ADDITIVE COMPOSITION FOR AQUEOUS DISPERSIONS OF HYDROPHOBIC POLYMERS

Abstract

Described are compositions comprising a defoamer mixture comprising mineral oil and hydrophobic particles such as for example wax particles; di- or monoalkyl sulfosuccinate having at least 9 carbon atoms in the alkyl group and certain ethylene oxide/propylene oxide block copolymers. Also described are aqueous dispersions of hydrophobic polymers comprising these compositions and the use of the aqueous polymer dispersions as an adhesive, for example for producing composite films from transparent polymer films.

Claims

1. A composition, comprising: (A) a defoamer mixture comprising (i) an oil selected from the group consisting of an aromatics-free white oil, a natural fatty acid oil, and mixtures thereof and (ii) hydrophobic particles; (B) a di- or monoalkyl sulfosuccinate, wherein each alkyl group independently has at least 9 carbon atoms; and (C) an ethylene oxide/propylene oxide block copolymer having a molecular weight of 1000 to 3000 and an ethylene oxide proportion of 10% to 40% by weight based on the block copolymer.

2. The composition of claim 1, wherein the oil is the aromatics-free white oil.

3. The composition of claim 1, wherein the hydrophobic particles are wax particles selected from the group consisting of a distearyl ethylenediamide, a paraffin wax, an ester wax, a fatty alcohol wax, waxes and a fatty acid amide amides, and mixtures thereof.

4. The composition of claim 1, wherein each alkyl group of the di- or monoalkyl sulfosuccinate independently has 10 to 20 carbon atoms.

5. The composition of claim 1, wherein the ethylene oxide/propylene oxide block copolymer has: a surface tension of at least 40 mN/m, measured in solution in distilled water at 23° C. and at a concentration of 1 g/1 according to DIN EN 14370:2004-11; and/or a cloud point of above 23° C., measured according to DIN EN 1890:2006.

6. The composition of claim 1, comprising: 0.8 to 1.2 parts by weight of the defoamer mixture (A); 1.6 to 2.4 parts by weight of the at least one di- or monoalkyl sulfosuccinate (B), and 0.8 to 1.2 parts by weight of the at least one ethylene oxide/propylene oxide block copolymer (C).

7. A method of producing a formulation, the method comprising adding the composition of claim 1 to an aqueous dispersion of a hydrophobic polymer having a free surface energy of less than 35 mN/m.

8. An aqueous polymer dispersion, comprising, (i) the composition of claim 1; and (ii) a hydrophobic polymer dispersed in an aqueous phase and having a free surface energy of less than 35 mN/m.

9. The aqueous polymer dispersion of claim 8, which comprises less than 1% by weight of emulsifiers that are distinct from the di- or monoalkyl sulfosuccinate (B) and the ethylene oxide/propylene oxide block copolymer (C) and that have a surface tension of less than 25 mN/m.

10. The aqueous polymer dispersion of claim 8, wherein a glass transition temperature of the hydrophobic polymer is at most 15° C. measured by differential scanning calorimetry according to ASTM D 3418-08 at a heating rate of 20° C./min.

11. The aqueous polymer dispersion of claim 8, wherein the hydrophobic polymer is produced from a) at least 60% by weight, based on a total amount of monomers, of at least one monomer selected from the group consisting of a C1 to C20-alkyl acrylate, a C1 -to C20-alkyl methacrylate, a vinyl ester of a carboxylic acid comprising up to 20 carbon atoms, a vinylaromatic comprising up to 20 carbon atoms, a vinyl halide, a vinyl ether of an alcohol comprising 1 to 10 carbon atoms, an aliphatic hydrocarbon comprising hydrocarbons having 2 to 8 carbon atoms and one or two double bonds, and mixtures thereof, b) at least 0.1 wt %, based on the total amount of monomers, of at least one monomer having at least one acid group; and c) optionally at least one further monomer distinct from the at least one monomer a) and the at least one monomer b).

12. The aqueous polymer dispersion of claim 11, wherein the at least one monomer a) is employed in an amount of at least 80% by weight, based on the total amount of monomers. and is selected from the group consisting of a C1-to C10-alkyl acrylate, a C1-to C10-alkyl methacrylate, styrene, and mixtures thereof; and the at least one monomer b) is employed in an amount of 0.5% to 5% by weight based on the total amount of monomers, and is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and mixtures thereof.

