(19)

*EP003387176B1*
(11) EP 3 387 176 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) International Patent Classification (IPC):
of the grant of the patent: D04H 1/587 (2012.01) C08F 218/04 (2006.01)
26.01.2022 Bulletin 2022/04 C08F 218/08 (2006.01) C08G 59/32 (2006.01)
D04H 1/64 (2012.01) C08L 79/02 (2006.01)
(21) Application number: 16822810.4
(52) Cooperative Patent Classification (CPC):
(22) Date of filing: 06.12.2016 (C-Sets available)
C08F 218/08; C08G 59/3227; C08G 73/022;
C08L 31/04; C08L 79/02; C09D 131/04;
D04H 1/587; D04H 1/64 (Cont.)

(86) International application number:

PCT/US2016/065057

(87) International publication number:

WO 2017/100152 (15.06.2017 Gazette 2017/24)

(54) CARBOXYLATED VINYL ACETATE/ETHYLENE COPOLYMER DISPERSIONS AND USES

THEREOF
CARBOXYLIERTE VINYLACETAT/ETHYLEN-COPOLYMER-DISPERSIONEN UND DEREN
VERWENDUNG
DISPERSIONS CARBOXYLÉES DE COPOLYMÈRE D’ACÉTATE DE VINYLE ET D’ÉTHYLÈNE ET
LEURS UTILISATIONS

(84) Designated Contracting States: (74) Representative: Herr, Ulrike Maria

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Patentanwälte
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Isenbruck Bösl Hörschler PartG mbB
PL PT RO RS SE SI SK SM TR Prinzregentenstraße 68
81675 München (DE)
(30) Priority: 09.12.2015 DE 102015015907
(56) References cited:
(43) Date of publication of application: EP-A1- 0 622 433 WO-A1-2013/072713
17.10.2018 Bulletin 2018/42 US-A1- 2012 028 527 US-B2- 7 189 307
US-B2- 7 678 856
(73) Proprietor: Celanese International Corporation
Irving, TX 75039 (US)

(72) Inventors:
• LICHERI, Cristiana
55011 Altopascio- Lucca (IT)
• MCLENNAN, Alistair John
61462 Königstein (DE)
• ROSSI, Ivan
21010 Cardano al Campo (VA) (IT)
EP 3 387 176 B1

• SCOTT, Paul Alexander

Stoneleigh
Epsom KT17 2LQ (GB)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR) (Cont. next page)

 EP 3 387 176 B1

(52) Cooperative Patent Classification (CPC): (Cont.)

C-Sets
C08F 218/08, C08F 210/02, C08F 220/06;
C08L 31/04, C08L 79/02;
C08L 79/02, C08L 31/04;
C09D 131/04, C08L 79/02

2
 EP 3 387 176 B1

Description

FIELD OF THE INVENTION

5 [0001] The present invention relates to the preparation of emulsion polymer-based binders comprising a vinyl es-
ter/ethylene copolymer containing copolymerized carboxylic acid groups or salts thereof blended with a wet strength
polyamidoamine-epichlorohydrin, (PAE), resin. This binder composition provides fibrous substrates with wet-strength
and yields very low levels of both free and bound formaldehyde. Fibrous substrates that benefit from the use of such
binder and finishing compositions include non-woven substrates, such as paper products and absorbent structures for
10 personal care products, non-woven fabric and textiles.

BACKGROUND OF THE INVENTION

[0002] Non-woven materials and other fibrous products consist of a loosely assembled mass of fibers which can be
15 bound together with a polymeric binder to form a self- sustaining web or substrate. Such webs or substrates can be
used to produce many items such as consumer paper towels, disposable wipes, absorbent media for feminine hygiene
applications and diapers, medical drapes, table-cloths, and high-grade napkins. The strength of the non-woven substrate
used, and especially wet tensile strength, is an important property in many applications.
[0003] One way to improve the tensile strength of a non-woven substrate is through the incorporation of cross-linking
20 co-monomers into the polymeric material, e.g., emulsion copolymers, used as the substrate binder or finishing agent.
The cross-linking co-monomers are capable of self-cross-linking between polymer chains after application to the non-
woven substrate and upon drying or curing of the polymeric binder or finishing agent. The most widely used cross-linking
co-monomer in such applications is N-methylol acrylamide (NMA).
[0004] There are two potential problems which can arise when using binder or finishing compositions wherein an
25 emulsion polymer of the composition contains cross-linking co-monomers. First, there is an upper limit to the amount of
the cross-linking co-monomer that can be incorporated to produce a useful binder or finishing agent using currently
available processing technology. Second, the N-methylol acrylamide (NMA) typically used as cross- linking co-monomer
is a recognized source of formaldehyde, which is undesirable in most applications.
[0005] Elimination or minimization of cross-linking co-monomers such as NMA in the emulsion polymers used can
30 provide binder and finishing compositions which yield lower formaldehyde levels. But such elimination or minimization
of cross-linking capability lowers the copolymer molecular weight which can in turn diminish the wet tensile strength
which the binder or finishing agent imparts to the substrates treated therewith.
[0006] US Patent No. 4,859,527 discloses the use of PAE resins in non-wovens. However, the method disclosed was
to pretreat cellulosic fibers with an adhesion promoting additive, which included PAE resins amongst its embodiments,
35 and to later bond the fibers together with a polymeric binder. It does not teach using a blend of VAE dispersion containing
copolymerized carboxyl groups (carboxylated VAE) with a specially selected PAE resin to bind the non-woven fibers to
avoid free or bound formaldehyde in the final non-woven article.
[0007] WO 2002/04133A2 discloses an aqueous composition comprising a water-soluble component comprising at
least one functional group that undergoes a crosslinking reaction, a film-forming polymer and a component that provides
40 vapour or moisture barrier properties. PAE resins are disclosed in claim 2 of said application.
[0008] US Patent No. 7,189,307 discloses a system to impart wet strength to soft, absorbent paper sheets, by topically
applying to one or both surfaces a cured binder composition. The cured binder composition comprises a carboxylated
vinyl acetate terpolymer, and an epoxy functional polymer. The epoxy functional polymer includes the kymene type of
resins. The invention focuses on reducing formaldehyde emissions, not on eliminating free and bound formaldehyde.
45 US Patent No. 7,678,856 B2 describes a low-formaldehyde containing dispersion of a vinyl ester/ethylene copolymer
blended with a wet strength polyamide-polyamine-epichlorohydrin (PAE) resin comprising 1299 ppm halogenated organic
compounds, i.e., 999 ppm of 1,3-dichloropropanol (DCP) and 300 ppm of monochloropropanediole (MPCD).
[0009] WO 2013/072713 A1 describes aqueous compositions, which are useful as binders and finishing agents for
nonwoven substrates, fabrics and textiles. Such compositions comprise a combination of an aqueous emulsion polymer
50 of the vinyl ester or acrylic acid ester type but having no formaldehyde-generating co-monomers therein, with an aqueous
functionalized polyolefin emulsion polymer.
[0010] Given the foregoing considerations, there is a continuing need to identify new binder and finishing compositions
for non-woven substrates which can be used to provide treated substrates that are very low in formaldehyde content,
i.e., less than 5 ppm bound and free, but which nevertheless possess desirably high tensile, particularly wet tensile,
55 strength. It has been found that selected types of cross-linker-free emulsion polymers can be blended with other selected
types of polymers to realize aqueous binder and finishing compositions which provide non-woven and other fibrous
substrates having this desirable combination of features.

