LOW-EMULSIFIER AQUEOUS POLYMER DISPERSIONS FOR PRODUCTION OF COMPOSITE FILMS

Abstract

Described are aqueous polymer dispersions and a method for producing them. The polymer dispersions comprise polymer particles having an average particle diameter of greater than 200 nm, monomodal particle size distribution, and uniform glass transition temperature, and are prepared by radical emulsion polymerization of a monomer mixture comprising ethylenically unsaturated, radically polymerizable monomers, using a polymer seed, less than 0.8 part by weight of emulsifier, and without protective colloids. The monomer mixture consists of a) at least 60 wt % of at least one monomer selected from the group consisting of C1 to C20 alkyl acrylates, C1 to C20 alkyl methacrylates, vinyl esters of carboxylic acids containing up to 20 carbons, vinylaromatics having up to 20 carbons, ethylenically ensaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbons, aliphatic hydrocarbons having 2 to 8 carbons and one or two double bonds, and mixtures of these monomers, b) at least 0.1 wt % of at least one monomer having at least one acid group; c) optionally further monomers, the acid groups of the monomers b) being wholly or partly neutralized during the emulsion polymerization. The aqueous polymer dispersions can be used as adhesives, more particularly for the production of composite films.

Claims

1. An aqueous polymer dispersion comprising polymer particles dispersed in water, having an average particle diameter of greater than 200 nm, a monomodal particle size distribution, and a uniform glass transition temperature, prepared by radical emulsion polymerization of a single monomer mixture comprising ethylenically unsaturated, radically polymerizable monomers, using a polymer seed, less than 0.8 part by weight of emulsifier per 100 parts by weight of monomers, without addition of protective colloids and without formation of protective colloids in situ, where the monomer mixture consists of a) at least 60 wt %, based on the total amount of monomers, of at least one monomer selected from the group consisting of C1 to C20 alkyl acrylates, C1 to C20 alkyl methacrylates, vinyl esters of carboxylic acids containing up to 20 carbons, vinylaromatics having up to 20 carbons, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbons, aliphatic hydrocarbons having 2 to 8 carbons and one or two double bonds, and mixtures of these monomers, b) at least 0.1 wt %, based on the total amount of monomers, of at least one monomer having at least one acid group; c) optionally at least one further monomer, different from the monomers a) and b); where a feed of the monomer mixture during the polymerization takes place with a first and with at least one second feed rate, the first feed rate being slower than the second feed rate, and where the acid groups of the monomers b) are wholly or partly neutralized during the emulsion polymerization by feeding of a base, where the feed of the base begins during the emulsion polymerization after at least 5 wt % of the total monomer mixture is present in the reaction vessel under polymerization conditions.

2. The polymer dispersion according to claim 1, wherein the monomers b) having at least one acid group are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinyllactic acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, and mixtures of these monomers.

3. The polymer dispersion according to claim 1, wherein the monomers a) are selected from the group consisting of C1 to C10 alkyl acrylates, C1 to C10 alkyl methacrylates, styrene, and mixtures of these monomers.

4. The polymer dispersion according to claim 1, wherein the monomers a) are used in an amount of at least 80 wt %, based on the total amount of the monomers, and are selected from the group consisting of C1 to C10 alkyl acrylates, C1 to C10 alkyl methacrylates, styrene, and a mixture thereof and the monomers b) are used in an amount of 0.5 to 5 wt %, based on the total amount of the monomers, and are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and a mixture thereof.

5. The polymer dispersion according to claim 1, wherein the glass transition temperature is in range from 40 C. to +15 C.

6. The polymer dispersion according to claim 1, wherein at least one chain transfer agent is used in the polymerization.

7. The polymer dispersion according to claim 1, wherein the polymer seed is used in an amount of 0.01 to 0.5 part by weight per 100 parts by weight of monomers and/or the polymer seed has an average particle diameter of 20 to 40 nm.

8. The polymer dispersion according to claim 1, wherein the monomers c) are used in an amount of 0.1 to 10 wt %, based on the total amount of the monomers, and are selected from the group consisting of amides of ethylenically unsaturated carboxylic acids, N-alkylolamides of ethylenically unsaturated carboxylic acids, phenyloxyethyl glycol mono(meth)acrylate, hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, monomers containing amino groups, nitriles of unsaturated C3 to C8 carboxylic acids, bifunctional monomers which as well as an ethylenically unsaturated double bond have at least one glycidyl group, oxazoline group, ureido group, ureido-analogous group or carbonyl group, and crosslinking monomers which have more than one radically polymerizable group.

