WO2001054896A2

WO2001054896A2 - Multilayer composite product comprising a pressure-sensitive and temperature-resistant adhesive polymer layer

Info

Publication number: WO2001054896A2
Application number: PCT/FR2001/000222
Authority: WO
Inventors: François COURT; Christian Laurichesse; Christophe Verge
Original assignee: Atofina
Priority date: 2000-01-28
Filing date: 2001-01-24
Publication date: 2001-08-02
Also published as: WO2001054896A3; AU3559301A; FR2804369B1; FR2804369A1

Abstract

The invention concerns a multilayer composite product comprising at least once successively a first soft or rigid material layer; a second layer consisting of a pressure-sensitive adhesive polymeric film formed by applying on the first layer at least a latex (L1), then by drying said latex; and a third layer consisting of a soft or rigid material, a latex (L1) obtained by emulsion polymerisation of the mixture of the following monomers, for 100 wt. %: 40-95 wt. % of at least a (meth)acrylic or vinyl monomer capable of resulting in a homopolymer having a Tg ≤ -40 °C; 2-50 wt. % of at least a (meth)acrylic or vinyl monomer capable of resulting in a homopolymer having a Tg ≥ 0 °C; 1-6 wt. % of at least a (meth)acrylic carboxylic monomer; 0.5 wt. % of at least (meth)acrylic monomer ethoxylated with 1-20 ethylene oxide moles; more than 0.075 wt. % to 5 wt. % of at least a (meth)acrylic or vinyl monomer comprising a ureido group; and 0-2 wt. % of at least an acrylic or vinyl monomer bearing a sulphonate function.

Description

MULTILAYER COMPOSITE PRODUCT HAVING A PRESSURE-SENSITIVE AND TEMPERATURE-RESISTANT ADHESIVE POLYMER LAYER

The present invention relates to a multilayer composite product comprising a layer of pressure-sensitive and temperature-resistant adhesive polymer.

By patent application FR-A-2 751 974, an adhesive pressure-sensitive polymer is known, obtained by emulsion polymerization of the mixture of the following monomers, for a total of 100% by weight:

(A) 40 to 95% by weight of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature less than or equal to -40 ° C; (B) 2 to 50% by weight of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature greater than or equal to 0 ° C;

(C) 0.5 to 6% by weight of at least one (meth) acrylic carboxylic monomer;

(D) 0 to 5% by weight ^'of at least one (meth) acrylic acid ethoxylated with 1 to 20 moles of ethylene oxide;

(E) 0.05 to 1% by weight of at least one (meth) acrylic or vinyl monomer comprising a ureido group; and

(F) 0 to 2% by weight of at least one acrylic or vinyl monomer carrying a sulfonate function.

One of the problems with pressure-sensitive adhesives is that they have to compromise in performance between often antagonistic properties such as tack (tackiness) and creep resistance, the compromise being all the more difficult to find at high temperature. . The tack will in particular be increased by an adhesive having an excellent wettability of a given surface, which will in particular be controlled by the glass transition temperature (Tg) of the copolymer and its molecular weight. The creep resistance will be inversely favored by a higher Tg and especially by a mass higher molecular. Raising the test temperature will finally cause the creep resistance to drop.

There is also an ongoing effort to improve the dynamic shear strength property of pressure sensitive adhesives.

In the above patent application, the beneficial effect of the monomer carrying a ureido group on the creep resistance at room temperature of the adhesives thus obtained is described.

The Applicant Company has now discovered that polymers belonging to this family not only make it possible to obtain a good compromise of properties in terms of tack and creep resistance at room temperature, but also to obtain excellent creep resistance at temperature. , which is of particular interest for certain applications in the fields of tapes and labels, as well as in the automotive industry (interior trim and sound insulation for example) which requires high thermal resistance. An improvement in the dynamic shear strength of pressure sensitive adhesives has also been found, a property sought after on the market.