3
 EP 3 387 176 B1

BRIEF SUMMARY OF THE INVENTION

[0011] This invention is directed to aqueous based polymer dispersions for use in paper, textile and non-woven ap-
plications that deliver wet strength without releasing free and/or bound formaldehyde, the latter under severe test con-
5 ditions of acidic steam distillation.
[0012] In one aspect, the present invention is directed to a low-formaldehyde containing dispersion of a vinyl ester/eth-
ylene copolymer containing copolymerized carboxylic acid groups or salts thereof, blended with a wet strength polyamido-
amine epichlorohydrin resin according to claim 1, to finishing compositions according to claim 2, and to their use as a
binder for non-woven substrates and textiles according to claim 3. Such compositions comprise a dispersion of a vinyl
10 ester/ethylene copolymer containing copolymerized carboxylic acid groups or salts thereof, blended with a wet strength
polyamido-amine epichlorohydrin resin, (PAE). The vinyl ester/ethylene copolymer dispersion is free of reactive N-
methylol acrylamide groups. The PAE is a second or a later generation of polyamidoamine-epichlorohydrin resins with
reduced levels of halogenated organic compounds (AOX) of below 0.60 wt.%, e.g., below 0.50 wt.% or below 0.20 wt.%.
The weight ratio of the vinyl ester/ethylene copolymer to the PAE resin is from 95:5 to 20:80. The pH is greater than 3.5,
15 e.g., greater than 6, greater than 7, or greater than 7.5.
[0013] The vinyl ester/ethylene copolymer may contain from 5 to 35 wt.%, preferably from 10 to 30 wt.%, more preferably
from 15 to 25 wt.% of units derived from ethylene. In some embodiments, the vinyl ester component of the copolymer
comprises a vinyl ester of a C1-C13 saturated carboxylic acid and is preferably vinyl acetate.
[0014] In another aspect, the present development is directed to a composition produced by blending the vinyl ace-
20 tate/ethylene copolymer (VAE) dispersion and a PAE resin. The present development is also directed to using the
composition as a binder for textile or non-woven substrate, and the composition has been applied to one or both sides
of the textile or non-woven fabric and then cured.
[0015] In yet another aspect, the present development is directed to a latex-bonded non-woven material comprising
a substrate that is bonded with a polymer binder comprising a vinyl acetate/ethylene (VAE) copolymer containing copo-
25 lymerized carboxylic acid groups or salts thereof, and a PAE resin according to any of claims 4 to 11. The non-woven
material has a wet tensile strength value of at least 35%, preferably 40% of its dry tensile strength value, and the material
has a bound formaldehyde content of less than 5 ppm as determined by the VdL-RL03(1997-05) method. In preferred
embodiments of this aspect, the weight ratio of dried VAE/PAE blend to the weight of the fibers is from 3 to 30 wt.%,
preferably from 5 to 20 wt.%, more preferably from 10 to 15 wt.%; and/or the weight ratio of the vinyl ester/ethylene
30 copolymer to PAE resin is from 95:5 to 20:80; and /or the wet/dry tensile strength ratio of the material is at least 40%,
preferably at least 45% and the bound formaldehyde is less than 5 ppm, preferably 1 ppm or less.
[0016] The PAE resin used in the present development is a Generation 2, Generation 2.5, or Generation 3 PAE (G2,
G2.5 or G3 PAE), more preferably a G2.5 or G3 PAE, and is an aqueous solution with solids content from 12.5 to 30%,
wherein the level of undesired byproducts has been reduced such that the level of 1,3-dichloropropanol, (DCP) is below
35 700 ppm, preferably below 500 ppm, more preferably below 150 ppm, most preferably below 50 ppm, the level of 3-
monochloropropan-1,2-diol, (MCPD), is below 600 ppm, preferably below 500 ppm, more preferably below 400 ppm
and most preferably below 50 ppm and the AOX level below 800 ppm.
[0017] The VAE copolymer used in the present development preferably comprises 0.1 to 10 wt.%, more preferably
0.25 to 5 wt.%, or 0.5 to 2.5 wt.% of units derived from at least one ethylenically unsaturated acid monomer and/or
40 anhydride thereof and/or salt thereof. Preferably, the ethylenically unsaturated acid is an α-β unsaturated mono- or di-
carboxylic acid containing 3 to 8 carbon atoms. Preferably, the α-β unsaturated mono-or di- carboxylic acid monomer
is one or more of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and C1 to C12 mono-alkyl esters
of itaconic or maleic acid. The vinyl ester/ethylene copolymer is preferably substantially free of anionic surfactants,
wherein substantially free means less than 2 wt.% of anionic surfactant on an active basis, preferably less than 1 wt.%.
45 The VAE copolymer may also comprise a protective colloid, or a combination of a colloid and non-ionic surfactant. The
VAE copolymer of the polymer binder is substantially free of N-methylol acrylamide and alkyl esters of N-methylol
acrylamide.
[0018] In yet another aspect, the present development is directed to the textiles, or personal care articles, or industry
or household cleaning cloth incorporating non-woven material described above.
50
DETAILED DESCRIPTION OF THE INVENTION

[0019] The compositions described herein are useful as binders for non-woven substrates such as fibrous webs and
also as finishing agents for textiles and non-woven fabrics. Such compositions comprise two types of polymeric materials
55 which are combined to form these compositions. The compositions are then applied to the non-woven substrates, textiles
or non-woven fabrics and subsequently cured. In some aspects, the non-woven substrates, textiles or non-woven fabrics
are used in a food contacting application. The present invention has combined the use of a dispersion with a PAE resin
to form a new binder by taking a non-crosslinking vinyl acetate/ethylene (VAE) copolymer, e.g., a dispersion not containing

4
 EP 3 387 176 B1

any reactive N-methylol acrylamide groups, and blending it with a food contact approved polyamidoamine-epichlorohydrin
wet strength agent. The vinyl ester/ethylene (emulsion) copolymer, e.g., the VAE (emulsion) copolymer, disclosed herein
contains carboxyl groups from the copolymerization of unsaturated carboxylic acid monomers, and is stabilized primarily
with nonionic surfactants.
5 [0020] In some embodiments, the present invention is directed to a low-formaldehyde containing dispersion of a vinyl
ester/ethylene copolymer containing copolymerized carboxylic acid groups or salts thereof blended with a wet strength
polyamidoamine-epichlorohydrin (PAE) resin; wherein: a) the vinyl ester/ethylene copolymer dispersion is free of reactive
N-methylol acrylamide groups; and b) the PAE resin comprises less than 800 ppm halogenated organic compounds
(AOX); c) the weight ratio the solid particles of the vinyl ester/ethylene copolymer to the solid particles in the aqueous
10 emulsion of the PAE resin is from 95:5 to 20:80; and d) the pH is greater than 6, preferably greater than 7, more preferably
greater than 7.5. The composition formed by the blending of the low-formaldehyde containing dispersion with the PAE
may be used as a binder for a textile or non-woven substrate, and may be applied to one or both sides of the substrate,
followed by curing. In further embodiments, the composition is a polymer binder that is used to bond a substrate for a
latex-bonded non-woven material comprising the substrate.
15
I. THE VINYL ESTER/ETHYLENE COPOLYMER

[0021] One essential polymeric component of the aqueous binder or finishing compositions applied to the non-woven
substrates(s) herein comprises a vinyl ester/ethylene emulsion copolymer. Preferred emulsion polymers of this type are
20 emulsion copolymers which comprise at least two different non-functional main co-monomers which, along with appro-
priately selected optional functional co-monomers, and which have been emulsion polymerized to form an aqueous
copolymer dispersion or latex.

Emulsion polymer monomers

25
[0022] One preferred type of primary non-functional monomer for use in forming this composition component comprises
vinyl ester co-monomers. Examples thereof are vinyl esters of monocarboxylic acids having one to eighteen, preferably
one to thirteen carbon atoms, e.g. vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl
benzoate, vinyl-2- ethyl-hexanoate, vinyl esters of an [alpha] -branched carboxylic acid having 5 to 11 carbon atoms in
30 the acid moiety, e.g., versatic acids which form vinyl esters such as VeoVa 9, VeoVa 10, and VeoVa 11, and the vinyl
esters of pivalic, 2-ethylhexanoic, lauric, palmitic, myristic, and stearic acid. Vinyl acetate is the preferred main monomer
for use in preparing the vinyl emulsion polymer component of the compositions herein.
[0023] Vinyl acetate and ethylene as the main co-monomers can also be copolymerized with other types of co-mon-
omers: non-functional co-monomers, such as other vinyl ester monomers or alkyl esters of acrylic or methacrylic acid,,
35 and functional co-monomers, such as unsaturated sulphonic acid or unsaturated carboxylic acid monomers or their salts
to form vinyl acetate-ethylene (VAE) co- or ter-polymers, which are especially useful in the binder and finishing compo-
sitions herein. In some embodiments, the ethylenically unsaturated acid comprises an α-β unsaturated mono- or di-
carboxylic acid, preferably, an α-β unsaturated mono- or di-carboxylic acid that contains 3 to 8 carbon atoms. In preferred
embodiments, the unsaturated mono- or dicarboxylic acid is one or more of acrylic acid, methacrylic acid, crotonic acid,
40 itaconic acid, maleic acid and C1 to C12 mono-alkyl esters of itaconic or maleic acid. In preferred VAE copolymers, the
primary vinyl acetate co-monomer is generally present in the copolymer in amounts from 60 to 90 wt.%, e.g., from 70
to 85 wt.%, based on the total weight main co-monomers in the copolymer. Ethylene is generally present in the copolymer
in amounts from 4 to 40 wt.%, e.g., from 5 to 35 wt.%, from 10 to 30 wt.%, or from 15 to 25 wt.%, based on the total
weight of the main co-monomers in this preferred type of VAE emulsion copolymer. The unsaturated carboxylic acid will
45 generally be present in amounts from 0.1 to 10 wt.%, e.g., from 0.25 to 5 wt.%, or from 0.5 to 2.5 wt.%, based on the
total main co-monomers in this preferred type of VAE emulsion copolymer.
[0024] The carboxylated vinyl ester/ethylene emulsion polymers used in binder/finishing compositions herein can also
optionally contain relatively minor amounts of other types of co-monomers besides the main co-monomer types, i.e.,
vinyl ester, e.g., vinyl acetate, ethylene or unsaturated carboxylic acid co- monomer types. Such other optional co-
50 monomers will frequently be those which contain one or more functional groups which can additionally stabilize the
polymer dispersion or and can serve to provide or facilitate cross-linking between copolymer chains within a copolymer
dispersion-containing aqueous composition, or upon the drying or curing of binders or finishing agent compositions.
[0025] One type of functional co-monomer which should not be incorporated into vinyl ester emulsion copolymers
used herein comprises any co-monomer which contains cross-linkable moieties that generate formaldehyde upon curing
55 of the binder or finishing agent compositions containing such copolymers. Thus the vinyl ester/ethylene copolymer in
the dispersion should be substantially free of such co- monomers, which include, for example, common cross-linkers
like N-methylol acrylamide (NMA) including low formaldehyde versions of N-methylol acrylamide such as NMA-LF.