13. The aqueous polymer dispersion of claim 8, wherein the hydrophobic polymer is a styrene/acrylate copolymer.

14. A method for producing an adhesive, the method comprising obtaining the polymer dispersion of claim 8.

15. A composite film produced from a first and at least a second polymer film which are bonded to one another using an adhesive comprising the aqueous polymer dispersion of claim 8.

16. The composite film of claim 15, wherein at least one of the polymer films is transparent.

17. A method for producing a composite film, the method comprising providing the aqueous polymer dispersion of claim 8 and bonding at least two films to one another using the aqueous polymer dispersion.

Description

Examples

[0078] Abbreviations and input materials

[0079] EO ethylene oxide unit (—CH2CH2O—)

[0080] PO propylene oxide unit (—CH(CH3)CH2O—)

[0081] 1) Defoamer

TABLE-US-00001 Foamaster ® MO Mineral oil based Foamaster ® NO Based on natural oils (fatty acid esters), for >90% renewable raw example soybean oil, rapeseed oil, materials, free from sunflower oil mineral oils and silicone oils Foamaster ® WO White oil with hydrophobic particles Pharma grade, Foodstuffs approved FoamStar ® SI Silicone oil based FoamStar ® PB Polymer based FoamStar ® ED Polymer emulsion FoamStar ® ST Polymer based, mineral oil and/or polysiloxane carrier

TABLE-US-00002 Foamaster ® WO 2310 Composition based on white oil and paraffin wax Foamaster ® WO 2323 Composition based on white oil and hydrophobized silica particles Foamaster ® NO 2306 Composition based on natural fatty acid ester oils and anionic and nonionic surfactants Foamaster ® NO 2331 Preparation based on glycerides, C16-18- and C18-unsaturated hydrophobic components and nonionic surfactants FoamStar ® ED 2522 Aqueous emulsion of modified polydimethylsiloxane Foamaster ® ED 2523 Aqueous emulsion based on polyalkoxylate, modified silicones and fatty acid esters FoamStar ® SI 2213 Modified polydimethylsiloxane FoamStar ® ST 2438 Modified polydimethylsiloxane with hyper-branched star polymer FoamStar ® PB 2724 Modified polyalkylene glycol Tego ® Antifoam 2291 Preparation based on mineral oil, free from hydrophobic particles Tego ® Antifoam 4-94 Aqueous emulsion of a polyether siloxane

[0082] 2) Dialkyl or monoalkyl sulfosuccinates

[0083] Dodecyl sulfosuccinate, sodium salt (dialkyl sulfosuccinate)

[0084] Diisooctyl sulfosuccinate

TABLE-US-00003 Disponil ® SUS IC 10 Diisodecyl sulfosuccinate, sodium salt Hydropalat ® WE 3475 Di-2-ethylhexyl sulfosuccinate, sodium salt Hydropalat ® WE 3488 Sodium 1,4-diisodecylsulfonatosuccinate Lumiten ® I-SC Di-2-ethylhexyl sulfosuccinate, sodium salt

[0085] 3) Alkoxylated nonionic additives Hydropalat® WE 3161, 3162, 3164, 3966 Ethylene oxide/propylene oxide block copolymers

TABLE-US-00004 Ethylene Molar Molar weight oxide weight Polypropylene proportion (from OH Surface Hydropalat ® block % by wt. number) tension.sup.1) WE 3161 1750 10 2000 40 mN/m WE 3162 1750 20 2450 41 mN/m WE 3164 1750 40 2900 41 mN/m .sup.1)DIN 53914, 1 g/l in water, 23° C.