9. A two-component adhesive comprising the polymer dispersion according to claim 1 in a first component, and at least one crosslinker reactive with the first component in a second component.

10. A method for producing an aqueous polymer dispersion comprising polymer particles dispersed in water and having an average particle diameter of greater than 200 nm, a monomodal particle size distribution, and a uniform glass transition temperature, prepared by radical emulsion polymerization of a single monomer mixture comprising ethylenically unsaturated, radically polymerizable monomers, using a polymer seed, less than 0.8 part by weight of emulsifier per 100 parts by weight of monomers, without addition of protective colloids and without formation of protective colloids in situ, where the monomer mixture consists of a) at least 60 wt %, based on the total amount of monomers, of at least one monomer selected from the group consisting of C1 to C20 alkyl acrylates, C1 to C20 alkyl methacrylates, vinyl esters of carboxylic acids containing up to 20 carbons, vinylaromatics having up to 20 carbons, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbons, aliphatic hydrocarbons having 2 to 8 carbons and one or two double bonds, and mixtures of these monomers, b) at least 0.1 wt %, based on the total amount of monomers, of at least one monomer having at least one acid group; c) optionally at least one further monomer, different from the monomers a) and b); where the feed of the monomer mixture during the polymerization takes place with a first and with at least one second feed rate, the first feed rate being slower than the second feed rate; and where the acid groups of the monomers b) are wholly or partly neutralized during the emulsion polymerization by feeding of a base, where the feed of the base begins during the emulsion polymerization after at least 5 wt % of the total monomer mixture is present in the reaction vessel under polymerization conditions.

11. An adhesive comprising the aqueous polymer dispersion according to claim 1.

12. A composite film comprising a first and at least one second film which are bonded to one another using an adhesive comprising the aqueous polymer dispersion according to claim 1.

13. A method for producing a composite film, which comprises providing the aqueous polymer dispersion according to claim 1 and bonding at least two films to one another using the aqueous polymer dispersion.

Description

EXAMPLES

ABBREVIATIONS

[0078] tBHP tert-butyl hydroperoxide [0079] IS itaconic acid [0080] AA acrylic acid [0081] MAA methacrylic acid [0082] EHA 2-ethylhexyl acrylate [0083] S styrene [0084] EA ethyl acrylate [0085] MA methyl acrylate [0086] MMA methyl methacrylate [0087] nBA n-butyl acrylate [0088] HPA hydroxypropyl acrylate [0089] DAAM diacetoneacrylamide [0090] iPOx 2-isopropenyl-2-oxazoline [0091] Basonat Basonat HW 100, water-dispersible polyisocyanate based on isocyanuratized hexamethylene diisocyanate [0092] Basonat LR 9056 water-dispersible polyisocyanate based on isocyanuratized hexamethylene diisocyanate [0093] Dowfax 2A1 alkyldiphenyl oxide disulfonate, emulsifier [0094] Disponil LDBS 20 emulsifier [0095] SC solids content [0096] LT light transmissibility; parameter for determining differences in particle size. In this case the polymer dispersion is diluted to a solids content of 0.01% and the light transmissibility is measured in comparison to pure water. [0097] Tg (calc.) glass transition temperature as calculated by the Fox equation from the glass transition temperature of the homopolymers of the monomers present in the copolymer and their weight fraction:

1/Tg=xA/TgA+xB/TgB+xC/TgC+. . . [0098] Tg: calculated glass transition temperature of the copolymer [0099] TgA: glass transition temperature of the homopolymer of monomer A [0100] TgB, TgC: Tg correspondingly for monomers B, C, etc. [0101] xA: mass of monomer A/total mass of copolymer, [0102] xB, xC correspondingly for monomers B, C etc. [0103] Tg from DSC: glass transition temperature as measured by DSC [0104] PS from HDC: average particle diameter as measured by photon correlation spectroscopy (ISO 13321:1996)

[0105] Example Dispersion 1a

[0106] A mixture of 136.38 g of water and 1.82 g of a 33% fine polystyrene seed (in water) is heated to 85 C. and stirred for 5 minutes. Then 8.57 g of 7% strength sodium peroxodisulfate solution are added and stirring is carried out again for 5 minutes. Next is the metered addition of 91.15 g of the monomer mixture over 1 hour, after which 820.4 g of the monomer mixture are metered in over 2 hours. Taking place in parallel with this is the metered addition of 34.29 g of sodium peroxodisulfate (7% strength solution in water) over 3 hours. As soon as the 2nd part of the monomers is metered in, the metered addition of 19.15 g of 3.1% strength ammonia solution takes place in parallel with this over 2 hours.

