhibits
a shrinkage onset temperature of at least 95°C, preferably at least 98°C and preferably at
least 100°C.
[00120] In all cases the shrinkage onset temperature is preferably measured by a
calorimeter, especially a differential scanning calorimeter (DSC), which is preferably
operated in accordance with BS EN ISO 11357-3:2013. The preferred temperature range is
20 to 140°C. The preferred scanning speed is 5°C/min. A preferred calorimeter is a : Mettler
Toledo 822e DSC. The shrinkage onset temperature is preferably recorded as the point (a)
where the baseline intersects with the tangent at the inflection point in the DSC curve as
shown in Figure 1 (i.e. the first inflection point in the DSC curve). Thermograms are
preferably analysed using Star Software (v 1.13) recording onset/ peak temperature and the
integral is preferably normalised (suitably assuming a normal distribution around the peak
temperature).
[00121] All features of the first aspect of the invention described hereinabove, and
combinations of said features, are applicable to the fourth and fifth aspect of the inventions.
[00122] The animal substrate of the second aspect of the invention exhibits an
improvement in one or more properties selected from the group consisting of:
(1) hydrothermal stability;
(2) photochemical and/or thermal resistance;
(3) the degree of incorporation of the tanning agent into said substrate; and
(4) the degree of penetration of the tanning agent into said substrate,
relative to an animal substrate prepared by a tanning method in which said solid particulate
material is not used. In particular, the animal substrate of the second aspect of the invention
preferably exhibits a shrinkage onset temperature of at least 95°C, preferably at least 98°C
and preferably at least 100°C.
[00123] According to a sixth aspect of the invention, there is provided a tanned animal
substrate which is chromium-free and which exhibits an improvement in one or more
properties selected from the group consisting of:
(1) hydrothermal stability;
(2) photochemical and/or thermal resistance;
(3) the degree of incorporation of the tanning agent into said substrate; and
(4) the degree of penetration of the tanning agent into said substrate,
relative to an animal substrate prepared by a tanning method in which a solid particulate
material is not used. In particular, the animal substrate of the sixth aspect of the invention
preferably exhibits a shrinkage onset temperature of at least 95°C, preferably at least 98°C
and preferably at least 100°C.
[00124] According to a seventh aspect of the invention, there is provided a tanned
animal substrate which is chromium-free and which exhibits a shrinkage onset temperature
of at least 95°C, preferably at least 98°C and preferably at least 100°C.
[00125] As used herein, the term "chromium-free" when applied to a tanned animal
substrate preferably means an extractable chromium content of less than 0.1 mg/kg,
preferably less than 0.01 mg/kg, preferably less than 0.001 mg/kg, and preferably 0 mg/kg
(expressed in mg of chromium per kg of animal substrate and preferably measured
according to ISO-17072).
[00126] According to an eighth aspect of the present invention there is provided an
article which is or comprises an animal substrate according to the sixth or seventh aspects of
the present invention wherein said article is selected from one or more of: articles of apparel
and personal accessories, footwear, bags, briefcases and suitcases, covers for phones,
tablets and laptops, saddlery, furniture and upholstered articles, sporting goods and
accessories, pet collars and leashes, and vehicle interior coverings.
DEFINITIONS
[00127] In the present invention any item mentioned in the singular is, unless the
invention indicates to the contrary to be regarded as also encompassing the plural. Thus, by
example, a chromium-free tanning agent includes one or more chromium-free tanning
agents. Equally, a solid particulate material includes one or more particulate solid materials.
EXAMPLES
[00128] The invention will now be further illustrated, though without in any way limiting the
scope thereof, by reference to the following examples.
COMPARATIVE EXAMPLE 1
[00129] In step A) wet pickled bovine hides (Scottish Leather Group, UK) were tanned
by tumbling the hides with 3wt% based on hides of a poly-glutaraldehyde product (Selletan
WL-G) (TFL GmbH) at pH 3.0-4.2, at a temperature of 35°C over a period of 4 hours..
[00130] In step i) the hides resulting from step A) were partially dried to a moisture
content of 35% using mechanical extraction and then shaved to thickness of 1.4mm, the
hides were then tanned by tumbling the hides with a vegetable tannin (10wt% based on
hides) Mimosa ME (Forestal Ltd. SA) at pH of 6.5 and a temperature of 35°C for a period of
4 hours.
[00131] In step ii) the hides resulting from step i) were further tanned by tumbling with
an oxazolidine tanning agent, namely Trupotan OXB (15wt% based on the hides) (Trumpler
GmbH, Worms, Germany) at a pH of 6.5, a temperature of from 40-60°C for a period of 4
hours.