5
 EP 3 387 176 B1

Stabilizers for the carboxylated vinyl ester/ethylene polymer dispersions

[0026] Both during polymerization and thereafter, the emulsion polymers used to prepare the aqueous binder or
finishing agents compositions herein are generally stabilized in the form of an aqueous polymer dispersion or latex. The
5 polymer dispersion therefore will be prepared in the presence of and will contain a stabilization system which generally
comprises surfactants, in particular nonionic surfactants. Mixtures of nonionic and anionic surfactants can also be em-
ployed.
[0027] The amount of surfactants employed will generally be at least 0.5 wt.%, based on the total quantity of main
monomers in the polymer dispersion. Generally surfactants can be used in amounts up to 8 wt.%, based on the total
10 quantity of main monomers in the polymer dispersion.. Preferably, the surfactants used to stabilize the polymer dispersions
comprises primarily nonionic surfactants, e.g. the weight ratio of nonionic to anionic surfactants may fluctuate within
ranges, between 2:1 and 50:1 preferably when anionic surfactants are present. In some preferred embodiments, the
carboxylated vinyl ester/ethylene emulsion dispersion is substantially free i.e., comprising less than 2 wt.% , or less than
1 wt.% of anionic surfactant on an active basis (i.e.., dry surfactant excluding water and other salts or byproducts). The
15 use of the primarily nonionic surfactants as stabilizers can avoid stability problems that may occur when the dispersion
is blended with PAE resin, a cationic resin, which is described in sections below.
[0028] Surfactants employed with preference in preparing the emulsion polymers herein are nonionic surfactants
having alkylene oxide groups and/or anionic surfactants having sulfate, sulfonate, phosphate and/or phosphonate groups.
Such surfactants, if desired, can be used together with water-soluble polymers, preferably together with polyvinyl alcohol
20 or hydroxyethyl cellulose. Preferably, the surfactants contain no alkylphenolethoxylates (APEO).
[0029] Examples of suitable nonionic surfactants include acyl, alkyl, oleyl, and alkylaryl ethoxylates. These products
are commercially available, for example, under the names Genapol®, Lutensol®, Emulan® or Emulsogen®. They include,
for example, ethoxylated mono-, di-, and trialkylphenols (EO degree: 3 to 50, alkyl substituent radical: C4 to C12) and
also ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C8 to C 36), especially C12-C14 fatty alcohol (3-40)
25 ethoxylates, linear and branched C11 oxo-process alcohol (3 - 40) ethoxylates, C13-C 15 oxo-process alcohol (3-40)
ethoxylates, C16-C18 fatty alcohol (11-80) ethoxylates, C10 oxo-process alcohol (3-40) ethoxylates, C13 oxo- process
alcohol (3-40) ethoxylates, polyoxyethylenesorbitan monooleate with 20 ethylene oxide groups, copolymers of ethylene
oxide and propylene oxide having a minimum ethylene oxide content of 10 wt.%, the polyethylene oxide (4-40) ethers
of oleyl alcohol, and the polyethylene oxide (4-40) ethers of nonylphenol. Particularly suitable are the polyethylene oxide
30 (10-40) ethers of Cn alkyl alcohols, an alcohol ethoxylate nonionic surfactant, e.g., Emulsogen® EPN 287, Clariant GmbH,
Functional Chemicals, Germany.
[0030] The amount of nonionic surfactants used in preparing the emulsion polymer dispersions used herein is typically
from 1 to 8 wt.%, preferably from 1 to 6 wt.%, more preferably from 2% to 6 wt.%, based on the total main monomer
quantity. Mixtures of nonionic surfactants can also be employed.
35 [0031] Examples of suitable anionic surfactants include sodium, potassium, and ammonium salts of linear aliphatic
carboxylic acids of chain length C 12-C20, sodium hydroxyoctadecanesulfonate, sodium, potassium, and ammonium salts
of hydroxy fatty acids of chain length C12-C20 and their sulfonation and/or sulfation and/or acetylation products, alkyl
sulfates, including those in the form of triethanolamine salts, alkyl(C10-C20) sulfonates, alkyl(C10-C20) arylsulfonates,
dimethyl-dialkyl (Cs-Cis) ammonium chloride, and their sulfonation products, lignosulfonic acid and its calcium, magne-
40 sium, sodium, and ammonium salts, resin acids, hydrogenated and dehydrogenated resin acids, and their alkali metal
salts, dodecylated sodium diphenyl ether disulfonate, sodium lauryl sulfate, sulfated alkyl or aryl ethoxylate with EO
degree between 1 and 10, for example ethoxylated sodium lauryl ether sulfate (EO degree 3) or a salt of a monoester
or diester, preferably of a C4-C8 Cis alkyl ester, of a sulfonated dicarboxylic acid having 4 to 8 carbon atoms, or a mixture
of these salts, preferably sulfonated salts of esters of succinic acid, more preferably salts, such as alkali metal salts, of
45 mono- or bis-C4-C8 is alkyl esters of sulfonated succinic acid, or phosphates of polyethoxylated alkanols or alkylphenols.
[0032] When present, the amount of anionic surfactants used can typically range from 0.001 to 2.0 wt.%, preferably
from 0.1 to 1.0 wt.%, more preferably from 0.25% to 0.75 wt.%, based on the total main monomer quantity. Mixtures of
anionic surfactants can also be employed.
[0033] The vinyl ester emulsion polymer dispersions may further comprise small amounts of polymeric stabilizers
50 (protective colloids). Protective colloids, if used, are generally present only in comparatively low concentrations, e.g.,
up to 3 wt.%, based on the total amount of the main monomers used. The vinyl ester dispersions employed herein will
more preferably contain no protective colloids or only up to 1 wt.% protective colloids, based on the total amount of the
main monomers employed in the emulsion polymer.
[0034] Examples of suitable protective colloids include water-soluble or water- dispersible polymeric modified natural
55 substances, such as cellulose ethers, examples being methyl-,ethyl-, hydroxyethyl- or carboxymethyl cellulose, water-
soluble or water-dispersible polymeric synthetic substances, such as polyvinylpyrrolidone or polyvinyl alcohols (with or
without residual acetyl content), and polyvinyl alcohol which is partially esterified or acetalized or etherified with saturated
radicals, and also with different molecular weights.

6
 EP 3 387 176 B1

[0035] The protective colloids can be used individually or in combination. In the case of combinations, the two or more
colloids can each differ in their molecular weights or they can differ in their molecular weights and in their chemical
composition, such as the degree of hydrolysis, for example.
[0036] In addition to the surfactants and, if appropriate, protective colloids that are used during the emulsion polym-
5 erization of the emulsion polymers herein, it is also possible for the polymer dispersions used herein to contain subse-
quently added water-soluble or water-dispersible polymers as hereinafter described. Additional surfactants may also be
added to the dispersions post-polymerization.

Emulsion polymer preparation

10
[0037] The polymer dispersions comprising the vinyl ester/ethylene copolymer dispersions described herein can be
prepared using emulsion polymerization procedures which result in the preparation of polymer dispersions in aqueous
latex form. Such preparation of aqueous polymer dispersions of this type is well known and has already been described
in numerous instances and is therefore known to the skilled artisan. Such procedures are described, for example, in
15 The U.S. Patent No. 5,633,334, and in the Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 ff (1987).
[0038] The polymerization may be carried out in any manner known per se in one, two or more stages with different
monomer combinations, giving polymer dispersions having particles with homogeneous or heterogeneous, e.g., core
shell or hemispheres, morphology. Any reactor system such as batch, loop, continuous, cascade, etc., may be employed.
[0039] The polymerization temperature generally ranges from 20°C to 150°C, more preferably from 50°C to 120°C.
20 The polymerization generally takes place under pressure if appropriate, preferably from 2 to 150 bar, more preferably
from 10 to 100 bar.
[0040] In a typical polymerization procedure involving, for example, vinyl acetate/ethylene copolymer dispersions, the
vinyl acetate, ethylene, stabilizing system and other co-monomers can be polymerized in an aqueous medium under
pressures up to 150 bar in the presence of one or more initiators. The aqueous reaction mixture in the polymerization
25 vessel can be maintained by a suitable buffering agent at a pH of 3 to 7.
[0041] The manner of combining the several polymerization ingredients, i.e., stabilizing system, co-monomers, initiator
system components, etc., can vary widely. Generally an aqueous medium containing at least part of the stabilizing
system can be initially formed in a polymerization vessel with the various other polymerization ingredients being added
to the vessel thereafter.
30 [0042] Co-monomers can be added to the polymerization vessel continuously, incrementally or as a single charge
addition of the entire amounts of co-monomers to be used. Co-monomers can be employed as pure monomers or can
be used in the form of a pre-mixed emulsion. Ethylene as a co-monomer may be pumped into the polymerization vessel
and maintained under appropriate pressure therein.
[0043] It is possible for the total amount of redox initiator system to be included in the initial charge to the reactor at
35 the beginning of the polymerization. Preferably, however, a portion of the initiator is included in the initial charge at the
beginning, and the remainder is added after the polymerization has been initiated, in one or more steps or continuously.
It is also possible to start the emulsion polymerization using a seed latex, for example with from 0.5 to 15 wt.% of the
polymerization mixture.

40 Carboxylated vinyl ester/ethylene copolymer characteristics

[0044] The molecular weight of the various vinyl ester/ethylene polymers used in the polymer dispersions herein can
be adjusted by adding small amounts of one or more molecular weight regulator substances. These regulators, as they
are known, are generally used in an amount of up to 2 wt.%, based on the total co-monomers to be polymerized. As
45 regulators, it is possible to use all of the substances known to the skilled artisan. Preference is given, for example, to
organic thio compounds, silanes, allyl alcohols, and aldehydes.
[0045] The vinyl ester/ethylene polymer dispersions as prepared herein will generally have a viscosity which ranges
from 20 mPas to 5000 mPas at 45 - 70 % solids, more preferably from 50 mPas to 2000 mPas, most preferably 50 -
1000 mPas, measured with a Brookfield viscometer at 25°C, 20 rpm, with appropriate spindle, e.g., spindle 2. Viscosity
50 may be adjusted by the addition of thickeners and/or water to the polymer dispersion. Suitable thickeners can include
polyacrylates or polyurethanes, such as Borchigel L75® and Tafigel PUR 60®. Alternatively, the polymer dispersion may
be substantially free of thickeners.
[0046] The vinyl ester/ethylene polymer dispersions as prepared herein will generally have a (mid-point) glass transition
temperature Tg, of from -25 °C to +30 °C, preferably -15 °C to +10 °C, most preferably -10 °C to +5 °C. The dispersions
55 will generally have a grit level below 0.1%, preferably below 0.01%
[0047] Following polymerization, the solids content of the resulting aqueous polymer dispersions can be adjusted to
the level desired by the addition of water or by the removal of water by distillation. Generally, the desired level of polymeric
solids content after polymerization is from 30 weight percent to 70 weight percent based on the total weight of the polymer

7
 EP 3 387 176 B1

dispersion, more preferably from 40 weight percent to 65 weight percent, most preferably from 50 weight percent to 60
weight percent.

