FR2744465A1 - OLEOPHOBIC AND HYDROPHOBIC FIBROUS SUBSTRATE AND PROCESS FOR PRODUCING THE SAME - Google Patents

Abstract

The invention relates to an oleophobic and hydrophobic fibrous substrate, very particularly usable as an oleophobic and hydrophobic packaging, in particular greaseproof, comprising a cationic binder and at least one oleophobic and hydrophobic fluorinated acrylic copolymer and glyoxal or at least one compound comprising it, in particular. a compound of glyoxal and urea. The invention also relates to the process for obtaining such a fibrous substrate by the papermaking route. It also relates to a treatment composition intended to impart an oleophobic and hydrophobic character to a fibrous substrate.

Description

The invention relates to an oleophobic and hydrophobic fibrous substrate. She

  also relates to the method of manufacturing this substrate by the paper route and a composition adapted in particular to the treatment of a substrate

  fibrous to make it oleophobic and hydrophobic.

  We know so-called greaseproof papers that must be barriers to fats and water. These papers are used to make packaging

  fatty foods such as animal kibbles.

  In the patent application FR-A-2679574, there is described greaseproof papers, the composition conferring them this quality comprises at least 0.03% of glyoxal, at least 0.01% of a ketene alkyl dimer as bonding agent at least 0.002% of a fluorinated salt chosen from the family of diethanolamine salts of

perfluoroalkyl ethyl phosphates.

  Fluoride salts provide a barrier effect to fat however it was necessary to add glyoxal and a fining agent to have better

water resistance.

  There are now fluorinated resins that perform better than these salts.

  European Patent Application EP-A-542598 describes fluorinated acrylic copolymers which have excellent grease resistance but also excellent water resistance. These polymers are presented as not having

  need adjuvants to give them hydrophobic or oleophobic properties.

  However, it turns out that the characteristics of oleophobicity and hydrophobicity of the substrates treated with these polymers do not develop.

  immediately and in some cases it takes up to two months.

  Those skilled in the art control the characteristics of a greaseproof paper in general according to the following tests: KIT TEST, method of the company 3M and defined according to the procedure TAPPI UM 557. A substrate having a score of at least 10 is supposed to have good greaseproof properties, the maximum of the scale being 12. In fact this test determines the surface tension of the substrate and is not sufficient to know

  really the fat barrier effect of kibble packaging.

  the method COBB water, defined according to the standard AFNOR NF Q 03-018, the COBB water is measured, 1 minute, to determine the resistance of the substrate to the

  water penetration. The COBB water, 1 minute, must be less than or equal to 21.

  This COBB test simply gives an idea of the hydrophobicity of the substrate. These two tests are combined to judge the non-greasability of a substrate, however, we can simultaneously obtain good results with these two

  tests without having a substrate that is sufficiently greaseproof.

  It is in fact essential to control the fibrous substrate according to the test

  said "Croquettes test". This test is described at the end of the present description, it

  gives the percentage of surface stained by fats; this percentage to be

less than 10.

  This test being done hot (60'C), under the pressure of a weight and for 3 days, it is more draconian than the previous ones as shown in Comparative Examples 1 to 4 described below. It is representative of fat resistance

  contained in pet kibbles.

  One of the known ways to accelerate the development of this greaseproof effect is to overheat the substrate, for example in the case of a paper it can be over-braised at 160C in the dryer of the paper machine. However, this consumes energy and slows down the manufacturing process on the machine.

  paper; moreover one obtains a paper very dry and thus brittle.

  The object of the invention is therefore to provide a fibrous substrate which has a good level of oleophy and hydrophobicity, in particular according to the "kibble test", that is to say a level of less than 10%, this level must be reached immediately, from the end of the substrate manufacturing without having to

overheating said substrate.

  The Applicant has found that this object is achieved if the fibrous substrate is treated with a composition of a synergistic mixture of a cationic binder, an olephobic and hydrophobic fluorinated acrylic copolymer and a compound

comprising glyoxal.

  The invention thus provides an oleophobic and hydrophobic fibrous substrate, characterized in that it contains at least one cationic binder, at least one oleophobic and hydrophobic fluorinated acrylic copolymer and at least one glyoxal or

  a compound comprising comprising

  In particular the substrate is characterized in that it contains: - 1 to 5% by dry weight of at least one cationic binder, - 0.25 to 1.25% by dry weight of at least one fluorinated acrylic copolymer oleophobic and hydrophobic and

  0.1 to 1.5% by weight of at least glyoxal or a compound containing it.