[0107] Monomer Feed 1a:

[0108] 228.84 g water

[0109] 3 g Disponil LDBS 20 (20% in water)

[0110] 85.71 g 7% itaconic acid solution

[0111] 6 g methacrylic acid

[0112] 90 g methyl acrylate

[0113] 498 g n-butyl acrylate

[0114] This is followed by metered addition of 49.25 g of 3.1% strength ammonia solution over 30 minutes. After that, 58.22 g of 1.85% strength acetone bisulfite solution and 61.98 g of tert-butyl hydroperoxide solution (0.195%) are metered in over 2 hours.

[0115] In examples 1 b-d, the polymerization procedure is retained while the monomer composition is varied. In the case of example 1d, additionally, at the end, 32.48 g of 4.62% strength adipic di-hydrazide solution are added.

[0116] Monomer Feed 1 b:

[0117] 228.84 g water

[0118] 3 g Disponil LDBS 20 (20% in water)

[0119] 85.71 g 7% itaconic acid solution

[0120] 72 g styrene

[0121] 57 g methyl acrylate

[0122] 465 g n-butyl acrylate

[0123] Monomer Feed 1 c:

[0124] 310 g water

[0125] 3 g Disponil LDBS 20 (20% in water)

[0126] 12 g acrylic acid

[0127] 120 g styrene

[0128] 468 g n-butyl acrylate

[0129] Monomer Feed 1 d:

[0130] 399.12 g water

[0131] 3 g Disponil LDBS 20 (20% in water)

[0132] 85.71 g 7% itaconic acid solution

[0133] 6 g methacrylic acid

[0134] 90 g methyl acrylate

[0135] 495 g n-butyl acrylate

[0136] 3 g diacetoneacrylamide

[0137] Example Dispersion 1e:

[0138] A mixture of 180 g of water and 1.82 g of a 33% fine polystyrene seed (in water) is heated to 85 C. and stirred for 5 minutes. Then 8.57 g of 7% strength sodium peroxodisulfate solution are added and stirring is carried out again for 5 minutes. Next is the metered addition of 608.9 g of the monomer mixture over 2 hours, after which 310.43 g of the monomer mixture are metered in over 1 hour. Taking place in parallel with this is the metered addition of 34.29 g of sodium peroxodisulfate (7% strength solution in water) over 3 hours 15 minutes. As soon as the 2nd part of the monomers is metered in, the metered addition of 68.4 g of 3.07% strength ammonia solution takes place in parallel with this over 15 minutes.

[0139] Monomer Feed 1 e:

[0140] 236.58 g water

[0141] 3 g Disponil LDBS 20 (20% in water)

[0142] 85.71 g 7% itaconic acid solution

[0143] 12 g methacrylic acid

[0144] 12 g styrene

[0145] 53.4 g methyl acrylate

[0146] 510.6 g n-butyl acrylate

[0147] 6 g 2-isopropenyl-2-oxazoline

[0148] Subsequently 49.25 g of 3.07% strength ammonia solution are metered in over 30 minutes. Thereafter 59.67 g of 2.11% strength acetone bisulfite solution with 2.41 g of Lumiten I-SC and 21 g of tert-butyl hydroperoxide solution (10%) are metered in over 2 hours.

COMPARATIVE EXAMPLES

[0149] In examples 2a and 2b below, metering takes place in two stages and both the monomer composition and the procedure are varied by comparison with examples la-le. Furthermore, in examples 2a and 2b, little or no emulsifier is used. The protocols are based on dispersion in accordance with W02011/154920.

[0150] Example Dispersion 2a (Comparative)

[0151] A mixture of 136.38 g of water and 5.45 g of a 33% fine polystyrene seed (in water) is heated to 80 C. and stirred for 5 minutes. Then 42.86 g of 7% strength sodium peroxodisulfate solution are added and stirring is carried out again for 5 minutes. This is followed by the metered addition of 20 g of the monomer mixture 2a1 over 10 minutes and subsequently 265.27 g of the monomer mixture 2a1 over 50 minutes. The temperature here is raised to 85 C. This is followed by the metered addition of 40 g of the monomer mixture 2a2 over 10 minutes and subsequently 581.45 g of the monomer mixture 2a2, and also 54 g of 5.55% strength ammonia solution and 8.57 g of sodium peroxodisulfate (7% strength solution in water) over 2 hours 50 minutes.