Polyamidoamine-epichlorohydrin wet strength resin (PAE)

5
[0048] Polyamidoamineepichlorohydrin wet strength resin (PAE) (also popularly known as "kymene") is used in adja-
cent industries, e.g., the paper-making industry, to boost wet properties in the finished, (dry), paper product. PAE resins
contain quaternary ammonium groups with the ability to adsorb onto negatively charged cellulose fibers, and azetidinium
reactive groups that typically continue to cross-link as the paper dries and cures, thereby increasing wet properties upon
10 storage. More specifically, PAE resins cure without formation or liberation of formaldehyde. Such chemistry has, in the
past, typically not been compliant with the food contact regulations typically required by the non-wovens industry, spe-
cifically the German BfR section XIV. Recent innovations by PAE resin manufacturers have now resulted in a generation
of products that are food contact compliant with low absorbable organic halogen, (AOX), levels, making them more
suitable for use in the target industries currently utilizing methylol based cross-linking dispersions. PAE resins are
15 commercially available from, for example, Mare spa or Solenis.
[0049] AOX levels are increased by all of the chlorine-containing by-products in the PAE manufacturing process,
including 1,3-dichloropropanol (DCP), 3-monochloropropan-1,2-diol (3-MCPD), aminochlorohydrin (ACH), and polymer
bound-1-chloro-2,3-propanediol (PB-CPD). Preferred PAEs to be used in the compositions disclosed herein are second
or later generations, so called G2, G2.5, or G3 PAE resins that have reduced AOX levels, e.g., AOX levels below 0.60
20 wt.%, e.g., below 0.25 wt.%, below 0.20 wt.%, or below 800 ppm. PAE is normally supplied as an aqueous solution with
solids content from 12.5 to 30% or from 15 to 25%. The level of undesired byproducts in the PAE disclosed herein has
been reduced so that the level of 1,3-dichloropropanol (DCP) in the PAE is below 700 ppm, e.g., below 500 ppm, below
150 ppm, below 50 ppm; the level of 3-MCPD is below 600 ppm, e.g., below 500 ppm, below 400 ppm, or below 50
ppm. Non-limiting examples of PAE suitable for the purpose of the invention are Maresin PST 150, Maresin M1 and
25 Maresin T35.

Polymer binder preparation

[0050] The polymer binder compositions disclosed herein are formed from a blend of the vinyl ester/ethylene copolymer
30 containing the copolymerized carboxylic acid groups with a PAE resin, as described above. This blend can be prepared
by combining the vinyl ester/ethylene copolymer and the aqueous emulsion of the PAE together in any suitable manner
or device.
[0051] In combining these components to form the compositions herein, the weight ratio of the solid particles of said
carboxylated vinyl ester/ethylene copolymer to the solid particles in the aqueous emulsion of PAE, within the blend,
35 ranges from 95:5 to 20:80, preferably, from 85:15 to 30:70, more preferably from 75:25 to 40:60. In some embodiments,
the weight ratio between the two is 50:50.
[0052] Other adjuvants may also be present in the binder and finishing agent compositions herein at concentrations
which range from 0 to 2 wt.% on a dry basis. Other additives that may optionally be incorporated into the binder composition
include, but are not limited to, suspension aids, thickening agents, parting agents, penetrating agents, wetting agents,
40 thermal gelling agents, sizing agents, defoaming agents, foam suppressors, blowing agents, coloring agents, oxidation
inhibitors, quenchers, antimicrobial agents, dispersants, antistatic agents, cross linking agents (to improve wet strength),
dispersants, lubricants, plasticizers, pH regulators, flow modifiers, setting promoters, and water-proofing agents, and
mixtures thereof. Any optional adjuvants which are added to the binder and finishing agent compositions herein should
not add any significant amounts of free and/or bound formaldehyde.
45
Characteristics of the binder

[0053] The solids content and viscosity of the binder and finishing agent compositions herein, which are aqueous in
nature, can vary widely depending upon the type of non-woven substrate or textile to be treated therewith, the amount
50 of binder or finishing agent composition to be applied, and the nature of the process and apparatus to be used in applying
the composition. Furthermore, aqueous polymer dispersions used as fibre bonding agents are typically diluted with water
prior to application to the fibres through a variety of methods including air-spray bonding, airless bonding, saturation
and foaming. The non-volatile content of the carboxylated VAE dispersion can vary between 30 and 70%, more typically
between 40 and 60%. The blend of VAE dispersion and PAE resin prior to application can vary between 5 and 40%,
55 typically between 10 and 30% solids.
[0054] The compositions herein when used as a binder for non-woven substrates have especially low formaldehyde
contents by virtue of containing no significant amount of components which can generate formaldehyde when the binder
compositions are cured. Such compositions, however, can nevertheless still impart desirable tensile strength charac-

8
 EP 3 387 176 B1

teristics, both wet and dry, to such treated non-woven substrates. This is true even though the compositions contain no
conventional wet strength-imparting cross-linking moieties of the type which tend to release formaldehyde upon com-
position curing.
[0055] Both of these composition properties can be quantified by means of the formaldehyde content and tensile
5 strength testing described hereinafter in the Test Methods section. Illustrative examples which can be used to quantify
free and bound formaldehyde involve application of binder at a 20 percent add-on to Whatman #1 CHR chromatography
paper which is then oven dried for 15 minutes at 60°C and cured for 20 seconds in one instance at 150°C and in another
instance at 200°C. These paper samples can then be tested for formaldehyde content in accordance with the formal-
dehyde content tests described hereinafter in the Test Methods section and for wet and dry tensile strength in accordance
10 with test procedure ED ANA 20.2-89 or Method WSP 110.4 (EDANA 2008). The retention was calculated by dividing
the wet tensile strength by the dry tensile strength, expressed as a percentage and known within the Industry as a wet/dry
tensile ratio.
[0056] When such testing is carried out, the binder compositions herein will generally exhibit a "free" formaldehyde
content less than 5 ppm, preferably less than 2 ppm, and a wet to dry tensile strength ratio (a.k.a. retention ratio) of
15 greater than 30%, preferably greater than 40%. Performance gains are evident after drying, and after drying with additional
cure (for example, at temperatures between 130 -200°C). For example, Whatman #1 CHR chromatography paper
saturated with the composition produced as described above at a 16 % add-on, dried for 15 minutes at 130°C, has a
dry tensile strength of greater than 200 N/5 cm wide strip, a wet tensile strength at least 35%, preferably at least 40%,
more preferably at least 45% of the dry tensile strength, and a bound formaldehyde content of less than 5 ppm as
20 determined by the VdL-RL03(1997-05) method.

Non-woven substrates, fabrics and textiles

[0057] The compositions described hereinbefore are useful as binders and finishing agents for non-woven substrate
25 and textiles. As used herein, a "non-woven substrate" means a web or sheet having a structure comprising individual
fibers or threads which are interlaid, but not in an identifiable, repeating manner. Such non-woven fibrous webs or sheets
can be conventionally formed from a wide variety of fibrous materials and by a wide variety of procedures and processes.
[0058] Fibers used to form the non-woven substrates treated with the compositions herein can be natural fibers, i.e.
latex bonded airlaid [LBAL], synthetic fibers, bicomponent fibers i.e. multi bonded airlaid [MBAL], or combinations of
30 such fiber types. Non-woven structures useful, for example, as absorbent cores in personal care products or in paper
are frequently natural fibers, including those which are cellulosic in origin. Synthetic fibers and bicomponent fibers are
generally fashioned from synthetic polymeric material. In some embodiments, the non-woven substrate primarily com-
prises cellulosic fibers, for example, a typical LBAL structure could consist of 90-70 parts dry cellulosic fibres with dry
binder content between 10-30% whereas an MBAL design is likely to contain dry binder, fluff pulp and bicomponent
35 fibres in the ratios of 6:84: 10.
[0059] The non-woven substrates herein can be in the form of a structure which is airlaid or wetlaid, but also not to
exclude drylaid carded. Airlaid non-woven webs can be prepared, for example, by laying down cellulosic fibres (i.e. fluff
pulp) onto a conveyor wire by means of an air stream through a forming head. Bicomponent fibres can also be introduced
into the fibre mix within the forming heads themselves. Wet laid substrates can include, for example, webs formed by
40 hydrogen-bonding of cellulosic based fibres. In both cases, application of a bonding agent is quite typical to consolidate
the structure and add strength plus functionality. A common wetlaid non-woven substrate is paper.
[0060] The aqueous binder compositions herein can be used to consolidate and strengthen non-woven substrates as
hereinbefore described. Thus the resulting structures formed after addition of the binder compositions herein can be a
latex-bonded airlaid web, a multi-bonded airlaid web, a drylaid carded web or a wetlaid web.
45 [0061] The binder compositions herein are generally used in a manufacturing process which produces structures in
the form of a chemically-bonded web, as opposed to mechanically tangled or thermally bonded webs. Alternatively, the
binder compositions herein can be used to post-treat and further strengthen mechanically tangled or thermally bonded
webs which have been pre-formed in the absence of a chemical bonding agent.
[0062] In the manufacturing process for chemically bonded non-woven substrates, the binder composition can be
50 applied to the non-woven fibrous structures described herein by any means known in the art, such as print, foam,
saturation, coating, and spraying application. The binder-containing structure can then be cured, i.e., dried, on steam
cans or in ovens as currently practiced in the production of non-woven rolled goods. Curing temperatures of from 100
°C to 220 °C are frequently employed. Most preferred is the spray application of the binder composition to the fibrous
structure in combination with drying and curing of the resulting web using heated ovens.
55 [0063] Binder add-on levels for non-woven fibrous substrates herein can be from 5 to 40 wt.%, e.g., from 5 to 30 wt.%,
from 5 to 20 wt.%, or from 10 to 15 wt.%, based on the total weight of the non-woven material, on a dry basis. Stated
alternatively, in the treated non-woven substrates herein, the fibers of the fibrous webs comprise from 60 to 95 parts by
dry weight of the treated substrate and the binder composition solids comprise from 5 to 40 parts by dry weight of the

9
 EP 3 387 176 B1

treated substrate.
[0064] The aqueous compositions herein can also be utilized as a finishing agent for woven or non-woven fabrics and
textiles. When used in this manner, the compositions herein can be applied to one or both surfaces of textiles or non-
woven fabrics or substrates and then subsequently cured. Finishing agent add-on levels of from 3 to 30 wt.%, on a dry
5 basis, are frequently employed to provide full latex bonding and surface finishing plus multi-bonded structures with the
finish on the upper and lower x/y surface planes only..