  Preferably, it is used as a compound comprising glyoxal,

compounds of glyoxal and urea.

  Preferably, the cationic binder is a starch, more particularly it is a quaternized starch having a degree of cationicity characterized by its content.

  Nitrogen on dry matter of at least 0.14%.

  As the fluorinated acrylic copolymer, any copolymer can be used

  fluorinated acrylic with an oleophobic and hydrophobic character.

  Preferably, the fluorinated acrylic copolymers are those claimed in the European patent application EP-A-542598 introduced in its

all by reference.

  It is more specifically fluorinated copolymers, optionally salified or quaternized, which comprise by weight: (a) 92 to 50%, preferably 90 to 70%, of one or more polyfluorinated monomers of general formula: BOCC = CH R (I)

R

  wherein: Rfrepresents a straight or branched chain perfluorinated radical containing 2 to 4 carbon atoms, preferably 4 to 16 carbon atoms; B represents a divalent linking linked to O by a carbon atom and possibly comprising one or more oxygen, sulfur and / or nitrogen atoms, one of the symbols R representing a hydrogen atom and the other one a a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms; (b) 1 to 25%, preferably 8 to 18%, of one or more monomers of the general formula: R1

N-B '-O-C-C = CH2 (II)

2 R '

  wherein: B 'represents a linear or branched alkylene radical containing 1 to 4 carbon atoms, R' represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms; R1 and R2, which may be identical or different, each represent a hydrogen atom or a linear or branched alkyl radical containing 1 to 18 carbon atoms, hydroxyethyl or benzyl or R1 and R2 together with the nitrogen atom to which they are bonded form a morpholino, piperidino or pyrrolidinyl-1 radical; (c) 1 to 25%, preferably 2 to 10%, of a vinyl derivative of general formula:

R "-CH = CH2 (III)

  wherein: R "may be an alkylcarboxylate or alkylether group containing from 1 to 18 carbon atoms; (d) 0 to 10%, preferably 0 to 8%, of any monomer other than

monomers of formulas I, II, III.

  Preferably, the cationic copolymers are used, more particularly

quaternized.

  As adjuvants necessary for the implementation of the composition, it is

  may include antifoams.

  The substrate of the invention may be any substrate comprising fibers.

  It is advantageously a substrate comprising fibers selected from natural organic fibers including cellulose fibers, fibers

synthetic organic compounds.

  According to a particular case of the invention, the substrate is a paper essentially comprising cellulose fibers and optionally conventional papermaking auxiliaries which do not adversely affect the characteristics of oleophobicity and

of hydrophobicity sought.

  The fibrous substrate may comprise in particular a wet strength agent. Preferably, the substrate is not bonded.

It can also be a cardboard.

  It may also be a non-woven substrate, especially a fiber-based substrate

  polyester or polyolefin, optionally obtained by paper.

It can also be a fabric.

  The invention also relates to a process for obtaining a fibrous substrate with improved oleophobic and hydrophobic character and, more particularly, a process

  for producing a fibrous substrate treated on the surface.

  Preferably, such a process for papermaking the fibrous substrate having oleophobic and hydrophobic properties is characterized in that: - the fibers and optionally adjuvants are mixed in an aqueous medium; web of a paper machine, - the wet sheet obtained is pressed, - the sheet is treated using a sizing press or an impregnator with a treatment composition containing at least one cationic binder, at least one oleophobic and hydrophobic fluorinated acrylic copolymer and glyoxal or at least one compound comprising

- the sheet is dried.

  The drying is advantageously carried out between 80 and 120, preferably

around 100 C.

  Such treatment is particularly applicable to

cellulose fiber base.

  The substrate can be obtained by a mass treatment, the composition

  of treatment being added in mass to the fibers.

  The invention also relates to oleophobic and hydrophobic packages, in particular grease-proof packaging, made from the fibrous substrate of the invention, in particular packaging intended to contain foodstuffs and more particularly foodstuffs of the type croquettes for

animals.

  The invention also relates to a composition, in particular intended for mass or surface treatment of a fibrous substrate with a view to conferring on it

  properties of oleophobia and hydrophobicity.

  This composition contains at least one cationic binder, at least one oleophobic and hydrophobic fluorinated acrylic copolymer and at least one glyoxal or

a compound comprising

  The dilution and the composition of this composition are adapted according to the capacity of the fibrous substrate to absorb this composition and

  conditions of implementation of the process for producing the substrate.