The subject of the present invention is therefore a multilayer composite product comprising two external layers and at least one intermediate layer, characterized in that, for all the successive layers which compose it, it comprises at least once the succession of the following three layers:

(I) the first being made of a soft or rigid material;

(II) the second consisting of a pressure-sensitive adhesive polymer film formed by applying to the layer (I) at least one latex (L1) optionally in admixture with at least one latex (L2) and / or at least one usual additive, then drying of said latex (s); and (III) the third being made of a soft or rigid material,

a latex (L1) being a latex obtained by emulsion polymerization of the mixture of the following monomers, for a total of 100% by weight:

(A1) 40 to 95% by weight, in particular 50 to 85% by weight, of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature less than or equal to -40 ° VS ;

(Bl) 2 to 50% by weight, in particular 10 to 45% by weight, of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature greater than or equal to 0 ° C. ;

(C1) 0.1 to 6% by weight, in particular 0.5 to 3% by weight, of at least one (meth) acrylic carboxylic monomer;

(Dl) 0 to 5% by weight, in particular 0 to 3% by weight, of at least one (meth) acrylic monomer ethoxylated with 1 to 20 moles of ethylene oxide;

(E1) more than 0.075% to 5% by weight, in particular 0.1 to 3% by weight, of at least one (meth) acrylic or vinyl monomer comprising a ureido group; and

(FI) 0 to 2% by weight, in particular 0 to 1.5% by weight, of at least one acrylic or vinyl monomer carrying a sulfonate function a latex (L2) being a latex obtained by emulsion polymerization of the mixture of the following monomers, for a total of 100% by weight:

(A2) 40 to 95% by weight, in particular 50 to 85% by weight, of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature less than or equal to -40 ° VS ;

(B2) 2 to 50% by weight, in particular 10 to 45% by weight, of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature greater than or equal to 0 ° C. ;

(C2) 0.1 to 5% by weight, in particular 0.5 to 3% by weight, of at least one (meth) acrylic carboxylic monomer;

(D2) 0 to 5% by weight, in particular 0, ^'l to 3% by weight of at least one (meth) acrylic acid ethoxylated with 1 to 20 moles of ethylene oxide;

(F2) 0 to 2% by weight, in particular 0 to 1.5% by weight, of at least one acrylic or vinyl monomer carrying a sulfonate function,

the latex (L1) representing 100 to 5% by weight, in particular from 100 to 10% by weight, of (L1) + (L2), and the latex (L2) representing 0 to 95% by weight, in particular from 0 at 90% by weight, of (L1) + (L2), and the monomer (s) (El) representing 0.01 to 5% by weight, in particular 0.05 to 3% by weight, of the sum of the monomers entering in the composition of (L1) + (L2); and the layer or layers of pressure-sensitive adhesive polymer film (II) resistant to high temperatures up to 200 ° C.

In particular, the latex (s) (L1) optionally in admixture with the latex (s) (L2) ^"~ sσnt such that they make it possible to reach temperatures above 180 ° C. in the test, the operating protocol of which is given in Example 17 below, and creep resistance at 80 ° C. greater than 20,000 minutes in the test, the operating protocol of which is given in Example 18 below. In other words, in particular, the the latexes (L1) optionally mixed with the latex (s) (L2) are such that they allow temperatures of 180 ° C. to be reached and creep resistance at 80 ° C. greater than 20,000 minutes in tests according to which the latexes are applied using an automatic applicator to poly (ethylene terephthalate) (PET) ribbons, the quantity deposited in dry form being 2-0 g / ^; the ribbons are then dried for 15 minutes at 60 ° C, then stored 24 hours ^' at 23 ^Q C, 50% relative humidity before evaluation; the ribbons are then applied by their coated side to a substantially vertical stainless steel plate so that the contact surface is 2.5 by 2.5 min and at the end of the ribbon hangs a weight of 1 kg; and either the assembly is then placed in a heating chamber and the sample is subjected to temperatures ranging from 25 ° C to 180 ° C by increasing the temperature by 0.4 ° C per minute and we note then the temperature reached during the weight drop, or else the assembly is then placed in an enclosure heated to 80 ° C. and the time in minutes necessary for the weight drop is noted.

Each of the latex-forming copolymers (L1) and (L2) has a glass transition temperature preferably less than or equal to -25 ° C, in particular less than or equal to -4O ° C.