Treated substrate characteristics

10 [0065] The treated non-woven substrates herein have a desirable combination of relatively low formaldehyde content
and relatively high tensile strength. This desirable combination of properties makes the treated substrates herein useful
in a variety of contexts.
[0066] With respect to formaldehyde content, the treated substrates herein will exhibit very low formaldehyde levels
even when exposed to relatively rigorous conditions which can extract bound formaldehyde as well as free formaldehyde
15 from the treated substrate. Thus the treated substrates herein will preferably exhibit formaldehyde levels of less than 5
ppm, preferably 1 ppm or less, when tested in accordance with Japanese Ministry JM 112:1973 procedure described
more fully hereinafter in the Test Methods section. Alternatively, the treated substrates herein will also preferably exhibit
bound formaldehyde levels of less than 5 ppm, preferably 1 ppm or less, when tested in accordance with the VdL-
RL03(1997-05) procedure also described more fully hereinafter in the Test Methods section.
20 [0067] With respect to tensile strength, the treated substrates herein can exhibit both good dry and wet tensile strength.
Tensile strength can be determined using the Method WSP 110.4 (EDANA 2008) test procedure which is also more
fully described hereinafter in the Test Methods section. The absolute tensile strength values obtained will, of course,
vary widely depending upon the type of treated substrate prepared and tested. Preferably, no matter what type of non-
woven substrate is treated with the binder and/or finishing agent compositions herein, the treated substrate will exhibit
25 a wet to dry tensile strength ratio of greater than 30 %, preferably greater than 40%, greater than 45%, or greater than 50%.

Substrate Uses

[0068] The treated substrates herein can be used in a wide variety of contexts wherein substrates of this type are
30 conventionally employed. Frequently, such non-woven substrates can be utilized in ways which take advantage of their
propensity to absorb and transport liquids. Thus, for example, the treated substrates herein can form part of a number
of consumer products including household or industrial cleaning products and personal care products.
[0069] With respect to personal care products, the treated non-woven substrates which are chemically bonded non-
woven fibrous structures can be used as both fluid acquisition/distribution elements and fluid storage elements in personal
35 care products designed to absorb alkaline body fluids such as infant or adult urine. Thus the structures herein are useful
in applications wherein wet integrity or resiliency are important, such as in, for example, infant diapers, adult incontinence
articles and devices and feminine hygiene products.
[0070] The use of non-woven fibrous structures as body fluid acquisition/distribution layers (ADLs) in personal care
article such as diapers is well known. Structures which perform this function are described, for example, in U.S. Patent
40 Nos. 5,217,455; 5,716,703; 7,138,561; 7,767,598; and 7,786,341. The treated non-woven substrates herein can function
as ADLs in analogous manner to the ADLs in such known contexts.

II. EXAMPLES

45 A. Test Methods

Solids Content

[0071] Solids content was measured by drying 1 to 2 grams of the aqueous dispersion at 105°C for 4 hours, and by
50 then dividing the weight of dried polymer by the weight of dispersion.

Viscosity

[0072] Viscosity was determined at 25°C using a Brookfield DV-I+ Viscometer, spindle 2, speed 20 rpm.
55
Grit

[0073] Grit was determined by filtering 100 g of dispersion through a 40mm filter, drying and weighing the dried grit.

10
 EP 3 387 176 B1

This was expressed as a percentage on the wet dispersion.

Glass Transition Temperature

5 [0074] Determination of the Glass Transition Temperature, (Tg), was according to ASTM E 1356 by Differential Scan-
ning Calorimetry, (DSC), using a Mettler DSC 820 with a fluid N2 cooling system. The tested range was from -80°C to
130°C with a heating rate of 10°C/min. The onset of the Tg range was the value which was reported.

Free Formaldehyde Content - Japanese Ministry Method JM 112:1973

10
[0075] Formaldehyde content of binder-containing non-woven substrates can be determined in accordance with the
extraction procedures of JM 112:1973 in combination with High Performance Liquid Chromatography (HPLC) which is
widely used within the absorbent non-wovens Industry. The procedure essentially extracts the HCHO in a known weight
of substrate by refluxing in water for 1 hour at 40°C followed by derivatization and quantification. The time/temperature
15 combination can be selected to mimic conditions associated with human skin contact i.e. body temperature. HPLC is
preferred over photometric techniques (i.e. absorbance at 412 nm using UV - vis.) since it only measures the HCHO
based on retention time of the H.CHO in the column therefore giving a very accurate result. Furthermore, the JM 112:
1973 procedure using HPLC can be modified with extended reflux conditions from 1 hour at 40 C to 4 hours at 40 C
invoking more demanding test conditions .
20
Bound Formaldehyde Content - VdL-RL03 Method (1997-05)

[0076] Formaldehyde content can also be determined in accordance with the procedures of the VdL-RL03 (1997-05)
method. This method differs from the JM 112:1973 procedure in that is uses steam distillation under acidic conditions.
25 Furthermore, no serum is separated before a Nash (derivatization) reactant is added. This most probably leads to higher
HCHO values compared to other methods (e.g. ISO 15373 or ASTM D 5910-05), where the serum is separated first, as
other aldehydes will also be derivatized and quantified in the total measured. Quantification in the VdL-RL03 (1997-05)
method is done using UV-vis photometry instead of HLPC. The VdL-RL03(1997-05) method has historically been used
in the paint industry where the acid is added to produce very severe test conditions designed to release all the "bound"
30 HCHO from the components of the system.

Tensile strength

[0077] Sample specimens for tensile testing were prepared as follows: The PAE resin was added slowly to the VAE
35 dispersion in the ratios shown in the following tables, then water was added to give a solids content of approximately
19%. Whatman # 1 filter paper sheets, commercially available from Whatman Inc., were saturated using a pad mangle
to give an add-on of 17% (dry). The wet, impregnated Whatman sheets were dried in an oven at 130°C for 15 minutes.
Strips 5 cm wide were prepared and were tested either dry or after 30 minutes immersion in water. Tensile strength was
measured according to Method WSP 110.4 (EDANA 2008). Quoted tensile strength values are the average of 8 meas-
40 urements on specimens cut from different sheets. The retention was calculated by dividing the wet tensile strength by
the dry tensile strength, expressed as a percentage.

B. Test Materials

45 [0078] In the following examples, PAE resins used in the examples were Maresin PST 150, Maresin M1 and Maresin
T35, which are commercially available from Mare spa. Abbreviations used for monomers are: VA = Vinyl Acetate, E =
Ethylene, AA = Acrylic Acid, CA = Crotonic Acid, IA = Itaconic Acid, SVS = Sodium Vinyl Sulphonate

C. Preparation of VAE dispersions

50
[0079] Vinyl Acetate / Ethylene, (VA/E), terpolymer dispersions were prepared as shown in Examples 1-11.

Example 1: A VA/E/AA terpolymer with monomer ratios 80/20/1

55 [0080] An aqueous solution was prepared by dissolving 125.7 g of a 70% active solution of an alcohol ethoxylate
nonionic surfactant, (Emulsogen EPN 287 from Clariant GmbH), in 2307.8 g of deionized water while stirring. 48.1 g of
a 25% active solution of sodium vinylsulphonate, (SVS), was added, followed by 0.24 g of ferrous sulphate heptahydrate,
then the pH was adjusted to pH 4.4 by the use of phosphoric acid. Then the aqueous solution was charged to a 10-litre

11
 EP 3 387 176 B1

pressure reactor equipped with a stirrer, dosage pumps and a mass flow meter for dosing ethylene. The reactor was
degassed by twice evacuating, then pressurizing with nitrogen to 2 bar, then finally evacuating.
[0081] 865.4 g of vinyl acetate was pumped to the reactor, and the temperature was raised by heating to 45C. 692.4
g of ethylene was metered to the reactor, followed by 10% of a reducer solution comprising 15.4 g of Brueggolite FF6
5 and 2.88 g of sodium bicarbonate dissolved in 346.2 g of deionised water.
[0082] A second aqueous solution, (Aqueous Slow-Add), was prepared comprising 247.3 g of the same nonionic
surfactant dissolved in 577 g of deionized water.
[0083] When the reactor temperature stabilised at 45°C, the additions of an oxidiser solution comprising 16.5 g of 70%
active t-butyl hydroperoxide dissolved in 274.6 g of deionised water and the remaining 90% of the reducer solution were
10 commenced at a constant rate to last 300 minutes. The water jacket temperature was increased to 80°C, and the internal
temperature allowed to rise by the combination of reaction and external heating.
[0084] At 55°C, the additions of a mixture comprising 57.7 g of Acrylic Acid, (AA) with 3750.2 g of VA and of the
Aqueous Slow-Add solution were started to last for 240 minutes at a constant rate. At the same time, a further 461 g of
ethylene was added at a rate to last 60 minutes or longer, with a pressure limit of 65 bar maximum pressure. When the
15 reactor temperature reached 72°C, it was switched to internal temperature control, and the water jacket temperature
was varied to keep the reaction temperature at 75°C until all additions were complete.
[0085] After the additions of the oxidizer and reducer solutions were finished, the reactor was cooled to 55°C, and the
contents transferred to a second vessel. When 50% had been transferred, a solution comprising 2.3 g of Brueggolite
FF6, 0.58 g of Agitan 282 defoamer and 0.12 g of ferrous sulphate heptahydrate in 57.7 g of deionised water was added
20 over 5 minutes. Once all of the reactor contents were transferred and the pressure was below 1 bar, a solution comprising
1.65 g of t-butylhydroperoxide and 3.85 g of 30% active hydrogen peroxide in 57.7 g of deionised water was added, and
the temperature was kept at 50°C for 30 minutes. The vessel was cooled, the contents discharged, and the resultant
dispersion was filtered through a 180m mesh. The resultant dispersion had a solids content of 60.0%, viscosity of 214
mPa.s, pH of 5.4, grit, (measured on a 40 m mesh), of 0.1% and a Tg, (onset, by DSC), of -8.1°C.
25
Example 2: A VA/E/CA terpolymer with monomer ratios 80/20/1

[0086] A similar procedure was followed as for Example 1, except that the Crotonic Acid, (CA), was dissolved in the
Aqueous Slow-add solution and not in the VA. The resultant dispersion had a solids content of 59.5%, viscosity of 254
30 mPa.s, pH of 5.6, grit of 0.01% and a Tg, (onset, by DSC), of -6.4°C.