  This composition advantageously contains: 2 to 5% by dry weight of at least one cationic binder, 0.3 to 1% by dry weight of at least one oleophobic and hydrophobic fluorinated acrylic copolymer and 0.2 to 1, 5% by weight of glyoxal or of at least one compound comprising, - aqueous and / or organic solvents and optionally adjuvants necessary for the implementation of the composition, in an amount sufficient to

  obtain a percentage of 100 by total weight.

  In the compositions, each of the three synergistic components is preferably in one of the forms previously described in the context of the present invention.

description of the substrate.

EXAMPLES:

  Embodiments of the invention are described in Examples 5 and 6 and

Examples 8 and 9.

  Examples 1 to 4 and 7 are comparative examples that do not meet

not to the invention.

  The examples are all made in the same way, only the nature and the quantities of the products used for the treatment composition differ. Tables 1 and 2 specify the products included in the treatment baths and their respective amounts as well as the characteristics of the papers treated with these compositions. Table 3 gives the concentrations in percentages by dry weight of the three synergistic constituents in the paper obtained after treatment and then drying according to Examples 8 and 9; such a paper containing a final moisture of about

5% by weight.

  The values for Cobb and KIT TEST are given for each side of the substrate. Some data is expressed at different times counted

  from the end of manufacture of the substrate (t - = 0).

  The cationic starch used is a quaternized starch having a degree of cationicity characterized by its dry matter nitrogen content of at least 0.14%. FORAPERLE 321 is a fluorinated acrylic copolymer, it is cationic and it has a dry extract of 25%, it is manufactured and marketed by the

ELF ATOCHEM company.

  DRYOL XF is a wax intended to reduce the hydrophilicity

  substrate, marketed by PROTEX.

  AQUAPEL 34B is a bonding agent, it is an alkyl ketene dimer marketed by HERCULES BOZEFIX TSI is a compound comprising glyoxal and urea,

  at 42% active ingredients, manufactured and marketed by HOESCHT.

  The glyoxal alone is diluted to 40% by weight with water.

  The amounts expressed in Tables 1 and 2 below are given by weight of the product in its marketed form except for the starch which

is expressed in dry weight.

  Embodiment of the Examples: A treatment composition is produced according to the respective components and the respective amounts of each example, the composition being completed with water in sufficient quantity so as to obtain a percentage of 100 by weight.

  total; the starch has been previously cooked.

  This composition is placed in the gluing press of a

pilot machine.

  On this pilot machine paper is made from cellulose fibers and a wet strength agent diluted in an aqueous medium. The wet sheet is pressed then it is treated in a size press by the composition of

treatment.

  The recovery of the composition by the paper is about 75% by wet weight.

RESULTS:

  Comparative Examples 2 to 4 show that the addition of a sizing agent has no noticeable effect on the improvement of greaseproofing, on the contrary they

  decrease it while these products are known for their barrier effect.

  Comparative Examples 1 and 7 in comparison with the examples according to the invention 5, 6, 8 and 9 show the synergy of the mixture of the three components to obtain a good result in "CROQUETFES TEST" immediately after the manufacture of the fibrous substrate. Moreover, results obtained with the test kit

  show that the solvanophobic nature of the substrate treated according to the invention is good.

  EXAMPLE EXAMPLE EXAMPLE EXAMPLE 5 EXAMPLE 6

  COMPARATIVE 1 COMPARATIVE 2 COMPARATIVE 3 COMPARATIVE 4

  Amidoncationic 3% * 3% * 3% * 3% * 3% 3% Forceps 321 2% ** 2% * * 2% ** 2% 2% ** Dryol XF 1% ** 2% ** Aquapel 34B 1 % ** Bozefix TSI 3% ** Glyoxal 3% ** Weight (g / m ') 63 62 62 62 64 64 Thickness (ium) 102 102 102 101 102 104 Porosity Bendtsen (ml / min) 1050 1180 1090 1160 960 570 Cobb water 1 mn 16 / 17,5 18 / 18,5 18/18 17/17 - 13/13 Test kit 12/12 10/11 11/12 9/10 11/12 12/12 Test kibble: t = 0 42 41 100 86 11 0 t = 2 weeks 0 0 0 16.5 7 0

TABI.EAU1

  * expressed as a percentage of dry product

  * * expressed as a percentage of commercial product.