The materials constituting the first layer (I) and the second layer (II) are chosen in particular from plastic films such as polypropylene, polyethylene, poly (ethylene terephthalate), poly (vinyl chloride) and polyamide films; aluminum films; protective non-stick coatings such as silicone paper; paper, cardboard, metals, floor coverings such as carpet and linoleum, wood, concrete, nonwovens, fabrics such as cotton, polyester-cotton and polyesters, and leather; and films of paints and varnishes. Mention may be made, inter alia, of three-layer systems of tape / adhesive / adhesive / substrate, and of five-layer systems such as, for example, double-sided adhesives of non-stick film / adhesive / substrate / adhesive / non-stick film. , all these systems leading to assemblies having good thermal resistance.

The monomers (Al) and (A2) have a glass transition temperature generally between -40 ° C and -80 ° C; they are chosen in particular from butyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate and 2-ethylhexyl versatate. A particularly preferred monomer (A1) or (A2) is 2-ethylhexyl acrylate.

The monomers (B1) and (B2) have a glass transition temperature generally between 10 ° C and 105 ° C; they are in particular chosen from methyl acrylate, butyl methacrylate, methyl methacrylate, vinyl acetate and acrylonitrile. Particularly preferred monomers (B1) or (B2) are methyl methacrylate, methyl acrylate, vinyl acetate and mixtures thereof.

The monomer (Cl) or (C2) is in particular acrylic acid or methacrylic acid, acrylic acid being preferred. As examples of the monomers (Dl) and (D2) which are optional, there may be mentioned methoxyethyl acrylate, ethyldiglycol acrylate, butyldiglycol (meth) acrylate, ethyltriglycol methacrylate, the latter being preferred. The monomers (Dl) and (D2) make it possible to increase the properties of sticking to the loop "loop tack", and of peeling.

Among the monomers (E1) with ureido group, there may be mentioned, those represented by the formulas (a) to (c) below:

R ² R ²

R ¹ -NCNH (a)

X

AT

/ \

R ^J N NH (b) \ /

VS

II

X

R ¹ - A / \

R - N NH (c)

\ /

VS

II X

in which :

- X represents 0 or S;

- R ¹ is an ethylenically unsaturated group, polymerizable by the radical route; - R ² is a hydrogen atom or an alkyl group C _j _- C _8; and

- A is an alkylene chain with 2 or 3 carbon atoms which may be substituted by lower alkyl and or hydroxy and / or C 1 -C 4 alkoxy, and / or which may be interrupted by carbonyl.

The group R ¹ above can be chosen from the groups CH ₂ = = CH-

CH ₂ = = CH-CH ₂ -

CH

CH ₂ = = C 1 -CH ₂ -

CH ₂ = = CH-C- II

II

0

OH

CH ₂ = CH-CH ₂ -0-CH ₂ -CH-CH ₂ -

R ³ -A ¹ -Alk- or

R represents hydrogen, 3-alkyloxy-2-hydroxypropyl, vinyl, methacryloyl, acryloyl or methacryloyloxyaceto

- A represents O, NH or NR;

- R ⁴ represents 3-allyloxy-2-hydroxypropyl when R represents 3-allyloxy-2-hydroxypropyl; - Alk represents a C ~ Cg alkylene chain; and

2- (β-carboxyacrylamido) ethyl.