Example 3: A VA/E/IA terpolymer with monomer ratios 80/20/1

[0087] A similar procedure was followed as for Example 1, except that the Itaconic Acid, (IA), was dissolved in the
35 Aqueous Slow-add solution and not in the VA. The resultant dispersion had a solids content of 60.1%, viscosity of 274
mPa.s, pH of 4.7, grit of 0.007% and a Tg, (onset, by DSC), of -8.0°C.

Example 4: A VA/E/AA terpolymer with monomer ratios 80/20/2

40 [0088] A similar procedure was followed as for Example 1, except that AA level was increased to 114.7 g. The resultant
dispersion had a solids content of 60.3%, viscosity of 230 mPa.s, pH of 5.0, grit, (measured on a 40 m mesh), of 0.02%
and a Tg, (onset, by DSC), of - 5.9°C.

Example 5: A VA/E/IA terpolymer with monomer ratios 80/20/2

45
[0089] A similar procedure was followed as for Example 3, except that the IA level was increased to 114.7 g. The
resultant dispersion had a solids content of 59.8%, viscosity of 410 mPa.s, pH of 5.0, grit of 0.02% and a Tg, (onset, by
DSC), of -8.0°C.

50 Example 6: A VA/E/CA terpolymer with monomer ratios 80/20/1

[0090] This was a repeat of Example 2. The resultant dispersion had a solids content of 57.8%, viscosity of 290 mPa.s,
pH of 5.6, grit of 0.04% and a Tg, (onset, by DSC), of -7.2°C.

55 Example 7: A VA/E/CA terpolymer with monomer ratios 80/20/1

[0091] This was a process modification of Example 2, where the jacket temperature was fixed and the oxidizer and
reducer addition rates allowed to vary to maintain the reaction temperature. The resultant dispersion had a solids content

12
 EP 3 387 176 B1

of 59.0%, viscosity of 290 mPa.s, pH of 5.6, grit of 0.02% and a Tg, (onset, by DSC), of -5.9°C.

Example 8: VA/E/AA/CA terpolymer with monomer ratios 80/20/0.5/0.5

5 [0092] A similar procedure was followed as for Example 1, except that half of the AA was replaced by CA, (which was
dissolved in the Aqueous Slow-add solution and not in the VA). The resultant dispersion had a solids content of 58.9%,
viscosity of 310 mPa.s, pH of 5.5, grit of 0.06% and a Tg, (onset, by DSC), of -8.1°C.

Example 9: A VA/E/CA terpolymer with monomer ratios 80/20/1

10
[0093] A similar procedure was followed as for Example 1, except that the initial water phase contained no SVS, only
83.2 g of the nonionic surfactant and 93.9 g of an anionic half-ester sulphosuccinate surfactant, (Rewopol SB FA 50
from Evonik). The resultant dispersion had a solids content of 58.8%, viscosity of 280 mPa.s, pH of 5.2, grit of 0.1% and
a Tg, (onset, by DSC), of -6.7°C.
15
Example 10: A VA/E/CA terpolymer with monomer ratios 80/20/1

[0094] A similar procedure was followed as for Example 1, except that the initial water phase contained 2779 g of
deionized water ansd an additional 48.1 g of SVS was added to the Aqueous Slow-Add. The resultant dispersion had
20 a solids content of 55.2%, viscosity of 78 mPa.s, pH of 5.9, grit of 0.03% and a Tg, (onset, by DSC), of -6.0°C.

Example 11: A VA/E/CA terpolymer with monomer ratios 80/20/1

[0095] A similar procedure was followed as for Example 1, except that the initial water phase contained 2769 g of
25 deionized water and 153 g of the alcohol ethoxylate nonionic surfactant, and the aqueous slow-add contained 229.5 g
of the alcohol ethoxylate nonionic surfactant. As a final step the dispersion was stripped using a rotary evaporator,
(Rotavapr R-220 SE, from Buchi), to reduce the total VOC’s, (Volatile Organic Compounds), to below 1000 ppm. The
resultant dispersion had a solids content of 56.3%, viscosity of 254 mPa.s, pH of 5.0, grit of 0.02% and a Tg, (onset, by
DSC), of -7.3°C.
30
Comparative Example 1

[0096] Elite 20, a state of the art, low-formaldehyde VAE dispersion utilizing NMA cross-linking and commercially
available from Celanese was used as the comparison in all of the testing. Elite 20 has a solids content of 50%, an average
35 viscosity of 250 mPas, and a Tg, (onset by DSC), of -6°C.

Example 12

[0097] Test sheets were prepared and tested as described above, using blends of Maresin PST 150 with various VAE
40 dispersions at a ratio of VAE to PAE of 50/50, on a dry basis. Results are shown in Table 1.

Table 1
Tensile Strength of VAE Resins with PST 100 at a 50/50 ratio

45 VAE Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1

Dry, (N/5cm) 203.6 202.6 201.0 196.9 171.2 184.2
Wet, (N/5 cm) 106.3 104.1 98.9 83.5 80.1 105.6
Retention, (%) 52.2 51.4 49.2 42.4 46.8 57.3

50
Example 13

[0098] Test sheets were prepared and tested as described above, using blends of VAE of Examples 2, 3 and 5 with
different PAE resins at a ratio of VAE to PAE of 50/50, on a dry basis. Results are shown in Table 2.
55

13
 EP 3 387 176 B1

Table 2
Tensile strength of CA and IA containing VAE dispersions with different PAE resins at a 50/50 ratio
VAE PAE Dry (N/5cm) Wet (N/5cm) Retention (%)
5
Example 2 PST 150 211.9 99.0 46.7
Example 2 M1 237.6 123.5 52.0
Example 2 T35 218.0 87.6 40.2
Example 3 PST 150 220.6 86.1 39.0
10 Example 3 M1 238.4 116.4 48.8
Example 3 T35 225.4 100.7 44.7
Example 5 PST 150 217.5 122.0 56.1
Example 5 M1 210.4 106.5 50.6
Example 5 T35 228.7 120.4 52.6
15
Comparative Example 1 --- 212.1 106.2 50.1

Example 14

20 [0099] Test sheets were prepared and tested as described above, using blends of crotonic acid (CA) containing VAE’s
with Maresin M1, at a ratio of VAE to PAE of 50/50 on a dry basis. Results are shown in Table 3.

Table 3
Tensile strength of CA containing VAE dispersions with Maresin M1 at a 50/50 ratio
25
VAE Example 2 Example 6 Example 7 Example 8 Example 9 Comparative Example 1
Dry, (N/5cm) 227.1 226.6 232.2 230.3 227.8 220.3
Wet, (N/5 cm) 112.5 109.7 113.2 116.2 113.6 116.1
Retention, (%) 49.5 48.4 48.8 50.5 49.9 52.7
30

Example 15

[0100] Test sheets were prepared and tested as described above, using blends of a crotonic acid containing VAE with
35 Maresin M1, at different VAE to PAE ratios on a dry basis. Results are shown in Table 4.

Table 4
Tensile strength of CA containing VAE dispersion Example 10 with Maresin M1 at different ratios
VAE / PAE ratio 75/25 70/30 65/35 60/40 55/45 Comparative Example 1
40
Dry, (N/5cm) 204.3 206.6 208.0 219.8 216.6 215.0
Wet, (N/5 cm) 105.8 107.1 111.3 114.3 116.4 112.4
Retention, (%) 51.8 51.8 53.5 52.0 53.7 52.3

45
Example 16

[0101] Test sheets were prepared and tested as described above, using blends of a crotonic acid containing VAE with
Maresin M1, at 70:30 VAE to PAE ratio on a dry basis at different pH values. Results are shown in Table 5.
50
Table 5
Tensile Strength of CA containing VAE dispersion Example 10 and Example 11 with Maresin M1 at 70:30 ratio
at different pH values
Comparative
55 VAE Example 10 Example 10 Example 11 Example 11
Example 1
pH value 8.1 8.6 8.1 8.7 4

14
 EP 3 387 176 B1

(continued)

Table 5
Tensile Strength of CA containing VAE dispersion Example 10 and Example 11 with Maresin M1 at 70:30 ratio
5 at different pH values
Comparative
VAE Example 10 Example 10 Example 11 Example 11
Example 1
dry strengths (N) 230.8 230.8 235.2 242.9 221.8
10 wet strengths (N) 118.0 123.3 119.2 128.9 115.4
Ratio 51% 53% 51% 53% 52%

Example 17

15 [0102] Samples of the wet VAE Example 11 of the wet blend VAE Example 11/Maresin M1 at a 60/40 ratio, sheets
prepared as described above using VAE in Example 10, the blend VAE in Example 11/Maresin M1 in ratio 60:40 were
sent for determination of free formaldehyde in textiles and polymer dispersions according to JM 112 modified by using
HPLC to separate the formaldehyde. Results are shown in Table 6.