TABLE-US-00005 Hydropalat ® WE 3120 alkoxylated C12-14-fatty alcohol + 5 EO + 4 PO Hydropalat ® WE 3130 alkoxylated C10-14-fatty alcohol + 3 EO Hydropalat ® WE 3197 ethoxylated C9-11-fatty alcohol

[0086] 4) Adhesive Polymers

[0087] Polymer A:

[0088] Polymer A is produced by emulsion polymerization from

[0089] 86.1 parts by wt. n-butyl acrylate

[0090] 8.9 parts by wt. methyl acrylate

[0091] 2 parts by wt. styrene

[0092] 2 parts by wt. methacrylic acid

[0093] 1 part by wt. itaconic acid

[0094] 0.1 parts by wt. polystyrene seed

[0095] 0.06 parts by wt. 2-ethylhexyl thioglycolate (molecular weight regulator)

[0096] Neutralized with ammonia; film surface energy: 23 mN/m; <1% emulsifier

[0097] Epotal® FLX 3628: Aqueous dispersion of a copolymer based on acrylate esters and methacrylate esters

[0098] Test methods

[0099] Free surface energy

[0100] Measuring Instrument: Drop Shape Analyzer-DSA 100 (Krüss)

[0101] The following reference liquids were employed (surface tension reported in mN/m):

TABLE-US-00006 Y.sub.l Y.sub.l.sup.d Y.sub.l.sup.p Deionized 72.8 21.8 51 water Formamide 58.0 39.0 19.0 Diiodomethane 50.8 50.8 0

[0102] A 350 μm doctor blade is used to produce films of the polymer dispersions on a PET film and the contact angles to the three reference liquids are measured at 23° C.

[0103] The free surface energy is determined from the measured contact angles using the

[0104] Owens-Wendt method (see for example Jorda-Vilaplana et al, J. Appl. Sci. 2015, DOI:

[0105] 10.1002/APP.42391; Owens et al, J. Appl. Polym. Sci. 1969, 13, 1741):

[0106] γ.sub.1 (1+cosθ)=2 (γ.sub.s.sup.dγ.sub.1.sup.d).sup.1/2+2 (γ.sub.s.sup.pγ.sub.1.sup.p).sup.1/2

[0107] θ Contact angle between the reference liquid and the dried film of the dispersion

[0108] γ.sub.1 Free surface energy of the reference liquid; y.sub.1=γ.sub.1.sup.d+γ.sub.1.sup.p

[0109] γ.sub.1.sup.d Disperse proportion of free surface energy of the reference liquid

[0110] γ.sub.1.sup.pPolar proportion of free surface energy of the reference liquid

[0111] γ.sub.sd Disperse proportion of free surface energy of the solid surface to be tested

[0112] γ.sub.s.sup.P Polar proportion of free surface energy of the solid surface to be tested

[0113] γ.sub.sFree surface energy of the solid surface to be tested; γ.sub.s=γ.sub.sd+γ.sub.s.sup.P

[0114] Plotting γ.sub.1(1+cosθ)/2 (y.sub.l.sup.d).sup.1/2 against (γ.sub.1.sup.d)1/2 /(y.sub.1.sup.d).sup.1/2 results in a regression line having the gradient (γ.sub.s.sup.P).sup.1/2 and the point of intersection with the Y-axis at (γ.sub.s.sup.d).sup.1/2. This makes it possible to calculate the free surface energy: γ.sub.s.sup.p) γ.sub.s=γ.sub.s.sup.d+γ.sub.s.sup.P.

[0115] Foaming test

[0116] 100 ml vials are filled with 35 ml of dispersion and diluted with 10 ml of distilled water. The defoamers and wetting agents are then added and the vials closed with their lid.

[0117] The test is performed in a Scandex shaker. For comparative measurements 16 samples are arranged on a shaker plate and shaken at 100 Hz for 10 min. At the end of the test, markings are made for the liquid phase and for the phase with micro and macro foam. Photos are taken at intervals of 1, 5 and 10 minutes for evaluation. The ratio of micro to macro foam is determined after 5 min and is considered to be constant during foam reduction.

[0118] The result is reported in % incorporated air.

[0119] Calculation example: % air=t(tr)−t(1) *100/t)

[0120] t(tr)=dispersion height in shaker jar at reference time tr in mm

[0121] t(l)=dispersion height in shaker jar at start time in mm

[0122] Visual assessment of film (degree of wetting)

[0123] The dispersion film is visually assessed with regard to structure formation a) after 24 hours and b) after 28 days after addition of the composition to be tested

[0124] Assessment is carried out according to the following criteria:

[0125] 4 marked wetting defects

[0126] 3 few wetting defects

[0127] 2 unsettled structure of the film, difficult to decide whether wetting defects already present or still homogenous film

[0128] 1 very good, no wetting defects

EXAMPLES 1 to 11

Comparative Experiments

[0129] The aqueous polymer dispersion of polymer A was mixed with various amounts of different defoamers and the degree of wetting was investigated.