[00132] During the tumbling steps the wet animal substrate: water ratio was 10 : 15 by
weight.
[00133] In each case the tumbling was performed in a Dose leather processing drum
(Ring Maschinenbau GmbH (Dose), Lichtenau, Germany) (model 08-60284 with an internal
volume of 85L).
[00134] This prepared Comparative Leather (1).
EXAMPLE 1
[001 35] Solid particulate material in the form of Teknor Apex™ grade TA10 1M
(Polyester - PET) beads supplied by Teknor Apex UK was used in this Example. The PET
beads had a particle size of about 4mm and a density of about 1.4g/cm3 the shape of the
particles was largely ellipsoidal. Example 1 was performed exactly as was Comparative
Example 1 except that beads were present with a wet animal substrate: PET beads: water
ratio of 10 : 14 : 1.0 on a weight basis. The beads were present in steps A), i) and ii).
[00136] This prepared Leather (1) by a method according to the first aspect of the
present invention.
LEATHER ANALYSIS
[00137] The shrinkage onset temperatures of leather prepared in the above examples
were measured using a differential scanning calorimeter (DSC) (model: Mettler Toledo 822e
DSC). A moist leather sample was scanned at 5°C/minute over the temperature range 20-
140°C with reference to an empty weighed, pierced aluminium pan. The calorimeter was
otherwise operated generally in accordance with BS EN ISO 11357-3:2013. The shrinkage
onset temperature is recorded as the point (a) where the baseline intersects with the tangent
at the inflection point in the DSC curve as shown in Figure 1 (i.e. the first inflection point in
the DSC curve). Thermograms were analysed using Star Software (v 1.13) recording onset/
peak temperature and the integral was normalised (suitably assuming a normal distribution
around the peak temperature).
RESULTS
[001 38] Table 1. Showing the effect of the presence of the particulate solid
material on shrinkage temperature.
[001 39] If the shrinkage onset temperature was equal to or greater than 100°C (as
measured by DSC) then the leather was deemed to have been especially well tanned. As
per Table 1, it was shown that the presence of a particulate solid material resulted in
significant improvements in shrinkage temperature compared with a method where the
particulate solid material was not present. The improved hydrothermal stability as shown by
the higher onset shrinkage temperature demonstrates that the tanning reactions progressed
to a greater extent in the method of the present invention.
[00140] In addition the process for making Leather (1) involved the use of a
significantly lower quantity of water as compared to the process used for making
Comparative Leather (1).

CLAIMS
1. A method for tanning an animal substrate comprising the steps:
i) agitating the animal substrate with a chromium-free tanning agent; and
ii) agitating the animal substrate with a tanning agent having an oxazolidine
group;
wherein at least some of the agitation is performed in the presence of a solid particulate
material, and wherein the solid particulate material has an average particle size of from 1 to
500mm.
2 . A method according to claim 1 wherein the steps i) and ii) are performed separately,
simultaneously or where steps i) and ii) overlap in time.
3 . A method according to claim 1 wherein steps i) and ii) are performed in the order step
i) followed by step ii).
4 . A method according to any one of the preceding claims wherein at least some of the
agitation in both steps i) and ii) is performed in the presence of the particulate solid material.
5 . A method according to any one of the preceding claims wherein the solid particulate
material has an average particle size of from 1 to 50mm.
6 . A method according to claim 5 wherein the solid particulate material has an average
particle size of from 1 to 10mm.
7 . A method according to any one of the preceding claims wherein the solid particulate
material has a density of from 1.0 to 5.0g/cm3.
8 . A method according to any one of the preceding claims wherein the chromium-free
tanning agent is one or more tanning agents selected from vegetable tanning agents,
synthetic tanning agents and aldehydes.
9 . A method according to claim 8 wherein the chromium-free tanning agent is or
comprises a vegetable tanning agent.
10. A method according to claim 9 wherein the vegetable tanning agent is or comprises a
catechol.
11. A method according to claim 9 wherein the vegetable tanning agent is or comprises
an extract selected from mimosa, birch, hemlock, quebracho, alder, fir and oak or a chemical
derivative thereof.
12. A method according to claim 11 wherein the vegetable tanning agent is or comprises
an extract from mimosa or a chemical derivative thereof.
13. A method according to claim 1 wherein the chromium-free tanning agent is not
sulphited.
14. A method according to any one of the preceding claims wherein the chromium-free
tanning agent(s) is/are present in a total amount of from 0.1 to 100wt% relative to the weight
of animal substrate.
15. A method according to any one of the preceding claims wherein the tanning agent
having an oxazolidine group has one or more oxazolidine groups of the chemical Formula (1)
or (2):
Formula (1)
Formula (2).