[0152] Monomer Feed 2a1:

[0153] 49.98 g water

[0154] 1.07 g Texapon NSO (28% in water)

[0155] 85.71 g 7% itaconic acid solution

[0156] 12 g styrene

[0157] 43.5 g methyl acrylate

[0158] 93 g n-butyl acrylate

[0159] Monomer Feed 2a2:

[0160] 171.66 g water

[0161] 4.29 g Texapon NSO (28% in water)

[0162] 60 g styrene

[0163] 13.5 g methyl acrylate

[0164] 372 g n-butyl acrylate

[0165] Taking place subsequently is the metered addition of 17.14 g of sodium peroxodisulfate (7% solution in water) over 15 minutes. Thereafter 58.22 g of 1.85% strength acetone bisulfite solution and 61.98 g of tert-butyl hydroperoxide solution (1.94%) are metered in over 1 hour.

[0166] Example Dispersion 2b (Comparative):

[0167] A mixture of 462 g of water and 5.45 g of a 33% fine polystyrene seed (in water) is heated to 80 C. and stirred for 5 minutes. Then 42.86 g of 7% strength sodium peroxodisulfate solution are added and stirring is carried out again for 5 minutes. This is followed by the metered addition of 20 g of the monomer mixture 2b1 over 10 minutes and subsequently 109.48 g of the monomer mixture 2b1 over 30 minutes. Taking place after that are the metered addition of 40 g of the monomer mixture 2b2 over 15 minutes and subsequently 441.26 g of the monomer mixture 2b2 over 2 hours 45 minutes. The temperature here is increased to 95 C. over 3 hours. 30 minutes after the start of the metering of monomer mixture 2b2, 94.74 g of 2.22% strength ammonia solution are metered in. This is followed by the metered addition of 70.11 g of 2.57% strength sodium peroxodisulfate solution over 25 minutes. The temperature here is cooled to 85 C.

[0168] Monomer Feed 2b 1:

[0169] 7.38 g water

[0170] 2.1 g 2-ethylhexyl thioglycolate

[0171] 15 g methacrylic acid

[0172] 105 g ethyl acrylate

[0173] Monomer feed 2b 2:

[0174] 1.26 g water

[0175] 72 g styrene

[0176] 360 g ethyl acrylate

[0177] 48 g n-butyl acrylate

[0178] In comparative examples 3a, 3b and 3c below, there is variation in the monomer composition and in the metering of the monomers. The sodium peroxodisulfate solution is metered in parallel to the monomer feed. Examples 3a, 3b and 3c are modeled on examples in accordance with DE 19908183.

[0179] Example Dispersion 3a (Comparative):

[0180] A mixture of 136.38 g of water and 0.91 g of a 33% fine polystyrene seed (in water) is heated to 85 C. and stirred for 5 minutes. Then 4.29 g of 7% strength sodium peroxodisulfate solution are added and stirring is carried out again for 5 minutes. This is followed by the metered addition of 20 g of the monomer mixture over 10 minutes and subsequently 963.27 g of the monomer mixture over 2 hours 50 minutes. Taking place in parallel is the metered addition of 38.57 g of sodium peroxodisulfate (7% strength solution in water) over 3 hours.

[0181] Monomer Feed 3a:

[0182] 274.98 g water

[0183] 8 g Dowfax 2A1

[0184] 20.57 g Lumiten I-SC

[0185] 85.71 g 7% itaconic acid solution

[0186] 6 g methacrylic acid

[0187] 90 g methyl acrylate

[0188] 498 g n-butyl acrylate

[0189] Subsequently a metered addition takes place of 58.22 g of 1.85% strength acetone bisulfite solution and 61.98 g of tert-butyl hydroperoxide solution (0.19%) over 2 hours.

[0190] Example Dispersions 3b and 3c (Comparative):

[0191] In comparative examples 3 b-c, the polymerization process is retained while the monomer composition is varied.