TABLE-US-00007 TABLE 1 Effect of defoamers on degree of wetting No. Defoamer Amount of defoamer Wetting 1 — .sup. 0% 1 2 Foamaster ® NO 2306 0.2% 2 3 Foamaster ® NO 2331 0.2% 2 4 Foamaster ® WO 2323 0.2% 3 5 Foamaster ® WO 2310 0.2% 4 6 Foamaster ® ED 2522 0.1% 3 7 Foamaster ® ED 2523 0.1% 2 8 Foamaster ® SI 2213 0.1% 4 (comprises silicone oil) 9 Foamaster ® ST 2438 0.1% 4 (comprises silicone oil) 10 Tego ® Antifoam 2291 0.2% 2 (paraffin oil) 11 Tego ® Antifoam 4-94 0.1% 4 (polyether siloxane)

[0130] Table 1 shows that an addition of silicone defoamers can result in highly structured dispersion films having marked wetting defects (table 1, examples 8, 9, 11). Defoamers based on white oils can also cause wetting defects when used without further measures (see table 1, experiments 4 and 5).

EXAMPLES 12 to 23

Comparative Experiments

[0131] The aqueous polymer dispersion of polymer A was mixed with various defoamers and wetting agents and the degree of wetting and the foaming behavior were investigated.

TABLE-US-00008 TABLE 2 Effect of defoamers and anionic wetting agents on degree of wetting 0.2% anionic 0.2% wetting Foam Foam Foam Foam No. defoamer agent Wetting 1 min 5 min 10 min Sum 12 — WE 3475 1 250 200 200 650 13 NO 2331 WE 3475 2 50 30 10 90 14 WO 2310 WE 3475 2 40 20 0 60 15 Tego AF 4- WE 3475 4 60 30 20 110 94 16 SI 2213 WE 3475 4 200 200 200 600 17 PB 2724 WE 3475 1 300 250 250 800 18 without SUS IC 10 1 200 150 50 400 19 NO 2331 SUS IC 10 2 30 20 10 60 20 WO 2310 SUS IC 10 2 20 10 0 30 21 Tego AF 4- SUS IC 10 3 30 10 0 40 94 22 SI 2213 SUS IC 10 3 200 150 150 500 23 PB 2724 SUS IC 10 1 300 250 250 800

[0132] Table 2 shows that in direct comparison sulfosuccinates having relatively long fatty acid ester chains (SUS IC 10) in each case exhibit less foaming than sulfosuccinates having relatively short fatty acid ester chains (WE 3475) in defoamer-comprising aqueous polymer dispersions, i.e. the defoamer is better emulsified.

EXAMPLES 23 to 31

[0133] The aqueous polymer dispersion of polymer A was mixed with various defoamers and wetting agents and the degree of wetting and the foaming behavior were investigated.

TABLE-US-00009 TABLE 3 Effect of defoamers on degree of wetting 0.2% 0.1% anionic nonionic 0.2% wetting wetting Foam Foam Foam Foam No. defoamer agent agent Wetting 1 min 5 min 10 min Sum 23*.sup.) — — — 80 50 40 170 24*.sup.) WO2310 WE 3475 WE 3130 2 50 10 5 65 25*.sup.) WO2310 WE 3475 WE 3162 1 30 20 10 60 26   WO2310 SUS IC 10 WE 3130 2 10 5 5 20 27a  WO2310 SUS IC 10 WE 3162 1 5 5 5 15 27b  WO2310 SUS IC 10 WE 3162 1 10 10 0 20 28*.sup.) PB 2724 WE 3475 WE 3130 2 400 400 350 1150 29*.sup.) PB 2724 WE 3475 WE 3162 1 400 400 350 1150 30*.sup.) PB 2724 SUS IC 10 WE 3130 2 350 300 300 950 31*.sup.) PB 2724 SUS IC 10 WE 3162 1 300 300 300 900 *.sup.)comparative

[0134] Table 3 shows that sulfosuccinates having relatively short fatty acid ester chains (WE 3475) in combination with strongly hydrophobic white oil/wax defoamers (Foamaster® WO 2310) exhibit more severe foaming in aqueous polymer dispersions than sulfosuccinates having relatively long fatty acid ester chains (SUS IC 10).

