U.S. patent application number 10/503132 was filed with the patent office on 2005-07-21 for use of acrylic graft polymers in the field of collagen-based substrates, and the substrates, skins and leathers thus obtained.
Invention is credited to Kensicher, Yves, Moro, Jean.
Application Number | 20050155157 10/503132 |
Document ID | / |
Family ID | 27676159 |
Filed Date | 2005-07-21 |
United States Patent
Application |
20050155157 |
Kind Code |
A1 |
Kensicher, Yves ; et
al. |
July 21, 2005 |
Use of acrylic graft polymers in the field of collagen-based
substrates, and the substrates, skins and leathers thus
obtained
Abstract
The invention concerns the technical sector of collagen-based
substrates, notably hides, leathers, undressed hides and
reconstituted leathers, and more specifically the use of acrylic
polymers grafted with one or more proteinic derivatives or natural
or synthetic fatty derivatives, together with the smoothing agents
consisting of the said grafted acrylic polymers. The invention also
concerns collagen-based substrates, notably hides, leathers,
undressed hides and reconstituted leathers smoothed using these
said grafted acrylic polymers. The invention also concerns leather
objects smoothed using these said grafted acrylic polymers.
Inventors: |
Kensicher, Yves; (Theize
69620, FR) ; Moro, Jean; (Toussieux, FR) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
27676159 |
Appl. No.: |
10/503132 |
Filed: |
August 10, 2004 |
PCT Filed: |
February 20, 2003 |
PCT NO: |
PCT/FR03/00565 |
Current U.S.
Class: |
8/94.1R |
Current CPC
Class: |
C14C 11/003
20130101 |
Class at
Publication: |
008/094.10R |
International
Class: |
D06M 019/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 28, 2002 |
FR |
02/02527 |
Claims
1. A method of treating collagen based substrates comprising:
applying acrylic polymer grafted with one or more proteinic
derivatives or natural or synthetic fatty derivatives to collagen
based substrates.
2. A method as claimed in claim 1, wherein said acrylic polymer
grafted with one or more proteinic derivatives or natural or
synthetic fatty derivatives is a product of radical polymerisation
of at least one monomer selected from the group consisting of
acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
fumaric acid, maleic anhydride, 2-acrylamido-2-methyl-1-propane
sulfonic acid, 2-methacrylamido-2-methyl-- 1-propane sulfonic acid,
3-methacrylamido-2-hydroxy-1-propane sulfonic acid, allylsulfonic
acid, methallylsulfonic acid, allyloxybenzene sulfonic acid,
methallyloxybenzene sulfonic acid, 2-hydroxy-3-(2-propenyl- oxy)
propane sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, ethylene
sulfonic acid, propene sulfonic acid, 2-methyl sulfonic acid,
styrene sulfonic acid, salts of styrene sulfonic acid, vinyl
sulfonic acid, sodium methallylsulfonate, sulfopropyl acrylate,
sulfopropyl methacrylate, sulfomethylacrylamide,
sulfomethylmethacrylamide, acrylamide, methylacrylamide, esters of
acrylic acid, esters of methacrylic acid, glycol propylene,
vinylpyrrolidone, vinylcaprolactam, isobutylene, diisobutylene,
vinyl acetate, styrene, alphamethylstyrene, vinylmethylether, and
allylics in the presence of one or more of the proteinic
derivatives or of the natural or synthetic fatty derivatives
selected from the group consisting of neat's foot oil, sheep's foot
oil, whale oil, synthetic spermaceti oil, seal oil, tallow, suint
grease, olein, stearin, suintin, lanolin, lecithin, phosphatidic
acids, cephaline, cholesterols, phytosterols, casein, eel oils,
herring oils, shark oil, sardine oil, fish oil, egg yolk, insect
wax, carnauba wax, candellila, ricin oil, olive oil, copra, palm
kernel oil, groundnut oil, cotton oil, colza oil, almond oil,
avocado oil, tung oil, borage oil, cocoa oil, camelia oil, cameline
oil, campher oil, carthame oil, chaulmoogra oil, hempseed oil,
croton oil, wheat seed oil, corn seed oil, jojoba oil, karite oil,
linseed oil, maize oil, marmot oil, menhaden oil, rapeseed oil,
hazelnut oil, walnut oil, apricot core oil, poppy oil, oiticica
oil, ongokea oil, palm oil, pecan oil, grape pip oil, perilla oil,
pine nut oil, pistachio nut oil, acetylated ricin oil, rice oil,
sesame oil, soya oil, tortoise oil, sunflower oil, liquid paraffin,
mink oil, abietic acid salts of abietic acid, naphthalene sulfonic
acid, salts of naphthalene sulfonic acid, formol melamines,
glutaric acid, glutamic acid, aspartic acid, butyric acid, caproic
acid, caprylic acid, capric acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachidic acid, behenic acid,
lignoceric acid, cerotic acid, elaidic acid, petroselinic acid,
lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid,
gadoleic acid, erucic acid, linoleic acid, linolenic acid,
eleostearic acid, licanic acid, parinaric acid, arachidonic acid,
clupanodonic acid, taririric acid, and isanic acid.
3. The method according to claim 2, wherein said at least one
monomer is selected from the group consisting of esters of acrylic
acid and esters of methacrylic acid, wherein said esters of acrylic
acid is alkyloxypolyalkylene glycol acrylate and said esters of
methacrylic acid is alkyloxypolyalkylene glycol methacrylate.