[0192] Monomer Feed 3b:

[0193] 274.98 g water

[0194] 8 g Dowfax 2A1

[0195] 20.57 g Lumiten I-SC

[0196] 85.71 g 7% itaconic acid solution

[0197] 72 g styrene

[0198] 57 g methyl acrylate

[0199] 465 g n-butyl acrylate

[0200] Monomer Feed 3c:

[0201] 355.86 g water

[0202] 8 g Dowfax 2A1

[0203] 20.57 g Lumiten I-SC

[0204] 0.6 g tert-dodecyl mercaptan

[0205] 6 g acrylic acid

[0206] 90 g methyl methacrylate

[0207] 504 g n-butyl acrylate

TABLE-US-00001 TABLE 1 Wet specimen values of the adhesive dispersions. Tg PS Tg from from Monomer composition Amount of (calc.) SC LT DSC HDC No. [%] emulsifier [ C.] [%] [%] [ C.] [nm] 1a. 1 IA, 1 MAA, 15 MA, 83 0.1% Disponil 33 47.6 53 33.6 280.6 nBA LDBS 20 1b. 1 IA, 9.5 MA, 12 S, 77.5 0.1% Disponil 25.1 47 52 24.5 258.7 nBA LDBS 20 1c. 2 AA, 20 S, 78 nBA 0.1% Disponil 21.1 47 42 20.2 282.8 LDBS 20 1d. 0.5 DAAM, 1 IA, 1 MAA, 15 0.1% Disponil 32.5 46.8 55 33.8 280.4 MA, 82.5 nBA LDBS 20 1e. 1 iPOx, 1 IA, 2 S, 2 MAA, 0.11% Disponil 33.2 45.1 56 33.9 274.1 8.9 MA, 85.1 nBA LDBS 20 2a. 1 MAA, 1 IA, 15 MA, 83 0.25% Texapon 33 47.7 68 10.7 220.3 nBA NSO 37.8 2b. 2.5 MAA, 8 nBA, 12 S, 77.5 2.9 46.9 78 1.3 55.9 EA 154.9 3a. 1 MAA, 1 IS, 15 MA, 83 0.6% Dowfax 33 46.9 47 35.1 378.5 nBA 2A1, 0.24% Lumiten I-SC 3b. 1 IA, 9.5 MA, 12 S, 77.5 0.6% Dowfax 25.1 46.7 43 27 312.1 nBA 2A1, 0.24% Lumiten I-SC 3c. 1 AA, 15 MMA, 84 nBA 0.6% Dowfax 27.6 47.4 45 30.1 341 2A1, 0.24% Lumiten I-SC

[0208] Applications-Related Tests

[0209] Substrates, laminating films:

[0210] Polyethylene film, 50 m thick, corona pretreated, surface tension >38 mN/m;

[0211] metallized cPP film 25 m thick;

[0212] cPP film 25 m thick, corona pretreated, surface tension >38 mN/m

[0213] Adhesive Application:

[0214] Directly to the corona pretreated side of the base film, with an application weight of 1.8-2.2 g/m.sup.2 or 2.5-3.0 g/m.sup.2 dry.

[0215] Dynamic Peel Resistance:

[0216] The base film is fixed on the laboratory coating unit with the pretreated side upward and the adhesive under test is knife-coated directly onto the film. The adhesive is dried for 2 minutes with a hot air blower and then the laminating film is placed on with a manual roller and pressed in the roller laminating station at 70 C. with a roll speed of 5 m/minute and a laminating pressure of 6.5 bar. After that, using a cutting stencil, the laminate is cut into strips 15 millimeters wide and subjected to various storage cycles. Following storage, the laminate strip is pulled apart on a tensile testing machine, and the force required to achieve this is recorded. The test takes place on a tensile testing machine at an angle of 90 degrees and a removal speed of 300 mm/min. The test strip is opened up on one side, with one of the resultant ends being clamped into the upper jaw and the other into the lower jaw of the tensile testing machine, and the test is commenced. The result reported is the average of the force from three individual measurements, in N/15 mm.

[0217] The specimens can be tested after different storage conditions: [0218] 1. immediately after laminating (<3 min) [0219] 2. after 24 h (at 23 C./50% rel. humidity) [0220] 3. after 7 d (at 23 C./50% rel. humidity) [0221] 4. after 24 h (at 23 C./50% rel. humidity) +7 d at 40 C./95% rel. humidity [0222] 5. after 24 h (at 23 C./50% rel. humidity) +7 d at 50 C. in Ketchup

[0223] Dynamic Peel Resistance at 90 C.:

[0224] The base film is fixed on the laboratory coating unit with the pretreated side upward and the adhesive under test is knife-coated directly onto the film. The adhesive is dried for 2 minutes with a hot air blower and then the laminating film is placed on with a manual roller and pressed in the roller laminating station at 70 C. with a roll speed of 5 m/minute and a laminating pressure of 6.5 bar. The laminate is then cut into strips 15 millimeters wide using the cutting stencil, and stored for a minimum of 24 hours at 23 C./50% relative humidity. Following storage, the laminate strip is pulled apart on a tensile testing machine with climate chamber at a temperature of 90 C., and the force required to achieve this is recorded. The test takes place on a tensile testing machine with climate chamber, at a removal speed of 300 mm/min. The test strip is opened up on one side, with one of the resultant ends being clamped into the upper jaw and the other into the lower jaw of the tensile testing machine, and the test is commenced. The measurement starts after a waiting time of 1 minute, for conditioning of the test strip. Evaluation: The result reported is the average of the force from three individual measurements, in N/15 millimeters.