Mention may be made, as examples of monomers (E1), of N- (2-methacryloyloxyethyl) -ethylene urea, N- (2-acryloyloxyethyl) -ethylene urea, N- (methacrylamidomethylene) -ethylene urea, N- (acrylamidomethylene) - ethylene urea, N- (β-methacrylamidoethyl) -ethylene urea, N- (β-acrylamidoethyl) -ethylene urea, N-vinyl-ethylene urea, N-vinyloxyethyl-ethylene urea, N- [(β-methacryl- oyloxyacetamido) -ethyl] -N, N '-ethylene urea, N - [(β-acryl- oyloxyacetamido) -ethyl] -ethylene urea, 1- [2- [[2 -hydroxy- 3- (2-propenyloxy) propyl] amino] ethyl] -2-imidazolidone, N- methacrylamidomethyl urea, N-methacryloyl urea, N- [3- (1, 3-diazacyclohexan-2-one) -propyl] methacrylamide, N- hydroxyethylethylene urea, N-aminoethyl ethylene urea, N- (3- allyloxy-2-hydroxypropyl) aminoethyl ethylene urea, N-methacrylaminoethyl ethylene urea, N-acrylaminoethyl ethylene urea, N-methacryloxyacetoxyethyl ethylene urea, N-methacryloxy-acetaminoethyl ethylene urea and N-di (3- allyloxy-2 -hydroxy-propyl) aminoethyl ethylene urea, N- (2-acryloyl-oxy-ethy) ethylene urea, N-methacrylamidomethyl urea, and allyl alkyl ethylene ureas.

The particularly preferred monomers (E1) are, inter alia, ethylimidazolidone (meth) acrylate, ethyl imidazolidone (meth) acrylamide (WAM II from the company "RHODIA"), 1- [2- [[ 2-hydroxy-3- (2-propenyloxy) - propyl] amino] ethyl] -2-imidazolidone, a monomer sold by the company "RHODIA" under the name "WAM III" and obtained from hydroxyethyl methacrylate, diisocyanate and an ureido amine, maleic acid or maleimide derivatives carrying ureido groups, such as those marketed by the company CYTEC (Cylink C4) and described in international applications WO97 / 49676, WO 97/49685 and WO 97/49686.

Among the monomers (FI) and (F2) containing a sulfonate group, mention may in particular be made of sodium vinylsulfonate, sodium acrylamidomethylpropane sulfonate, sodium allyl ether sulfonate. Among these, sodium vinyl sulfonate is preferred. The monomers (FI) and (F2) make it possible to improve the colloidal stability of the dispersions for pressure-sensitive adhesive polymers, as well as the wetting properties of the supports.

The latex polymers (PI) and (P2) used according to the invention are prepared by emulsion polymerization under conditions well known to those skilled in the art. Thus, the reaction is preferably carried out under an inert atmosphere in the presence of radical initiators. The priming system used can be a Red-Ox system such as K ₂ S ₂ O _g , (NH ₄ ) ₂ S ₂ 0g / Na ₂ S ₂ 0 ₅ , Na S0 ₃ , a system thermal such as (NH ^) ₂ S 0g, the amounts used being between 0.2 and 1.0% by weight relative to the total mass of the monomers, preferably between 0.25 and 0.5% by weight. It is also possible to use organic initiators (hydroperoxides, peroxides and azo initiators).

The emulsion polymerization reaction according to the invention is carried out at a temperature between 65 and 85 ° C and depends on the nature of the initiation system used: 65-75 ° C for Red-Ox systems based on peroxodisulfate and metabisulfite, 70-85 ° C for thermal systems based on peroxodisulfate alone.

The preparation of the dispersions according to the invention is preferably carried out according to a semi-continuous type process, making it possible to limit the composition drifts which are a function of the differences in reactivity of the different monomers. The introduction of the monomers in the form of a pre-emulsion with part of the water and of the surfactants is thus generally carried out - over a period of time from 3 hours 30 to 5 hours. It is also useful, although not essential, to seed 5 to 15% of the monomers. The emulsifying systems used in the emulsion polymerization process according to the invention are chosen from the range of emulsifiers having a suitable hydrophilic / lipophilic balance. The preferred systems are constituted by the association of an anionic surfactant, such as sodium lauryl sulfate, nonylphenol sulfates ethoxylated in particular with 20 - 25 moles of ethylene oxide, benzene dodecylsulfonate and ethoxylated fatty alcohols sulfates, and of a nonionic surfactant, such as ethoxylated nonylphenols in particular with 10 - 40 moles of ethylene oxide and ethoxylated fatty alcohols.

The total amount of emulsifier is in the range from 1 to 5% by weight and preferably from 2 to 4% by weight relative to the monomers.

The polymer dispersions intended to be applied as self-adhesive according to the invention are preferably synthesized for high dry extracts, of the order of 50 to 65% by weight, to allow rapid drying during application.