4. The method according to claim 2, wherein between 2.5% and 40%,
by mass, of the proteinic derivatives or of natural or synthetic
derivatives, is present relative to the total quantity of the
monomer.
5. The method according to claim 1, wherein 0.8% to 6% by dry
weight of acrylic polymers grafted with one or more proteinic
derivatives or natural or synthetic fatty derivatives, relative to
the weight of the "wet blue" support, is applied.
6. A smoothing agent wherein said smoothing agent comprises acrylic
polymers grafted with one or more proteinic derivatives or natural
or synthetic fatty derivatives.
7. The smoothing agent according to the claim 6, wherein said
smoothing agent is produced by the radical polymerisation of at
least one monomer selected from the group consisting of acrylic
acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid,
maleic anhydride, 2-acrylamido-2-methyl-1-propane sulfonic acid,
2-methacrylamido-2-methyl-- 1-propane sulfonic acid,
3-methacrylamido-2-hydroxy-1-propane sulfonic acid, allylsulfonic
acid, methallylsulfonic acid, allyloxybenzene sulfonic acid,
methallyloxybenzene sulfonic acid, 2-hydroxy-3-(2-propenyl- oxy)
propane sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, ethylene
sulfonic acid, propene sulfonic acid, 2-methyl sulfonic acid,
styrene sulfonic acid, salts of styrene sulfonic acid, vinyl
sulfonic acid, sodium methallylsulfonate, sulfopropyl acrylate,
sulfopropyl methacrylate, sulfomethylacrylamide,
sulfomethylmethacrylamide, acrylamide, methylacrylamide, esters of
acrylic acid, esters of methacrylic acid, glycol propylene,
vinylpyrrolidone, vinylcaprolactam, isobutylene, diisobutylene,
vinyl acetate, styrene, alphamethylstyrene, vinylmethylether, and
allylics in the presence of one or more of the proteinic
derivatives or of the natural or synthetic fatty derivatives
selected from the group consisting of neat's foot oil, sheep's foot
oil, whale oil, synthetic spermaceti oil, seal oil, tallow, suint
grease, olein, stearin, suintin, lanolin, lecithin, phosphatidic
acids, cephaline, cholesterols, phytosterols, casein, eel oils,
herring oils, shark oil, sardine oil, fish oil, egg yolk, insect
wax, carnauba wax, candellila, ricin oil, olive oil, copra, palm
kernel oil, groundnut oil, cotton oil, colza oil, almond oil,
avocado oil, tung oil, borage oil, cocoa oil, camelia oil, cameline
oil, campher oil, carthame oil, chaulmoogra oil, hempseed oil,
croton oil, wheat seed oil, corn seed oil, jojoba oil, karite oil,
linseed oil, maize oil, marmot oil, menhaden oil, rapeseed oil,
hazelnut oil, walnut oil, apricot core oil, poppy oil, oiticica
oil, ongokea oil, palm oil, pecan oil, grape pip oil, perilla oil,
pine nut oil, pistachio nut oil, acetylated ricin oil, rice oil,
sesame oil, soya oil, tortoise oil, sunflower oil, liquid paraffin,
mink oil, abietic acid, salts of abietic acid, naphthalene sulfonic
acid, salts of naphthalene sulfonic acid, formol melamines,
glutaric acid, glutamic acid, aspartic acid, butyric acid, caproic
acid, caprylic acid, capric acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachidic acid, behenic acid,
lignoceric acid, cerotic acid, elaidic acid, petroselinic acid,
lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid,
gadoleic acid, erucic acid, linoleic acid, linolenic acid,
eleostearic acid, licanic acid, parinaric acid, arachidonic acid,
clupanodonic acid, taririric acid, and isanic acid.
8. The smoothing agent according to claim 7, wherein said at least
one monomer is selected from the group consisting of esters of
acrylic acid and esters of methacrylic acid, wherein said esters of
acrylic acid is alkyloxypolyalkylene glycol acrylate and said
esters of methacrylic acid is alkyloxypolyalkylene glycol
methacrylate.
9. The smoothing agent according to claim 7, wherein said smoothing
agent comprises between 2.5% and 40% by mass the proteinic
derivatives or of the natural or synthetic fatty derivatives,
relative to the total quantity of the monomers.
10. A collagen-based substrate comprising the smoothing agent as
claimed in claim 6.
11. The collagen-based susbstrate according to claim 10 wherein
said substrate comprises 0.8% to 6% by dry weight of the smoothing
agent, relative to the support of the "wet blue" support.
12. A leather article comprising the smoothing agent as claimed in
claim 6.
Description
[0001] The present invention concerns the technical sector of
collagen-based substrates and notably hides, leathers, undressed
hides and reconstituted leathers, and more specifically the use of
acrylic polymers grafted with one or more proteinic derivatives or
natural or synthetic fatty derivatives in the aim of allowing
smoothing of the said substrate without the use of crosslinking
agents, notably formol.
[0002] The invention also concerns smoothing agents consisting of
the said acrylic polymers grafted with one or more proteinic
derivatives or natural or synthetic fatty derivatives.
[0003] The invention also concerns collagen-based substrates,
notably hides, leathers, undressed hides and reconstituted leathers
smoothed using these said grafted acrylic polymers.
[0004] The invention also concerns leather objects smoothed using
these said grafted acrylic polymers.