20 Table 6
Latex, free and bound formaldehyde levels in VAE dispersion Example 10 and of blend VAE Example
10/Maresin M1 at a 60/40 ratio
Example 11: Maresin M1 Comparative Example 1
25 Example 11 ratio 60/40 (Elite 20)
Wet Latex Formaldehyde (ppm) 13 5 67
Sheet1 (extractable, free) Formaldehyde
3 2 17
(ppm)
30 Bound 2 Formaldehyde (ppm) in 100%
solids dried film <5 >300
Sheet1: method is based on Japanese Ministry procedure but with High Performance Liquid Chromatography (HPLC)
and photometric quantification where HPLC is used to accurately separate the free HCHO
Bound 2: VdL-RL03 test method
35

Claims

1. A low-formaldehyde containing dispersion of a vinyl ester/ethylene copolymer containing copolymerized carboxylic

40 acid groups or salts thereof blended with a wet strength polyamidoamine-epichlorohydrin (PAE) resin; wherein:

a) the vinyl ester/ethylene copolymer dispersion is free of reactive N-methylol acrylamide groups;
b) the PAE comprises less than 800 ppm halogenated organic compounds (AOX);
c) the weight ratio of the solid particles of the vinyl ester/ethylene copolymer to the solid particles in the aqueous
45 emulsion of the PAE resin is from 95:5 to 20:80; and
d) the pH is greater than 6, preferably greater than 7, more preferably greater than 7.5.

2. A composition produced by blending the vinyl ester/ethylene copolymer dispersion and a PAE resin according to
claim 1, wherein the vinyl ester is vinyl acetate and wherein when Whatman #1 CHR chromatography paper is
50 saturated with the composition at a 16 % add-on, dried for 15 minutes at 130°C, the treated Whatman paper has a
dry tensile strength of greater than 200 N/5 cm wide strip, a wet tensile strength at least 35%, preferably at least
40%, more preferably at least 45% of the dry tensile strength, and a bound formaldehyde content of less than 5
ppm as determined by the VdL-RL03 method (1997 - 05).

55 3. Use of a dispersion according to claim 1 or a composition according to claim 2, wherein the dispersion or composition
is used as a binder for a textile or non-woven substrate, wherein the dispersion or composition has been applied to
one or both sides of the textile or non-woven fabric and then cured.

15
 EP 3 387 176 B1

4. A latex-bonded non-woven material comprising a substrate, wherein the substrate is bonded with a polymer binder
comprising a dispersion according to claim 1 or a composition according to claim 2, wherein:

a) the non-woven material has a wet tensile strength value of at least 35%, preferably 40% of its dry tensile
5 strength value;
b) the material has a bound formaldehyde content of less than 5 ppm as determined by the VdL-RL03 (1997-05)
method; and
c) the material has a free formaldehyde content of less than 5 ppm as determined using the JM 112; 1973 method.

10 5. The latex-bonded non-woven material of claim 4, wherein the weight ratio of dried vinyl ester/ethylene copolymer
to PAE blend to the weight of the fibers is from 3 to 30 wt.%, preferably from 5 to 20 wt.%, more preferably from 10
to 15 wt.%.

6. The latex-bonded non-woven material of claim 4 or 5, wherein the wet/dry tensile strength ratio of the material is at
15 least 45% and the bound formaldehyde is 1 ppm or less.

7. The latex-bonded non-woven material of any of claims 4 to 6, wherein the PAE is a so-called G2, G2.5 or G3 PAE
resin, and is an aqueous solution with solids content from 12.5 to 30%, wherein the level of undesired byproducts
has been reduced such that the level of 1,3-dichloropropanol, (DCP) is below 700 ppm, preferably below 500 ppm,
20 more preferably below 150 ppm, most preferably below 50 ppm, the level of 3-monochloropropan-1,2-diol, (MCPD),
is below 600 ppm, preferably below 500 ppm, more preferably below 400 ppm and most preferably below 50 ppm.

8. The latex-bonded non-woven material of any of claims 4 to 7, wherein the vinyl ester/ethylene copolymer of the
polymer binder is substantially free of anionic stabilization agent, wherein substantially free means less than 2 wt.%
25 of anionic surfactant on an active basis, preferably less than 1 wt.%.

9. The latex-bonded non-woven material of any of claims 4 to 8, wherein the vinyl ester/ethylene copolymer of the
polymer binder comprises a nonionic surfactant, a protective colloid, preferably polyvinyl alcohol or hydroxyethyl
cellulose, or combinations of a nonionic surfactant and a protective colloid.
30
10. The latex-bonded non-woven material of any of claims 4 to 9, wherein the fibres used to form the non-woven material
are selected from natural fibres, synthetic fibres, bicomponent fibres and combinations thereof, preferably wherein
the fibers used primarily comprise cellulosic fibers.

35 11. The latex-bonded non-woven material of any of claims 4 to 10, wherein the non-woven material is a latex-bonded
airlaid web, a multi-bonded airlaid web, a drylaid carded web or a wetlaid web.

12. Use of the latex-bonded non-woven material according to any of claims 4 to 11, wherein the non-woven material is
used, either alone or fabricated into a structure, to absorb liquids.
40
13. Use of the latex-bonded non-woven material according to any of claims 4 to 11, as a fluid acquisition/distribution
element or a fluid storage element of a personal care article.

14. A personal care article incorporating the latex-bonded non-woven material according to any of claims 4 to 11.
45
15. A household or industrial cleaning cloth or wipe incorporating the latex-bonded non-woven material according to
any of claims 4 to 11.

50 Patentansprüche

1. Formaldehydarme Dispersion eines Vinylester/Ethylen-Copolymers, das copolymerisierte Carbonsäuregruppen

oder Salze davon enthält, gemischt mit einem nassfesten Polyamidoamin-Epichlorhydrin (PAE)-Harz, wobei:

55 a) die Vinylester/Ethylen-Copolymer-Dispersion frei von reaktiven N-Methylol-Acrylamid-Gruppen ist;

b) das PAE weniger als 800 ppm halogenierte organische Verbindungen (AOX) umfasst;
c) das Gewichtsverhältnis der festen Teilchen des Vinylester/EthylenCopolymers zu den festen Teilchen in der
wässrigen Emulsion des PAE-Harzes 95:5 bis 20:80 ist; und

16
 EP 3 387 176 B1

d) der pH-Wert größer als 6, vorzugsweise größer als 7, noch bevorzugter größer als 7,5 ist.

2. Zusammensetzung, hergestellt durch Mischen der Vinylester/EthylenCopolymer-Dispersion und eines PAE-Harzes

gemäß Anspruch 1, wobei der Vinylester Vinylacetat ist und wobei, wenn Whatman #1 CHR-Chromatographiepapier
5 mit der Zusammensetzung bei einer 16%igen Zugabe gesättigt, 15 Minuten lang bei 130°C getrocknet wird, das
behandelte Whatman-Papier eine Trockenzugfestigkeit von mehr als 200 N/5 cm breiten Streifen, eine Nasszug-
festigkeit von mindestens 35 %, vorzugsweise mindestens 40 %, noch bevorzugter mindestens 45 % der Trocken-
zugfestigkeit und einen Gehalt an gebundenem Formaldehyd von weniger als 5 ppm, bestimmt nach dem Verfahren
VdL-RL03 (1997 - 05), aufweist.
10
3. Verwendung einer Dispersion gemäß Anspruch 1 oder einer Zusammensetzung nach Anspruch 2, wobei die Dis-
persion oder die Zusammensetzung als Bindemittel für ein Textil oder Vlissubstrat verwendet wird, wobei die Dis-
persion oder die Zusammensetzung auf eine oder beide Seiten des Textils oder Vliesstoffes aufgetragen und dann
gehärtet wurde.
15
4. Latexgebundenes Vliesmaterial, umfassend ein Substrat, wobei das Substrat mit einem Polymerbindemittel, um-
fassend eine Dispersion gemäß Anspruch 1 oder eine Zusammensetzung gemäß Anspruch 2, gebunden ist, wobei:

a) das Vliesmaterial einen Nasszugfestigkeitswert von mindestens 35%, vorzugsweise 40%, seines Trocken-
20 zugfestigkeitswertes aufweist;
b) das Material einen Gehalt an gebundenem Formaldehyd von weniger als 5 ppm, bestimmt nach dem Verfahren
VdL-RL03 (1997-05), aufweist; und
c) das Material einen Gehalt an freiem Formaldehyd von weniger als 5 ppm aufweist, bestimmt nach dem
Verfahren JM 112;1973.
25
5. Latexgebundenes Vliesmaterial nach Anspruch 4, wobei das Gewichtsverhältnis von getrocknetem Vinylester/Ethy-
len-Copolymer zu PAE-Mischung zum Gewicht der Fasern von 3 bis 30 Gew.-%, vorzugsweise von 5 bis 20 Gew.-
%, besonders bevorzugt von 10 bis 15 Gew.-% ist.

30 6. Latexgebundenes Vliesmaterial nach Anspruch 4 oder 5, wobei das Verhältnis der Nass-/Trocken-Zugfestigkeit des
Materials mindestens 45 % ist und der gebundene Formaldehyd 1 ppm oder weniger ist.