To obtain dry extracts greater than 60%, it is moreover preferable to properly control the sequences of addition of surfactants so as to obtain the appropriate particle size distribution to avoid excessive viscosity.

In order to obtain better applicability to the supports, it is possible to adjust the rheology by adding a suitable thickener in small quantities: generally less than 0.2% by weight relative to the final dispersion. It is also possible, although not essential, to add a wetting agent to improve the adhesion to non-polar supports such as polyethylene, a tackifying agent, an anti-foaming agent.

The polymers obtained in the process according to the invention lead to pressure-sensitive adhesives having a high level of cohesion while retaining good peel and tack values. These new adhesives can thus be used to replace polymers in solvent phase which are costly and harmful to the environment.

As already indicated, the significant increase in cohesive force is obtained by copolymerization of at least one monomer having a group during ureido, such as ethylimidazolidone methacrylate.

The copolymerization of the ureido monomer can be carried out according to a semi-continuous process in a single stage but also according to a semi-continuous process in two stages where the ureido monomer is preferably distributed in the second stage without however excluding its use in the first stage .

To maintain the necessary peeling and sticky properties with good cohesive properties, it is preferable to adjust the molecular weight of the polymer by using a suitable quantity of a transfer agent, such as alkyl mercaptans (tert. dodecyl mercaptan, n-dodecylmercaptan), alkyl mercaptopropionates, or thioglycolic acid. The optimal amounts of transfer agent according to the invention can range in particular up to 0.25% by weight of the monomers, being preferably from 0.05 to 0.2% by weight. It is also possible to increase the amount of initiator used to reduce the molecular weight.

It is also demonstrated that the combination of at least one ethoxylated acrylic monomer as defined above made it possible to contribute to the preservation of good peeling and tacky properties alongside the strong cohesive properties provided by the monomer (s) with structure. ureido.

The high cohesive force associated with the adhesives according to the present invention also makes the latter compatible with the use of wetting agents used to increase adhesion to low surface energy supports, such as polyolefins.

The present invention will now be described with the aid of examples and comparative examples. In these Examples, all "parts" and percentages are by weight unless otherwise indicated.

EXAMPLES 1 to 11: Preparation of the various latexes General operating mode In a glass reactor, with a capacity of

2 liters, provided with mechanical stirring, 349.07 g of demineralized water are introduced, to which 1.43 g of the surfactant nonylphenol ethoxylated sodium sulfate is added to 25 moles of ethylene oxide in aqueous solution at 35% (marketed by the company "WITCO" under the name "REWOPOL® NOS 25"), then the mixture is brought to 80 ° C. with stirring.

Also prepared is an ^aqueous solution of ammonium persulfate by dissolving 3.5 g of ammonium persulfate in 60 g of deionized water. A preemulsion is also prepared which consists of 344.29 g of water, to which are added:

- 35.71 g of the surfactant nonylphenol ethoxylated sodium sulfate with 25 moles of ethylene oxide in 35% aqueous solution (marketed by the

Company "WITCO" under the brand "REWOPOL® NOS 25"); and

- 12.50 g of the surfactant nonylphenol ethoxylated to

25 moles of ethylene oxide in 80% aqueous solution (marketed by the Company

"WITCO" under the brand "REWOPAL® HV 25"); as well as

- 1000 g of monomers as indicated in the

Table below for Examples 1 to 11, respectively.

When the reaction medium reaches 85 ° C., the feeding of the initiator solution and of the monomer mixture is started in parallel, the introduction taking place over 4 hours while maintaining the temperature at 85 ° C. At the end of the flows, the reaction medium is maintained for an additional 2 hours at 85 ° C. Then cooled to room temperature to obtain the latex at acidic pH as indicated in the Table which is used as it is. The pH can also be adjusted to 9 (cf. Examples 7 and 8) using a sodium hydroxide solution or a 20% by volume ammonia solution, and the reactor is drained.

The latexes obtained have the characteristics set out in Table 1 below.