[0005] Currently the finishing of hides, leathers, undressed hides
and reconstituted leathers intended for the end consumer requires a
treatment of these substrates by a process consisting essentially
of five stages.
[0006] The first is a stage of sorting of the passes or hides or
again substrates, which is undertaken in the abattoirs and/or in
the tanneries, as desired by the client.
[0007] It will be noted that to facilitate reading of the present
description, the Applicant has chosen to use the word hide to
designate all types of collagen-based substrates, including notably
hides, leathers, undressed hides and reconstituted leathers.
[0008] Thus the term hide will be understood to include all the
substrates mentioned above.
[0009] Concerning the widely used hide finishing process, the
second stage, still called river work, constitutes a stage in the
preparation of the sorted hide, which is still, at this stage,
putrescible.
[0010] This stage comprises firstly the soaking or dressing of the
hide to clean the said hide, followed by the unhairing and liming
of this cleaned hide to create points for mounting of the hide,
which points will enable the various hide treatment additives to be
fixed subsequently.
[0011] When this liming has been accomplished, the hide can be
subjected to a skiving action followed by a shaving action
corresponding to the removal of the subcutaneous part, which has no
purpose, followed by actions of bating and finally of drenching,
which is an enzymatic reaction to clean the keratin remains and the
interfibrillary spaces.
[0012] When these various handling operations which constitute the
stage known as river work have been accomplished the hide is
subjected to a third stage of treatment, a stage which is broken
down firstly into pickling, i.e. acid conditioning of the hide to
allow the penetration of tannins into the hide, and subsequently
the tanning itself to make the hide rot-proof.
[0013] This tanning of the hide habitually makes use of mineral
derivatives such as, notably, chromium-, aluminium- or
zirconium-based salts, together with organic derivatives such as
hydrolysable vegetal tannins such as, for example, glucosides of
the chestnut tree, Vallonnee, vinegar plant or Myrobolam types, or
of organic derivatives such as condensed vegetal tannins, including
among others catechic oligomers of the Quebrach, mimosa or gambir
type.
[0014] These organic derivatives can also be synthetic tannins
which can replace the vegetal tannins. They are then called
substitution tannins.
[0015] These substitution tannins are compounds rich in OH.sup.- in
their structure and are mainly formol phenolic or naphtol-phenol
condensates.
[0016] These synthetic organic derivatives can also be secondary
tannins used as a supplement to other tannins. They have less
tanning power, but have other properties, notably including
dispersing, filling or "full" properties, or lightening or other
properties.
[0017] These secondary tannins are also sulfonic naphthalene
condensates, sulfonic aromatic acid, urea-formol, or again
precondensed melamine and other condensates, but are also other
than synthetic tannins such as, notably, aldehydes of the formol
type, glyoxal, glutaraldehyde, aldehyde derivatives mainly
multi-function products such as aldehyde-alcohols, phosphoniums,
fatty chain sulfochlorides and other sulfochlorate paraffins.
[0018] When the third stage of the treatment is completed and the
hide has become rot-proof, the fourth stage of the process is
undertaken, consisting in all the operations undertaken after
tanning, which is called currying.
[0019] This currying includes the wet operations such as curing,
which consists in allowing the hides to stay stacked for 24 hours
to perfect the tanning, neutralisation, retanning, dyeing,
nourishing agents to soften the hide, and mechanical operations
such as draining, drying, tempering or re-wetting, staking, which
consists in stretching the hide to soften it at a degree of
humidity of around 23% to 28%, framing, which consists in
stretching the staked hides on to frames to flatten them, and
sliding these frames into a drying machine to eliminate the
previous moisture, trimming, which is a manual operation consisting
of eliminating the frayed edges of the hide which make the skin
unpresentable, and smoothing.
[0020] This mechanical smoothing operation consists in smoothing
the hide using a metal, glass or agate cylinder, or cylinder of any
other material, or again using a plate or any other method for
shining the hide.
[0021] This operation is accompanied by a heating which encourages
the shine to "rise", since it is undertaken on a dry hide during
currying, after trimming and framing, or again after the fifth
stage of the process, which is the finishing of the hide on
conclusion of manufacture.
[0022] Currently, for this smoothing operation, the skilled man in
the art must generally use casein to give the skin shine, and must
spray a casein crosslinking agent, notably formol, to fix the
casein and attain the friction resistance specifications required
by the end user.
[0023] This operation using casein following by a spraying of a
casein crosslinking agent, notably formol, arises to the skilled
man in the art problems of handling and environmental problems.
[0024] The specifications sheet generally applied requires that the
formol contents in the hides have:
[0025] a content of less than or equal to 400 ppm for industrial
leathers,
[0026] a content of less than or equal to 300 ppm for leathers
intended for clothing,
[0027] a content of less than or equal to 40 ppm for leathers
intended for baby clothing.
[0028] Secondly, the handling problems are constituted by the need
to use casein and then to spray, during a second stage, the
crosslinking agent of the said casein.
[0029] Completely unexpectedly, the Applicant has found that the
use, on collagen-based substrates, and notably hides, leathers,
undressed hides and reconstituted leathers, of acrylic polymers
grafted with one or more proteinic derivatives or natural or
synthetic fatty derivatives enables the abovementioned problems
posed to arisen to the skilled man in the art to be resolved; i.e.
allows firstly problems relating to manipulation due to the use of
casein followed by a spraying of crosslinking agent to be avoided,
secondly allows all or part of the casein crosslinking agent,
notably formol, to be eliminated, and thirdly enables the smoothing
operation before the finishing operation, giving by this means the
advantage of obtaining the smoothed appearance, which will enhance
the finishing operation.