7. Latexgebundenes Vliesmaterial nach einem beliebigen der Ansprüche 4 bis 6, wobei das PAE ein sogenanntes G2,
G2.5 oder G3 PAE-Harz ist und eine wässrige Lösung mit einem Feststoffgehalt von 12.5 bis 30 % ist, wobei der
35 Gehalt an unerwünschten Nebenprodukten so reduziert wurde, dass der Gehalt an 1,3-Dichlorpropanol (DCP) unter
700 ppm, vorzugsweise unter 500 ppm, besonders bevorzugt unter 150 ppm, am meisten bevorzugt unter 50 ppm
ist, der Gehalt an 3-Monochlorpropan-1,2-diol, (MCPD), unter 600 ppm, vorzugsweise unter 500 ppm, besonders
bevorzugt unter 400 ppm und am meisten bevorzugt unter 50 ppm ist.

40 8. Latexgebundenes Vliesmaterial nach einem beliebigen der Ansprüche 4 bis 7, wobei das Vinylester/Ethylen-Copo-
lymer des Polymerbindemittels im Wesentlichen frei von anionischem Stabilisierungsmittel ist, wobei im Wesentli-
chen frei weniger als 2 Gew.-% anionisches Tensid auf aktiver Basis bedeutet, vorzugsweise weniger als 1 Gew.-%.

9. Latexgebundenes Vliesmaterial nach einem beliebigen der Ansprüche 4 bis 8, wobei das Vinylester/Ethylen-Copo-
45 lymer des Polymerbindemittels ein nichtionisches Tensid, ein Schutzkolloid, vorzugsweise Polyvinylalkohol oder
Hydroxyethylcellulose, oder Kombinationen aus einem nichtionischen Tensid und einem Schutzkolloid umfasst.

10. Latexgebundenes Vliesmaterial nach einem beliebigen der Ansprüche 4 bis 9, wobei die zum Bilden des Vliesma-
terials verwendeten Fasern aus Naturfasern, synthetischen Fasern, Bikomponentenfasern und Kombinationen da-
50 von ausgewählt sind, vorzugsweise wobei die verwendeten Fasern primär Cellulosefasern umfassen.

11. Latexgebundene Vliesmaterial nach einem beliebigen der Ansprüche 4 bis 10, wobei das Vliesmaterial ein latex-
gebundenes Airlaid-Vlies, ein mehrfach gebundenes Airlaid-Vlies, ein trockengelegtes kardiertes Vlies oder ein
nassgelegtes Vlies ist.
55
12. Verwendung des latexgebundenen Vliesmaterials gemäß einem beliebigen der Ansprüche 4 bis 11, wobei das
Vliesmaterial entweder allein oder zu einer Struktur verarbeitet verwendet wird, um Flüssigkeiten zu absorbieren.

17
 EP 3 387 176 B1

13. Verwendung des latexgebundenen Vliesmaterials gemäß einem beliebigen der Ansprüche 4 bis 11 als Element zur
Aufnahme/Verteilung von Flüssigkeiten oder als Element zur Speicherung von Flüssigkeiten in einem Körperpfle-
geartikel.

5 14. Körperpflegeartikel, der das latexgebundene Vliesmaterial gemäß einem beliebigen der Ansprüche 4 bis 11 enthält.

15. Haushalts- oder Industriereinigungstuch oder -wischtuch, das das latexgebundene Vliesmaterial gemäß einem
beliebigen der Ansprüche 4 bis 11 enthält.

10
Revendications

1. Dispersion à faible teneur en formaldéhyde d’un copolymère d’ester vinylique/éthylène contenant des groupes
acides carboxyliques copolymérisés ou leurs sels mélangés avec une résine de polyamidoamine-épichlorhydrine
15 (PAE) présentant une résistance à l’état humide, dans laquelle :

a) la dispersion de copolymère d’ester vinylique/ éthylène est exempte de groupes N-méthylolacrylamide

réactifs ;
b) la PAE comprend moins de 800 ppm de composés organiques halogénés (AOX) ;
20 c) le rapport en poids des particules solides du copolymère d’ester vinylique/éthylène aux particules solides
dans l’émulsion aqueuse de la résine PAE est de 95/5 à 20/80 ; et
d) le pH est supérieur à 6, de préférence supérieur à 7, mieux encore supérieur à 7,5.

2. Composition produite par mélange de la dispersion de copolymère d’ester vinylique/éthylène et d’une résine PAE
25 selon la revendication 1, dans laquelle l’ester vinylique est l’acétate de vinyle et dans laquelle, quand un papier de
chromatographie Whatman #1 CHR est saturé avec la composition à un appoint de 16 %, séché pendant 15 minutes
à 130°C, le papier Whatman traité a une résistance à la traction à l’état sec supérieure à 200 N/5 cm de largeur de
bande, une résistance à la traction à l’état humide d’au moins 35 %, de préférence d’au moins 40 %, mieux encore
d’au moins 45 %, de la résistance à la traction à l’état sec, et une teneur en formaldéhyde lié inférieure à 5 ppm,
30 telle que déterminée par la méthode Vdl-RL03 (1997-05).

3. Utilisation d’une dispersion selon la revendication 1 ou d’une composition selon la revendication 2, dans laquelle
la dispersion ou composition est utilisée en tant que liant pour un textile ou un substrat non tissé, dans laquelle la
dispersion ou composition a été appliquée sur l’un ou les deux des côtés du textile ou du tissu non tissée et ensuite
35 durcie.

4. Matériau non tissé collé par un latex comprenant un substrat, dans lequel le substrat est collé avec un liant polymère
comprenant une dispersion selon la revendication 1 ou une composition selon la revendication 2, dans lequel :

40 a) le matériau non tissé a une valeur de résistance à la traction à l’état humide d’au moins 35 %, de préférence
40 %, de sa valeur de résistance à la traction à l’état sec ;
b) le matériau a une teneur en formaldéhyde lié inférieure à 5 ppm, telle que déterminée par la méthode Vdl-
RL03 (1997-05) ; et
c) le matériau a une teneur en formaldéhyde libre inférieure à 5 ppm, telle que déterminée par utilisation de la
45 méthode JM 112 ; 1973.

5. Matériau non tissé collé par un latex selon la revendication 4, dans lequel le rapport en poids du mélange de
copolymère d’ester vinylique/éthylène séché au PAE ramené au poids des fibres est de 3 à 30 % en poids, de
préférence de 5 à 20 % en poids, mieux encore de 10 à 15 % en poids.
50
6. Matériau non tissé collé par un latex selon la revendication 4 ou 5, dans lequel le rapport de résistance à la traction
à l’état humide/sec du matériau est d’au moins 45 % et le formaldéhyde lié représente 1 ppm ou moins.

7. Matériau non tissé collé par un latex selon l’une quelconque des revendications 4 à 6, dans lequel la PAE est une
55 résine PAE dite G2, G2.5 ou G3, et est une solution aqueuse ayant une teneur en extrait sec de 12,5 à 30 %, dans
lequel le niveau de sous-produits non souhaités a été réduit de façon que le niveau de 1,3-dichloropropanol (DCP)
soit inférieur à 700 ppm, de préférence inférieur à 500 ppm, mieux encore inférieur à 150 ppm, tout spécialement
inférieur à 50 ppm, le niveau de 3-monochloropropan-1,2-diol (MCPD) soit inférieur à 600 ppm, de préférence

18
 EP 3 387 176 B1

inférieur à 500 ppm, mieux encore inférieur à 400 ppm et tout spécialement inférieur à 50 ppm.

8. Matériau non tissé collé par un latex selon l’une quelconque des revendications 4 à 7, dans lequel le copolymère
d’ester vinylique/éthylène du liant polymère est pratiquement exempt d’agent de stabilisation anionique, dans lequel,
5 par pratiquement exempt, on entend moins de 2 % en poids de tensioactif anionique sur une base active, de
préférence moins de 1 % en poids.

9. Matériau non tissé collé par un latex selon l’une quelconque des revendications 4 à 8, dans lequel le copolymère
d’ester vinylique/éthylène du liant polymère comprend un tensioactif non-ionique, un colloïde protecteur, de préfé-
10 rence le poly(alcool vinylique) ou l’hydroxyéthylcellulose, ou des combinaisons d’un tensioactif non-ionique et d’un
colloïde protecteur.

10. Matériau non tissé collé par un latex selon l’une quelconque des revendications 4 à 9, dans lequel les fibres utilisées
pour former le matériau non tissé sont choisies parmi les fibres naturelles, les fibres synthétiques, les fibres bicom-
15 posées et leurs combinaisons, de préférence dans lequel les fibres utilisées comprennent principalement des fibres
cellulosiques.

11. Matériau non tissé collé par un latex selon l’une quelconque des revendications 4 à 10, lequel matériau non tissé
est une toile obtenue par jet d’air collée par un latex, une toile obtenue par jet d’air multi-collée, une toile cardée
20 obtenue par voie sèche, ou une toile obtenue par voie humide.

12. Utilisation du matériau non tissé collé par un latex de l’une quelconque des revendications 4 à 11, dans laquelle le
matériau non tissé est utilisé soit seul soit en étant fabriqué selon une structure, pour absorber des liquides.

25 13. Utilisation du matériau non tissé collé par un latex de l’une quelconque des revendications 4 à 11, en tant qu’élément
d’acquisition/distribution de fluides ou élément de stockage de fluides d’un article d’hygiène personnelle.

14. Article d’hygiène personnelle incorporant le matériau non tissé collé par un latex de l’une quelconque des revendi-
cations 4 à 11.
30
15. Etoffe ou chiffon de nettoyage à usage domestique ou industriel incorporant le matériau non tissé collé par un latex
de l’une quelconque des revendications 4 à 11.

35

40

45

50

55

19
 EP 3 387 176 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 4859527 A [0006] • US 5217455 A [0070]

• WO 200204133 A2 [0007] • US 5716703 A [0070]
• US 7189307 B [0008] • US 7138561 B [0070]
• US 7678856 B2 [0008] • US 7767598 B [0070]
• WO 2013072713 A1 [0009] • US 7786341 B [0070]
• US 5633334 A [0037]

Non-patent literature cited in the description

• Encyclopedia of Polymer Science and Engineering,

1987, vol. 8, 659 [0037]

20