EXAMPLES 12 and 13: Preparation of Latex

General procedure

Into a reactor with a capacity of 3 liters, fitted with mechanical stirring, 348.70 g of demineralized water are introduced to which 2 g of nonyl phenol ethoxylated sodium sulfate in 35% aqueous solution are added. (marketed by the company "COGNIS" under the brand "DISPONIL® AES 72 IS"), then the mixture is brought to 67 ° C. We also prepare:

- a solution of sodium metabisulfite by dissolving 4.90 g of sodium metabisulfite in 28 g of demineralized water;

- a solution of ammonium persulfate by dissolving 4.90 g of ammonium persulfate in 84 g of demineralized water; - a preemulsion consisting of 479.50 g of demineralized water to which 50 g of DISPONIL® AES 72 IS are successively added with stirring, 20 g of ethoxylated nonyl phenol in 70% aqueous solution (sold by the company "COGNIS" under the brand "DISPONIL® NP 307"), and 1400 g of the monomers as indicated in Table 2 below.

When the temperature reaches 67 ° C, the metabisulfite solution is added -and the temperature is allowed to stabilize again at 67 ° C, then 3% - of the pre-emulsion is introduced and 10% of the solution is poured in 6 minutes persulfate. The reaction is left to react for an additional 20 minutes, then the remaining 97% of preemulsion and the remaining 90% of persulfate solution are poured separately while maintaining the temperature at 67 ° C. The temperature is then increased to 80 ° C. and left to react for an additional hour. Finally, the reaction medium is cooled to around 30 ° C. and the pH is adjusted using a 20% ammonia solution.

The latexes obtained have the characteristics set out in Table 2 below.

EXAMPLES 14 to 16

Mixtures of the latexes of Examples 1 and 5 were prepared in the proportions indicated in Table 3 for each of Examples 14 to 16. EXAMPLE 17 Measurement of the Resistance of Latexes to Creep in Temperature

The method used is inspired by standard ASTM 4498: The latexes of Examples 1 to 11 and the latex mixtures of Examples 14 to 16 are applied using an automatic applicator to PET ribbons, the quantity deposited in dry being 20 g / m ² . The ribbons are then dried for 15 minutes at 60 ° C, then stored for 24 hours at 23 ° C, 50% relative humidity before evaluation.

The ribbons are then applied by their coated side to a substantially vertical stainless steel plate so that the contact surface is 2.5 by 2.5 mm, and a weight of 1 kg is suspended from the end of the ribbon. . The assembly is then placed in a heating chamber, and the sample is subjected to temperatures ranging from 25 ° C to 180 ° C by increasing the temperature by 0.4 ° C per minute. We then note the temperature reached when the weight fell. The results are shown in Tables 1 and 3.

EXAMPLE 18 Measurement of the resistance of latexes to creep at 80 ° C.

The method used is inspired by the FINAT FTM 8 standard,

The latexes of Examples 1 to 8, 12 and 13 are applied using an automatic applicator to PET ribbons, the quantity deposited in dryness being 20 g / m. The ribbons are then dried for 15 minutes at 60 ° C, then stored for 24 hours at 23 ° C, 50% relative humidity before evaluation.

The ribbons are then applied by their coated side to a substantially vertical stainless steel plate so that the contact surface is 2.5 by 2.5 mm, and a weight of 1 kg is suspended from the end of the ribbon. . The assembly is then placed in an enclosure heated to 80 ° C., and the time in minutes necessary for the weight to drop is then noted. The results are shown in Tables 1 and 2.

EXAMPLE 19 Measurement of the dynamic shear strength according to the FINAT method No. 18

The latexes are applied using an automatic applicator to PET ribbons 12.7 mm wide and 60 mm long, the quantity deposited in dry form being 22 g / m. The ribbons are then dried for 15 minutes at 60 ° C and then stored for 24 hours at 23 ° C / 50% RH before evaluation. The ribbons are then applied by their coated side to a stainless steel plate so that the contact surface is 12.7 x 12.7 mm, and two passages of FINAT standardized roller are practiced in order to promote adhesion. After 20 minutes of contact, the stainless steel plate is then placed on the one hand, and on the other hand the free end of the ribbon in the jaws of a traction device so that the distance between the jaws is 40 mm. .