[0030] In addition to responding to the increasingly strict
toxicity requirements and to the specifications of friction
resistance required by the end user, this elimination of the use of
substantial quantities of crosslinking agent, notably formol,
together with the elimination of this double stage of spraying
enables the collagen substrate and more particularly the hide or
leather to be given properties of fullness, fineness of grain and
increased shine. These properties of increased shine thus result in
the natural appearance of the collagen substrate being preserved,
and more particularly of the hide or of the leather.
[0031] To resolve these problems, the skilled man in the art has no
prior art which might offer them any solution. The skilled man in
the art is, indeed, familiar with the German patent DE 44 16 877
which teaches use of grafted polymers by proteins to resolve the
problems of the lightening of colours, or of resistance to light
and to heat.
[0032] The skilled man in the art familiar with patent GB 2 137
654, which teaches use of these grafted polymers to garnish the
flanks of the hide and to fill hides tanned with chromium.
[0033] Another patent (U.S. Pat. No. 4,631,063) describes the use
of grafted polymers as a dyeing aid to give the hide stronger
colour.
[0034] None of these techniques known until today enable the
skilled man in the art is to free themselves from the operations to
use casein and to spray a crosslinking agent.
[0035] These aims are attained as claimed in the invention thanks
to the use as a smoothing agent, on collagen-based substrates and
notably hides, leathers, undressed hides and reconstituted
leathers, of acrylic polymers grafted with one or more proteinic
derivatives or natural or synthetic fatty derivatives.
[0036] This use is characterised in that the said grafted acrylic
polymers are acrylic polymers grafted with one or more proteinic
derivatives or natural or synthetic fatty derivatives.
[0037] This use is, preferably, characterised in that it is used at
a rate of 0.8% to 6% by dry weight, relative to the so-called "wet
blue" support weight, and more particularly at a rate of 1.2% to
2.4% by dry weight, relative to the so-called "wet blue" support
weight, of the said acrylic polymers grafted with one or more
proteinic derivatives or of the natural or synthetic fatty
derivatives.
[0038] The weight of the so-called "wet blue" support is the weight
of the hide after the river work, chromium tanning, wringing and
skiving operations.
[0039] More particularly, these grafted acrylic polymers, according
to the invention as a smoothing agent, result from various radical
polymerisation processes in the presence of the proteinic
derivatives or of the natural or synthetic fatty derivatives for
grafting.
[0040] Even more particularly, use as a smoothing agent of these
polymers resulting from homopolymerisation or radical
copolymerisation of unsaturated ethylene monomers in the presence
of a proteinic derivative or derivatives, or from the natural or
synthetic fatty derivative or derivatives for grafting is
characterised in that the said agent is a product of radical
polymerisation of at least one of the monomers from among: acrylic
acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid,
maleic anhydride and/or 2-acrylamido-2-methyl-1-propane sulfonic
acid, 2-methacrylamido-2-methyl-1-propane sulfonic acid,
3-methacrylamido-2-hydroxy-1-propane sulfonic acid, allylsulfonic
acid, methallylsulfonic acid, allyloxybenzene sulfonic acid,
methallyloxybenzene sulfonic acid, 2-hydroxy-3-(2-propenyloxy)
propane sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, ethylene
sulfonic acid, propene sulfonic acid, 2-methyl sulfonic acid,
styrene sulfonic acid and/or its salts, vinyl sulfonic acid, sodium
methallylsulfonate, sulfopropyl acrylate or methacrylate,
sulfomethylacrylamide, sulfomethylmethacrylamide, or again from
acrylamide, methylacrylamide, esters of acrylic or methacrylic
acids such as, notably, ethyl acrylate, butyl acrylate, methyl
methacrylate, acrylate phosphate or ethylene methacrylate or glycol
propylene, or from vinylpyrrolidone, vinylcaprolactam, isobutylene,
diisobutylene, vinyl acetate, styrene, alphamethylstyrene,
vinylmethylether, allylics such as, notably, allylamine and its
derivatives, preferentially chosen from acrylic acid or methacrylic
acid in the presence of one or more of the proteinic derivatives or
of the natural or synthetic fatty derivatives chosen from neat's
foot oil, sheep's foot oil, whale oil, synthetic spermaceti oil,
seal oil, tallow, suint grease, olein, stearin, suintin, lanolin,
lecithin, phosphatidic acids, cephaline, cholesterols,
phytosterols, casein, eel oils, herring oils, shark oil, sardine
oil, fish oil, egg yolk, insect wax, for example of bees, carnauba
wax, candellila, ricin oil, olive oil, copra, palm kernel oil,
groundnut oil, cotton oil, colza oil, almond oil, avocado oil, tung
oil, borage oil, cocoa oil, camelia oil, cameline oil, campher oil,
carthame oil, chaulmoogra oil, hempseed oil, croton oil, wheat seed
oil, corn seed oil, jojoba oil, karite oil, linseed oil, maize oil,
marmot oil, menhaden oil, rapeseed oil, hazelnut oil, walnut oil,
apricot core oil, poppy oil, oiticica oil, ongokea oil, palm oil,
pecan oil, grape pip oil, perilla oil, pine nut oil, pistachio nut
oil, acetylated ricin oil, rice oil, sesame oil, soya oil, tortoise
oil, sunflower oil, liquid paraffin, mink oil, abietic acids and
their salts, naphtalene sulfonic acids and their salts, formol
melamines, glutaric, glutamic, aspartic, butyric, caproic,
caprylic, capric, lauric, myristic, palmitic, stearic, arachidic,
behenic, lignoceric, cerotic, elaidic, petroselinic, lauroleic,
myristoleic, palmitoleic, oleic, gadoleic, erucic, linoleic,
linolenic, eleostearic, licanic, parinaric, arachidonic,
clupanodonic or taririric acids, or again isanic acids, preferably
chosen from among casein, lecithin or linseed oil.