[0225] Assessment of the Fracture Mode: [0226] DT=printing ink transfer [0227] MT=metal transfer [0228] F=tack-free film on the substrate [0229] A100=adhesive layer remains completely on the base film (adhesive fracture) [0230] A0=adhesive layer detaches from the base film and passes to the laminating film (transfer) [0231] A0/R=adhesive layer passes to the laminating film, but local residues are on the base film. [0232] K=separation in the adhesive layer without detachment from a material (cohesive fracture) [0233] K*=separation in the adhesive layer without detachment from a material (cohesive fracture); the adhesive has no residual tack [0234] MB=partial or complete fracture of a film [0235] Z=zippy, adhesive layer flakes away (clattering noise)

[0236] A100/R=adhesive layer remains fully on the base film, but local residues on the laminating film In-between stages are indicated by reporting the percentage adhesive remaining on the laminating film. Example: A30=30% of the adhesive has remained on the base film, 70% has passed to the laminating film.

TABLE-US-00002 TABLE 2 Adhesive values of selected adhesive dispersions, without crosslinking, for various substrate surfaces Peel resistance Peel resistance Peel resistance after <3 min after <24 h at 90 C. [N/15 mm]/ [N/15 mm]/ [N/15 mm]/ fracture fracture fracture Ex. mode mode mode Films 1a 1.1/A80 0.9/A0 0.3/F oPP 1b 0.8/A100 0.9/A0 0.4/K (unprinted)/ 1c 0.7/A100 1.1/A100 0.2/K metallized oPP 2a 0.7/A100 0.9/R 0.3/K 3a 0.7/A95 1.2/A50 0.4/K 3b 0.6/A100 1.3/A100/K 0.5/K 3c 0.7/A100 1.3 K/A0 0.1/K 1a 0.9/R 1.3/K 0.2/A10 oPP (printed)/ 1b 0.7/A100 0.8/A100 0.5/K metalized oPP 1c. 0.6/A100 0.8/R 0.2/K 2a 0.6/A100 0.9/R 0.1/A0 1a 1.3/R 1.8/F/R 0.6/K PET (printed)/ 1b 1.3/A100 1.6/F/R 0.5/K metallized oPP 1c 1.2/A100 1.8/F/R 0.4/K 2a 0.9/A100 1.3/A100 0.4/F/R

[0237] This table shows that both the inventive examples and the comparative examples lend themselves well to use as adhesives in composite film lamination.

TABLE-US-00003 TABLE 3 Adhesive values of selected adhesive dispersions, with and without crosslinking, for various substrate surfaces. Peel resistance Peel resistance Peel resistance after <3 min after <24 h at 90 C. [N/15 mm]/ [N/15 mm]/ [N/15 mm]/ fracture fracture fracture Ex. mode mode mode Films 1a 1.6/A 100 1.6/A 100 0.4/A 50 PET (printed)/ 1a.sup.1) 3.0/K 3.2/A0 0.7/A 50 PE (printed) 1d 2.6/A100 3.2/K 0.7/A K 1e 2.1/A100 3.0/MB 0.4/F .sup.1)+ 3% Basonat LR 9056

[0238] Frit Foam Test:

[0239] The dispersion under test is filled up to the mark (corresponding to 50 ml of dispersion at about 6.5 cm) in a glass tube whose lower end has a glass frit located in it. This tube is located on a glass flask with air admission. The air is passed by means of a flowmeter (1 bar, 1 I/h) over the glass flask and through the glass frit, from below, into the dispersion contained in the glass tube. Measurement was made of the time taken to reach a foam height of 40 cm.

TABLE-US-00004 TABLE 4 Foam behavior of the adhesive dispersions Foam height 40 cm reached Dispersion [min] 1a >60.sup.1) 1b >60.sup.1) 1c >60.sup.1) 1e >60.sup.1) 2a 37 2b 13 3a 14 3b 13 3c 16 .sup.1)The test was discontinued after 60 minutes, the dispersions having shown no significant buildup of foam.