A tensile test is then carried out at a speed of 5 mm / minute and the maximum force is measured during the test as well as the type of rupture.

The results are shown in Table 2. The addition of ethylimidazolidone methacrylate therefore results in an increase in the dynamic shear strength.

EXAMPLE 20 Comparative evaluation of a commercial latex

A commercial latex proposed by the BASF company under the name of Acronal V210 was evaluated comparatively according to the protocol of Examples 17 to 19 to lead to:

- A temperature of 104 ° C (according to the method of Example 17);

- a creep resistance at 80 ° C of 10,000 (according to the method of Example 18); and

- a maximum force of 47.4 ± 3.2 N (cohesive rupture)

(according to the method of Example 19).

Marketed by ATOFINA under the brand NORSOCRYL 104

Table 2

* Marketed by ATOFINA under the brand. NORSOCRYL® 104

** Temperature creep (SAFT SHEAR ADHESION FAILURE TEMPERATURE) Table 3

Claims

1 - Multi-layer composite product comprising two external layers and at least one intermediate layer, characterized in that, for all the successive layers which compose it, it comprises at least once the succession of the following three layers:

(I) the first being made of a soft or rigid material;

(II) the second consisting of a pressure-sensitive adhesive polymer film formed by application to the layer (I) of at least one latex (Ll) optionally mixed with at least one latex (L2) and/or minus a usual additive, then drying said latex(es); And

(III) the third being made of a soft or rigid material,

a latex (Ll) being a latex obtained by emulsion polymerization of the mixture of the following monomers, for a total of 100% by weight:

(Al) 40 to 95% by weight of at least one (meth)acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature less than or equal to -40 °C;

(Bl) 2 to 50% by weight of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature greater than or equal to 0°C;

(Cl) 0.1 to 6% by weight of at least one (meth)acrylic carboxylic monomer; (Dl) 0 to 5% by weight of at least one (meth)acrylic monomer ethoxylated with 1 to 20 moles of ethylene oxide;

(El) more than 0.075% to 5% by weight of at least one (meth)acrylic or vinyl monomer comprising a ureido group; And

(FI) 0 to 2% by weight of at least one acrylic or vinyl monomer carrying a sulfonate function; And

a latex (L2) being a latex obtained by emulsion polymerization of the mixture of the following monomers, for a total of 100% by weight:

(A2) 40 to 95% by weight of at least one monomer

(meth) acrylic or vinyl capable of leading to a homopolymer having a glass transition temperature less than or equal to -40 °C;

(B2) 2 to 50% by weight of at least one (meth) acrylic or vinyl monomer capable of leading to a homopolymer having a glass transition temperature greater than or equal to 0°C;

(C2) 0.1 to 5% by weight of at least one (meth)acrylic carboxylic monomer;

(D2) 0 to 5% by weight of at least one (meth)acrylic monomer ethoxylated with 1 to 20 moles of ethylene oxide;

(F2) 0 to 2% by weight of at least one acrylic or vinyl monomer carrying a sulfonate function,

the latex (Ll) representing 100 to 5% by weight of (Ll) + (L2) and the latex (L2) representing 0 to 95% by weight of 0.01 to 5% by weight of the sum of the monomers included in the composition of (Ll) + (L2); And

said. structure of at least three layers resistant to high temperatures of up to 200°C.

2 - Composite product according to claim 1, characterized in that the latex(es). (Ll) optionally mixed with the latex(es) (L2) are such that they make it possible to reach temperatures above 180°C and creep resistance at 80°C greater than 20,000 minutes in tests according to which the latex are applied using an automatic applicator on poly (ethylene terephthalate) (PET) ribbons, the quantity deposited in ^' dry being 20 g/rrr; the ribbons are then dried for 15 minutes at 60°C, then stored -24 hours at 23°C, 50% relative humidity before evaluation; the ribbons are then applied by their coated side to a substantially vertical stainless steel plate such that the contact surface is 2.5 by 2.5 mm and a weight of 1 kg ^is suspended at the end of the ribbon; and or the whole is then placed in a heating chamber and the sample is subjected to temperatures ranging from 25°C to 180°C, increasing the temperature by 0.4°C per minute and we note then the temperature reached during the drop in weight, or the assembly is then placed in an enclosure heated to 80°C and the time in minutes necessary for the drop in weight is noted.