[0041] In a particular manner also, use as a smoothing agent of
these polymers is characterised in that the acrylic or methacrylic
acid esters are chosen from alkyloxypolyalkylene glycol acrylate or
methacrylate and particularly is methoxypolyethylene glycol
methacrylate.
[0042] These polymers resulting particularly from
homopolymerisation or from radical copolymerisation of the monomers
previously listed in the presence of the proteinic derivative or
derivatives or from the natural or synthetic fatty derivatives, or
from their mixtures mentioned above, are characterised even more
particularly in that the mass rate of proteinic derivatives or of
natural or synthetic fatty derivatives, relative to the total
quantity of monomers, is between 2.5% and 40%, and preferably
between 5% and 10%.
[0043] These polymers can be obtained by radical polymerisation or
copolymerisation of the abovementioned monomers in the acid state,
partially neutralised or totally neutralised, and preferably in the
acid state in a polymerisation medium which can be water, one of
the alcohols or a water-alcohol mixture, or again one of the
solvents chosen from methanol, ethanol, propanol, isopropanol, the
butanols, or mixtures of them, or again dimethylformamide,
dimethylsulfoxide, tetrahydrofuran, acetone, methylethylketone,
ethyl acetate, butyl acetate, hexane, heptane, benzene, toluene,
xylene, halogenated solvents such as carbon tetrachloride,
chloroform, methylene chloride, or again the glycol monopropylene
ethers, or mixtures of them and their analogues.
[0044] However, the skilled man in the art will adapt the pH of the
polymerisation medium according to the proteinic derivative or
derivatives, or of the natural or synthetic fatty derivative or
derivatives, or according to the mixtures of thereof used in this
polymerisation reaction.
[0045] These neutralisation agents are chosen either from the group
constituted by the compounds containing alkaline cations,
particularly sodium and potassium, or again lithium, ammonium, or
indeed the primary or secondary aliphatic and/or cyclic amines such
as, for example, the ethanolamines, mono- and diethylamine, or
again cyclohexylamine, or from the group constituted by the
compounds containing alkaline-earth divalent cations, particularly
magnesium and calcium, or again zinc, or the group constituted by
the compounds containing trivalent cations, in particular
aluminium, or again by certain compounds containing cations of
higher valences, or are a mixture of at least two of the
abovementioned agents.
[0046] In another variant, the homopolymer or copolymer produced
from the polymerisation reaction in the presence of the proteinic
derivative or derivatives or of the natural or synthetic fatty
derivative or derivatives may be treated and separated into several
phases, according to static or dynamic processes known to the
skilled man in the art, by one or more polar solvents belonging
notably to the group constituted by water, methanol, ethanol,
propanol, isopropanol, the butanols, acetone, tetrahydrofuran, or
mixtures of thereof. One of the phases then corresponds to the
polymer used according to the invention as a smoothing agent.
[0047] The invention also concerns smoothing agents consisting of
the said acrylic polymers grafted with the said proteinic
derivatives or natural or synthetic fatty derivatives.
[0048] Thus, the smoothing agents according to the invention are
characterised in that they are products of radical polymerisation
of at least one of the monomers from among: acrylic acid,
methacrylic acid, itaconic acid, crotonic acid, fumaric acid,
maleic anhydride and/or 2-acrylamido-2-methyl-1-propane sulfonic
acid in acid or partially neutralised form,
2-methacrylamido-2-methyl-1-propane sulfonic acid in acid or
partially neutralised form, 3-methacrylamido-2-hydroxy-1-propane
sulfonic acid in acid or partially neutralised form, allylsulfonic
acid, methallylsulfonic acid, allyloxybenzene sulfonic acid,
methallyloxybenzene sulfonic acid, 2-hydroxy-3-(2-propenyloxy)
propane sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, ethylene
sulfonic acid, propene sulfonic acid, 2-methyl sulfonic acid,
styrene sulfonic acid and/or its salts, vinyl sulfonic acid, sodium
methallylsulfonate, sulfopropyl acrylate or methacrylate,
sulfomethylacrylamide, sulfomethylmethacrylamide, or again from
acrylamide, methylacrylamide, esters of acrylic or methacrylic
acids such as, notably, ethyl acrylate, butyl acrylate, methyl
methacrylate, acrylate phosphate or ethylene methacrylate or glycol
propylene, or from vinylpyrrolidone, vinylcaprolactam, isobutylene,
diisobutylene, vinyl acetate, styrene, alphamethylstyrene,
vinylmethylether, allylics such as, notably, allylamine and its
derivatives, preferentially chosen from acrylic acid or methacrylic
acid in the presence of one or more of the proteinic derivatives or
of the natural or synthetic fatty derivatives chosen from neat's
foot oil, sheep's foot oil, whale oil, synthetic spermaceti oil,
seal oil, tallow, suint grease, olein, stearin, suintin, lanolin,
lecithin, phosphatidic acids, cephaline, cholesterols,