16. A method according to any one of the preceding claims wherein the tanning agent
containing an oxazolidine group is of the Formula (3), (4) and (5):
Formula (3)
Formula (5).
17. A method according to any one of the preceding claims wherein the tanning agent
having an oxazolidine group is present in an amount of from 0 .1 to 100% by weight relative
to the weight of animal substrate.
18. A method according to any one of the preceding claims wherein step i) is performed
at a pH of no more than 5 .
19. A method according to claim 18 wherein step i) is performed at a pH of no more than
4.5.
20. A method according to any one of the preceding claims wherein step ii) is performed
at a pH of at least 5 .
2 1. A method according to claim 20 wherein step ii) is performed at a pH of at least 6 .
22. A method according to any one of the preceding claims which additionally comprises a
tanning step A) of agitating the animal substrate with an aldehyde-containing tanning agent.
23. A method according to claim 22 wherein the aldehyde-containing tanning agent in step A) is
or comprises glutaraldehyde.
24. A method according to claim 22 or claim 23 wherein the tanning step A) precedes step i).
25. A method according to any one of the preceding claims wherein the solid particulate
material is or comprises a polymeric or non-polymeric material.
26. A method according to claim 25 wherein the solid particulate material is a polymeric
material selected from polyalkylenes, polyesters, polyamides and polyurethanes
including mixtures and copolymers thereof.
27. A method according to any one of the preceding claims wherein the weight ratio of
animal substrate : solid particulate material is from 5:1 to 1:5.
28. A method according to any one of the preceding claims wherein at least some of the
agitation steps are performed for at least some of the time in the presence of water.
29. A method according to claim 28 wherein the weight ratio of animal substrate to water is
from 1:5 to 100:1.
30. A method according to any one of the preceding claims wherein the animal substrate is a
moistened animal substrate, preferably wherein said moistened animal substrate
exhibits a weight ratio of water : animal substrate of from about 1:10 to about 10:1.
3 1. A method according to any one of the preceding claims wherein the animal substrate is
or comprises an animal hide.
32. A method according to claim 3 1 wherein the animal hide is selected from animal hides
obtained from cows, pigs, goats and sheep.
33. A method according to any one of the preceding claims comprising one or more
subsequent steps selected from dyeing, drying, coating, lacquering, polishing, cutting,
shaping, forming, embossing, punching, gluing, sewing, stapling and packaging the
tanned animal substrate.
34. An animal substrate obtained by the method according to any one of the preceding
claims.
35. The use of a solid particulate material in a method for tanning an animal substrate
wherein said method comprises the steps of (i) agitating the animal substrate with a
chromium-free tanning agent and (ii) agitating the animal substrate with a tanning agent
having an oxazolidine group, wherein at least some of the agitation is performed in the
presence of a solid particulate material, wherein the solid particulate material has an
average particle size of from 1 to 500mm, and wherein said use is for the purpose of
improving one or more properties selected from the group consisting of:
(1) hydrothermal stability;
(2) photochemical and/or thermal resistance;
(3) the degree of incorporation of the tanning agent into said substrate; and
(4) the degree of penetration of the tanning agent into said substrate.
36. A tanning method for improving one or more properties of an animal substrate, wherein
said properties are selected from the group consisting of:
(1) hydrothermal stability;
(2) photochemical and/or thermal resistance;
(3) the degree of incorporation of a tanning agent into said substrate; and
(4) the degree of penetration of a tanning agent into said substrate,
wherein said method comprises the steps of (i) agitating the animal substrate with a
chromium-free tanning agent and (ii) agitating the animal substrate with a tanning agent
having an oxazolidine group, wherein at least some of the agitation is performed in the
presence of a solid particulate material, and wherein the solid particulate material has an
average particle size of from 1 to 500mm.
37. A tanned animal substrate which is chromium-free and which exhibits an improvement
in one or more properties selected from the group consisting of:
(1) hydrothermal stability;
(2) photochemical and/or thermal resistance;
(3) the degree of incorporation of the tanning agent into said substrate; and
(4) the degree of penetration of the tanning agent into said substrate,
relative to an animal substrate prepared by a tanning method in which a solid particulate
material is not used.
38. A tanned animal substrate which is chromium-free and which exhibits a shrinkage onset
temperature of at least 95°C, preferably at least 98°C and preferably at least 100°C.
39. An article which is or comprises an animal substrate according to claim 34, 37 or 38
wherein said article is selected from one or more of: articles of apparel and personal
accessories, footwear, bags, briefcases and suitcases, covers for phones, tablets and
laptops, saddlery, furniture and upholstered articles, sporting goods and accessories,
pet collars and leashes, and vehicle interior coverings.