  COMPARATIVE EXAMPLE 7 EXAMPLE 8 EXAMPLE 9

  Cationic starch 3% * 3% * 3% * Forceps 321 2% * * 2% ** 2% ** Bozefix TSI 2% ** t3% ** Viscosity BROOKFIELD 100 very 41 40 40 (mPas) 2 Pas) 62 63 63 Weight (g / m2)

101 100 102

  Thickness (m) CD Porosite Bendtsen (ml / min) 1240 760 740 Test kit 12/12 12/12 12/12 Cobb water lmn t = 0 18 / 17,5 16/16 15/15 Test kibble t = 0 85 10 0 t = 2 weeks 0 0 0

IABLLAIU2 0

  * expressed as a percentage of dry product

  * * expressed as a percentage of commercial product.

Table 3

EXAMPLE 8 EXAMPLE 9

  Cationic starch 2,18 2,17 Foraperle 321 0,36 0,36 Bozefix TSI 0,61 0,87 DESCRIPTION OF THE "CROOUCH TEST":

  This test is derived from a test developed by the company 3M.

  On a grid allowing to pass the ambient atmosphere (air

  wet and warm), an untreated paper is placed.

  On this paper the substrate to be tested is placed.

  On top of this substrate is placed 250 ml of dog croquettes, brand CROQ MIX marketed by QUAKER, these croquettes being held inside a wooden frame of 10 cm x 10 cm and 5 cm high . On these croquettes we place a corrugated cardboard and over a weight of

2.5 kg.

  This set is placed in an oven at 60C and whose humidity

  relative is 65% for 3 days.

  On the face in contact with the test paper of the untreated paper, the stained surface is determined with a graph paper. The exposed surface

  being 100 cm 2, the percentage of stained surface is directly obtained.

Claims (12)

  An oleophobic and hydrophobic fibrous substrate, characterized in that it contains at least one cationic binder, at least one oleophobic and hydrophobic fluorinated acrylic copolymer and at least one glyoxal or a compound comprising glyoxal.   2. fibrous substrate according to claim 1, characterized in that it contains: - 1 to 5% by dry weight of at least one cationic binder, 0.25 to 1.25% by dry weight of at least one oleophobic and hydrophobic fluorinated acrylic copolymer and - 0.1 to 1.5% by weight of glyoxal or at least one compound comprising glyoxal.   3. Substrate according to one of claims 1 or 2, characterized by the fact   that the compound comprising glyoxal is a compound of glyoxal and urea.   Substrate according to one of Claims 1 to 3, characterized in that   that the cationic binder is a cationic starch.   Fibrous substrate according to one of claims 1 to 4, characterized by   the fact that it comprises fibers selected from natural organic fibers, in particular   particularly cellulose fibers, synthetic organic fibers.   Fibrous substrate according to claim 5, characterized in that   the fibers are cellulose fibers.   7. Process for the papermaking of a fibrous substrate according to   one of claims 1 to 6, characterized by the fact that:   the fibers and optionally adjuvants are mixed in an aqueous medium, the mixture is sent onto the web of a paper machine, the wet sheet obtained is pressed, the sheet is treated using a press; gluing machine or an impregnator with a composition containing at least one cationic binder, at least one oleophobic and hydrophobic fluorinated acrylic copolymer and at least one glyoxal or a compound comprising - the sheet is dried.   8. Oleophobic and hydrophobic packaging, in particular greaseproof packaging, characterized in that it is manufactured from a fibrous substrate   according to one of claims 1 to 6 or obtained according to claim 7.   9. A composition intended in particular to confer oleophobicity and hydrophobicity properties, characterized in that it contains at least one cationic binder, at least one oleophobic and hydrophobic fluorinated acrylic copolymer and   glyoxal or at least one compound comprising   10. Composition according to claim 9, characterized in that it contains: - 2 to 5% by dry weight of at least one cationic binder, - 0.3 to 1% by dry weight of at least one acrylic copolymer oleophobic and hydrophobic fluorinated and - 0.2 to 1.5% by weight of glyoxal or of at least one compound comprising, - aqueous and / or organic solvents and optionally adjuvants necessary for the implementation of the composition, in sufficient quantity to   obtain a percentage of 100 by total weight.   11. Composition according to claim 9 or 10, characterized by the fact   that the compound comprising glyoxal is a compound of glyoxal and urea.   12. Composition according to one of claims 9 to 11, characterized by   the fact that the cationic binder is a cationic starch.