phytosterols, casein, eel oils, herring oils, shark oil, sardine
oil, fish oil, egg yolk, insect wax, for example of bees, carnauba
wax, candellila, ricin oil, olive oil, copra, palm kernel oil,
groundnut oil, cotton oil, colza oil, almond oil, avocado oil, tung
oil, borage oil, cocoa oil, camelia oil, cameline oil, campher oil,
carthame oil, chaulmoogra oil, hempseed oil, croton oil, wheat seed
oil, corn seed oil, jojoba oil, karite oil, linseed oil, maize oil,
marmot oil, menhaden oil, rapeseed oil, hazelnut oil, walnut oil,
apricot core oil, poppy oil, oiticica oil, ongokea oil, palm oil,
pecan oil, grape pip oil, perilla oil, pine nut oil, pistachio nut
oil, acetylated ricin oil, rice oil, sesame oil, soya oil, tortoise
oil, sunflower oil, liquid paraffin, mink oil, abietic acids and
their salts, naphtalene sulfonic acids and their salts, formol
melamines, glutaric, glutamic, aspartic, butyric, caproic,
caprylic, capric, lauric, myristic, palmitic, stearic, arachidic,
behenic, lignoceric, cerotic, elaidic, petroselinic, lauroleic,
myristoleic, palmitoleic, oleic, gadoleic, erucic, linoleic,
linolenic, eleostearic, licanic, parinaric, arachidonic,
clupanodonic or taririric acids, or again isanic acids, preferably
chosen from among casein, lecithin and linseed oil.
[0049] In a particular manner also, the smoothing agent according
to the invention is characterised in that the acrylic or
methacrylic acid esters are chosen from alkyloxypolyalkylene glycol
acrylate or methacrylate and particularly is methoxypolyethylene
glycol methacrylate.
[0050] More particularly, the smoothing agents according to the
invention are characterised in that the mass rate of the proteinic
derivatives or of the natural or synthetic fatty derivatives or of
mixtures of thereof, relative to the total quantity of the
monomers, is between 2.5% and 40%, preferably between 5% and
10%.
[0051] The smoothing agent according to the invention, obtained by
radical polymerisation or copolymerisation of the abovementioned
monomers, is in the acid state, or in the partially neutralised
state, or the totally neutralised state, and is preferably in the
acid state, i.e. a pH of under 7.
[0052] The neutralisation agents are chosen from among those
previously described. In another variant, the smoothing agent
according to the invention produced from the polymerisation
reaction in the presence of the proteinic derivative or derivatives
or from the natural or synthetic fatty derivative or derivatives
may, as previously described, be treated and separated into several
phases.
[0053] The invention also concerns collagen substrates smoothed
using the said acrylic polymers grafted with the said proteinic
derivative or derivatives or natural or synthetic fatty
derivatives.
[0054] These hides, with the general meaning described above,
according to the invention, are characterised in that they contain
the said acrylic polymers grafted with the said proteinic
derivatives or natural or synthetic fatty derivatives or mixtures
of thereof, and are characterised more particularly in that they
contain 0.8% to 6% by dry weight, relative to the weight of the
so-called "wet blue" support, and particularly 1.2% to 2.4% by dry
weight relative to the weight of the so-called "wet blue" support,
of the said acrylic polymers grafted with proteinic derivatives or
natural or synthetic fatty derivatives.
[0055] The invention also concerns leather objects smoothed using
the said acrylic polymers grafted with the said proteinic
derivative or derivatives, or natural or synthetic fatty
derivatives.
[0056] The invention will be better understood on reading the
description of the non-limitative examples below.
EXAMPLE 1
[0057] The aim of this example is to highlight is also the shining
properties obtained through the use of acrylic polymers grafted
with one or more proteinic derivatives or natural or synthetic
fatty derivatives according to the invention.
[0058] In this aim, for each of the tests in the example, a goat's
hide is prepared called "wet blue" after the river works, chromium
tanning, wringing and skiving operations. The "wet blue" hide is
then weighed, and this weight is the reference weight for the
stages of neutralisation, retanning, dyeing and nourishment which
follow.
[0059] All these stages are undertaken in identical way for all
tests.
[0060] To accomplish this, the "wet blue" hide is introduced in a
cleaning drum at 40.degree. C. containing a cleaning bath
consisting of 150% by weight of water relative to the weight of the
"wet blue" hide and of 1% by weight, relative to the weight of the
"wet blue" hide, of the cleaning agent Actol DB sold by the company
ATC. This bath containing the hide is stirred for 20 minutes at a
speed of between 10 and 12 revolutions per minute, before being
emptied from the drum.
[0061] The stage of neutralisation at 35.degree. C. is then
undertaken up to a pH of 4.5, by addition, into the drum, of the
neutralising medium, consisting of 100% by weight of water relative
to the weight of the "wet blue" hide, and 1% by weight, relative to
the weight of the "wet blue" hide, of the neutralising agent Actan
NH sold by the company ATC.