3 - Composite product according to one of claims 1 and 2, characterized in that the materials constituting the first layer (I) and the second layer (II) are chosen from plastic films, aluminum films, coatings non-stick protectors, paper, cardboard, metals, floor coverings, wood, concrete, non-wovens, fabrics, leather and paint and varnish films. 4 - Composite product according to one of claims 1 to 3, characterized in that the latex (Ll) is obtained by copolymerization of:

50 to 85% by weight of (Al)

10 to 45% by weight of (Bl)

0.5 to 3% by weight of (Cl)

0 to 3% by weight of (Dl);

0.1 to 3% by weight of (El); And

0 to 1.5% by weight of (FI).

5 - Product according to one of claims 1 to 4, characterized in that the latex copolymer (Ll) has a glass transition temperature less than or equal to -25°C, in particular less than or equal to -40°C .

6 - Product according to one of claims 1 to 5, characterized in that _the latex (L2) is obtained by emulsion copolymerization of:

50 to 85% by weight of (A2)-

10 to 45% by weight of (B2)

0.5 to 3% by weight of (C2) • 0.1 to 3% by weight of (D2); And

0 to 1.5% by weight of (F2).

7 - Product according to one of claims 1 to 6, characterized in that the latex copolymer (L2) has a glass transition temperature less than or equal to -25°C, in particular less than or equal to -40°C .

8 - Product according to one of claims 1 to 7, characterized in that:

the monomers (Al) and (A2) are chosen from butyl acrylate, n-octyl acylate, isooctyl acrylate, 2-ethylhexyl acrylate and 2-ethylhexyl versatate;

the monomers (Bl) and (B2) are chosen from methyl acrylate, butyl methacrylate, methyl methacrylate, vinyl acetate and acrylonitrile;

- the monomers (Cl) and (C2) are chosen from acrylic acid and methacrylic acid;

- the monomers (Dl) and (D2) are chosen from methoxyethyl acrylate, ethyl glycol acrylate, ethyltriglycol methacrylate, butyldiglycol methacrylate and butyl diglycol acrylate;

- the monomers (El) are chosen from (meth) ethylimidazolidone acrylate, (meth) ethylimidazolidone acrylamide, 1- [2- [[2-hydroxy-3- (2- propenyloxy) propyl] amino] ethyl] -2-imidazolidone, a monomer obtained from hydroxyethyl methacrylate, diisocyanate and a ureido amine, and maleic acid or maleimide derivatives carrying a ureido group; And

- the monomers (FI) and (F2) are chosen from sodium vinyl sulfonate, sodium acrylamidomethyl sulfonate and sodium allyl ether sulfonate.

9 - Product according to one of claims 1 to 8, characterized in that the copolymers of the latexes (Ll) and (L2) were obtained by emulsion polymerization of mixtures of respective monomers in the presence of 1 to 5% by weight with respect to the monomers of at least one emulsifying agent chosen from anionic surfactants, such as sodium laurysulfate, nonylsulfates ethoxylated in particular with 20-25 moles of ethylene oxide, benzene dodecylsulfonate and alcohols fatty ethoxylated sulfates, and nonionic surfactants, such as nonylphenols ethoxylated in particular with 10-40 moles of ethylene oxide and ethoxylated fatty alcohols. 10 - Composite product according to one of claims 1 to 9, characterized in that the latex (Ll) represents 100 to 10% by weight of (Ll) + (L2) and the latex (L2) represents 0 to 90% in weight of (Ll) + (L2). 11 - Composite product according to one of claims 1 to 10, characterized in that the monomer(s) (El) represent 0.05 to 3% of the total sum of monomers entering into the composition of (Ll) + (L2 ) .

12 - Composite product according to any one of claims 1 to 11, characterized in that the usual additive is chosen from thickening agents, wetting agents, tackifying agents and antifoaming agents.