[0062] After 30 minutes of stirring at a speed of between 10 and 12
revolutions per minute, the neutralising bath is, in its turn,
emptied from the drum to allow room for the retanning stage. To
accomplish drum, to this drum containing the hide, 50% by weight of
water is added relative to the weight of the "wet blue" hide and 3%
by weight, relative to the weight of the "wet blue" hide, of a
black colouring agent sold by the company ATC under the name Dyacor
Black ANT, and it is then stirred 3 times 10 minutes, at a speed of
between 10 and 12 revolutions per minute, before adding 50% by
weight of water, relative to the weight of the "wet blue" hide, and
1.5% by weight, relative to the weight of the "wet blue" hide, of a
nourishment for hide sold by the company ATC under the name Actoil
NM.
[0063] After this addition, the whole mixture is stirred for 20
minutes, still at a speed of 10 to 12 revolutions per minute,
before adding 3% by weight, relative to the weight of the "wet
blue" hide, of a synthetic tannin sold by the company ATC under the
name Actan PO.
[0064] After this addition, the whole mixture is stirred for 20
minutes at the same speed, before adding 10% by weight, relative to
the weight of the "wet blue" hide, of a vegetal mimosa tannin sold
by the company Seta under the name Seta Sun. The whole mixture is
also stirred for one hour at the same speed before adding 1% by
weight, relative to the weight of the "wet blue" hide, of formic
acid.
[0065] After adding formic acid and stirring for 20 minutes at a
speed of between 10 and 12 revolutions per minute, the bath is
emptied and then rinsed.
[0066] The retanning operation then continues for all tests by
adding at 50.degree. C. of 50% by weight of water, relative to the
weight of the "wet blue" hide, and of 0.1% by weight, relative to
the weight of the "wet blue" hide, of a biocide sold by the company
ATC under the name Biocide C3, and then by stirring the mixture for
5 minutes at a speed of between 10 and 12 revolutions per
minute.
[0067] It is then continued by adding at 50.degree. C. of 50% by
weight of water, relative to the weight of the "wet blue" hide, and
of 0.5% by weight, relative to the weight of the "wet blue" hide,
of a neutralising agent sold by the company ATC under the name
Actan NH.
[0068] The whole mixture is then stirred for 10 minutes at the same
speed before adding 1% by weight, relative to the weight of the
"wet blue" hide, of a nourishment for hide sold by the company ATC
under the name Actoil VI, 2.5% by weight, relative to the weight of
the "wet blue" hide, of another nourishment for hide sold by the
company ATC under the name Actoil SGC, and finally before adding
0.5% by weight, relative to the weight of the "wet blue" hide, of a
final nourishment for hide sold by the company ATC under the name
Actoil NLP.
[0069] Once these three previously described stages of cleaning,
neutralisation and then retanning have been undertaken, the various
tests of the example then implement the various polymers to be
tested as a smoothing agent through the addition into the drum of
the various agents for testing under stirring at 10 to 12 rpm for
30 minutes. When these agents have been implemented, a final
addition of 1% of formic acid by weight relative to the weight of
the "wet blue" hide is made.
[0070] This having been done, for each of the tests, smoothing is
undertaken using a smoothing machine fitted with a glass cylinder.
A measurement of the shine of the smoothed hide is then undertaken
by simple application, to the smoothed hide, of a shine meter of
the "micro Tri gloss" type manufactured by BYK-GARDNER GmbH.
[0071] Test No. 1
[0072] This test is a control test which implements 1.2% by dry
weight, relative to the weight of the "Wet blue" hide, of an
acrylic acid homopolymer.
[0073] The value of the shine obtained is equal to 4.1.
[0074] Test No. 2
[0075] This test illustrates the invention and implements 1.2% by
dry weight, relative to the weight of the "Wet blue" hide, of a
casein-grafted acrylic acid polymer in a weight ratio of equal to
92.5% acrylic acid and 7.5% casein.
[0076] The value of the shine obtained is equal to 4.8.
[0077] If the sample of hide used in this test is subjected to a
subsequent polishing stage, the value of shine, measured under the
same conditions, is equal to 24.1.
[0078] Test No. 3
[0079] This test illustrates the invention and implements 4.5% by
dry weight, relative to the weight of the "Wet blue" hide, of a
casein-grafted acrylic acid polymer in a weight ratio of equal to
97.5% acrylic acid and 2.5% casein.
[0080] The value of the shine obtained is equal to 5.3.
[0081] Test No. 4
[0082] This test illustrates the invention and implements 0.8% by
dry weight, relative to the weight of the "Wet blue" hide, of a
casein-grafted acrylic acid polymer in a weight ratio of equal to
80% acrylic acid and 20% casein.
[0083] The value of the shine obtained is equal to 4.7.
[0084] Test No. 5
[0085] This test illustrates the invention and implements 1.2% by
dry weight, relative to the weight of the "Wet blue" hide, of a
casein-grafted acrylic acid polymer in a weight ratio of equal to
95% acrylic acid and 5% casein.
[0086] The value of the shine obtained is equal to 5.2.
[0087] Test No. 6
[0088] This test illustrates the invention and implements 1.2% by
dry weight, relative to the weight of the "Wet blue" hide, of a
casein-grafted acrylic acid polymer in a weight ratio of equal to
90% acrylic acid and 10% casein.
[0089] The value of the shine obtained is equal to 8.1.
[0090] Test No. 7
[0091] This test illustrates the invention and implements 0.9% by
dry weight, relative to the weight of the "Wet blue" hide, of a
linseed oil-grafted acrylic acid polymer in a weight ratio of equal
to 90% acrylic acid and 10% linseed oil.
[0092] The value of the shine obtained is equal to 5.9.
[0093] Test No. 8
[0094] This test illustrates the invention and implements 1.8% by
dry weight, relative to the weight of the "Wet blue" hide, of a
linseed oil-grafted acrylic acid polymer in a weight ratio of equal
to 90% acrylic acid and 10% linseed oil.
[0095] The value of the shine obtained is equal to 6.3.
[0096] Test No. 9
[0097] This test illustrates the invention and implements 1.8% by
dry weight, relative to the weight of the "Wet blue" hide, of a
casein-grafted acrylic acid polymer in a weight ratio of equal to
90% acrylic acid and 10% casein.
[0098] The value of the shine obtained is equal to 5.9.
[0099] Test No. 10
[0100] This test illustrates the invention and implements 1.8% by
dry weight, relative to the weight of the "Wet blue" hide, of a
polymer of acrylic acid and methacrylic acid grafted with lecithin,
in a weight ratio of equal to 45% acrylic acid, 45% methacrylic
acid and 10% lecithin.
[0101] The value of the shine obtained is equal to 5.5.
[0102] Test No. 11
[0103] This test illustrates the invention and implements 1.8% by
dry weight, relative to the weight of the "Wet blue" hide, of a
linseed oil-grafted acrylic acid polymer in a weight ratio of equal
to 60% acrylic acid and 40% linseed oil.
[0104] The value of the shine obtained is equal to 4.9.
[0105] Test No. 12
[0106] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
copolymer, of pH 5, of acrylic acid grafted with olein in a weight
ratio of equal to 75.6% acrylic acid, 14.4% maleic anhydride and
10% olein.
[0107] The value of the shine obtained is equal to 7.9.
[0108] Test No. 13
[0109] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
copolymer, of pH 5, of acrylic acid grafted with casein in a weight
ratio of equal to 85.5% acrylic acid, 9.5%
2-acrylamido-2-methyl-1-propane sulfonic acid and 5% casein.
[0110] The value of the shine obtained is equal to 8.6.
[0111] Test No. 14
[0112] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
copolymer, of pH 5, of acrylic acid grafted with linseed oil in a
weight ratio of equal to 68% acrylic acid, 15.3% acrylamide, 1.7%
sodium methallylsulfonate and 15% linseed oil.
[0113] The value of the shine obtained is equal to 5.6.
[0114] Test No. 15
[0115] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
copolymer, of pH 5, of acrylic acid grafted with lanolin in a
weight ratio of equal to 73.6% acrylic acid, 13.8% methacrylic
acid, 4.6% methacrylamide and 8% lanolin.
[0116] The value of the shine obtained is equal to 6.1.
[0117] Test No. 16
[0118] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
copolymer, of pH 6.5, of methacrylic acid grafted with ricin oil in
a weight ratio of equal to 81% methacrylic acid, 4.5% butyl
acrylamide, 4.5% styrene and 10% ricin oil.
[0119] The value of the shine obtained is equal to 10.1.
[0120] Test No. 17
[0121] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
polymer, of pH 5, of acrylic acid grafted with fish oil in a weight
ratio of equal to 80% of acrylic acid and 20% fish oil.
[0122] The value of the shine obtained is equal to 5.9.
[0123] Test No. 18
[0124] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
copolymer, of pH 5, of acrylic acid grafted with copra oil in a
weight ratio of equal to 76% acrylic acid, 4.75% ethylene glycol
methacrylate phosphate, 14.25% methoxypolyehthylene glycol
methacrylate of molecular weight 750 and 5% copra oil.
[0125] The value of the shine obtained is equal to 8.7.
[0126] Test No. 19
[0127] This test illustrates the invention and implements 2.3% by
dry weight, relative to the weight of the "wet blue" hide, of a
copolymer, of pH 5, of acrylic acid grafted with neat's foot oil in
a weight ratio of equal to 85.5% acrylic acid, 4.5% vinyl acetate
and 10% neat's foot oil.
[0128] The value of the shine obtained is equal to 8.1.
[0129] Test No. 20
[0130] This test illustrates the invention and implements 1.8% by
dry weight, relative to the weight of the "wet blue" hide, of a
polymer, of pH 5, of acrylic acid grafted with casein and linseed
oil in a weight ratio of equal to 90% of acrylic acid, 5% casein
and 5% linseed oil.
[0131] The value of the shine obtained is equal to 6.0.
[0132] Test No. 21
[0133] This test illustrates the invention and implements 0.9% by
dry weight, relative to the weight of the "wet blue" hide, of a
polymer, of pH 5, of acrylic acid grafted with lecithin in a weight
ratio of 90% acrylic acid and 10% lecithin and 0.9% by dry weight,
relative to the weight of the "wet blue" hide, of a polymer, of pH
5, of acrylic acid grafted with lanolin in a weight ratio of equal
to 90% acrylic acid and 10% lanolin.
[0134] The value of the shine obtained is equal to 5.9.
[0135] Reading all these results shows that the use of acrylic
polymers grafted with proteinic derivatives or natural or synthetic
fatty derivatives according to the invention enables increased
shine properties to be obtained on the exclusively smoothed hide,
and enables the smoothing operation to be undertaken before the
finishing operation.
[0136] This shine value enables the natural appearance of the hide
to be preserved.
* * * * *