EXAMPLES 32 to 34

[0135] To compare the defoaming effect of silicone oil with white oil, aqueous polymer dispersions were admixed with defoamers based on white oil and based on silicone oil and also with wetting agents, and the short- and long-term foaming behavior was investigated.

TABLE-US-00010 TABLE 4.1 Composition of examples 32 to 34 No. Polymer ED 2522 WO2310 SUS IC 10 WE3120 WE3475 32*.sup.) Polymer A — 33*.sup.) Epotal ® FLX 3628 0.1% — 0.1% 0.1% 0.1% 34   Epotal ® FLX 3628 0.1% 0.1% 0.1% 0.1% *.sup.)comparative

TABLE-US-00011 TABLE 4.2 Foaming behavior of examples 32 to 34 After 1 day 23° C. After 14 days at 40° C. storage Foam Foam Foam Foam 10 Foam Foam Foam 10 Foam No. 1 min 5 min min Sum 1 min .sup.1) 5 min .sup.1) min .sup.1) Sum .sup.1) 32*.sup.) 200 100 100 400 200 200 190 590 33*.sup.) 150 90 90 330 200 200 190 590 34   10 10 10 30 30 20 10 60 *.sup.)comparative; .sup.1) defoaming effect after 14 days warm storage at 40° C.

EXAMPLES 35-41

[0136] The aqueous polymer dispersion of polymer A was mixed with defoamers and wetting agents and the degree of wetting and the foaming behavior were investigated.

TABLE-US-00012 TABLE 5.1 Compositions of polymer dispersions; reported amounts in parts by weight Polymer Foamaster ® Na dodecyl Additive No. dispersion WO 2310 sulfosuccinate Hydropalat ® . . . Wetting 35 *.sup.) 100 Polymer A 0 0 0 4 36 *.sup.) 100 Polymer A 0.1 0.2 0.1 WE 3120 4 37 *.sup.) 100 Polymer A 0.1 0.2 0.1 WE 3130 4 38  100 Polymer A 0.1 0.2 0.1 WE 3161 2 39  100 Polymer A 0.1 0.2 0.1 WE 3162 1 40  100 Polymer A 0.1 0.2 0.1 WE 3164 1 41 *.sup.) 100 Polymer A 0.1 0.2 0.1 WE 3197 3 *.sup.) comparative

TABLE-US-00013 TABLE 5.2 Foaming test results; reported as % incorporated air No. After 1 min After 5 min After 10 min Sum 35 *.sup.) 200 200 200 600 36 *.sup.) 190 190 150 530 37 *.sup.) 180 180 150 510 38  150 150 130 430 39  150 150 140 440 40  150 150 150 450 41 *.sup.) 200 190 180 570 *.sup.) comparative

TABLE-US-00014 TABLE 5.3 Foaming test results after 1 week storage at 40° C.; Reported as % incorporated air No. After 1 min After 5 min After 10 min Sum 35 *.sup.) 200 200 150 550 36 *.sup.) 200 150 120 470 37 *.sup.) 150 100 100 350 38  150 120 90 360 39  180 150 100 430 40  200 200 120 520 41 *.sup.) 200 300 150 650 *.sup.) comparative

EXAMPLE 42

[0137] When adding Hydropalat® WE 3488 (dialkyl sulfosuccinate) and Hydropalat® WE 3162 (ethylene oxide/propylene oxide block copolymer) it has proven particularly advantageous to premix these two wetting additives before adding them to the polymer dispersion. This makes it possible to avoid gelling at the dropping point such as may otherwise occur during addition of dialkyl sulfosuccinates. The gelation behavior for various additives and combinations is reported in table 6 below.

TABLE-US-00015 TABLE 6 Gelation behavior 20% aqueous 40% aqueous 60% aqueous 80% aqueous solution solution solution solution Lumiten ® I-SC Cloudy/trapped Gelled mass/ Gelled mass/ Clear/with (sulfosuccinate air bubbles trapped air trapped air trapped air type) bubbles/not bubbles/not bubbles flowable flowable Hydropalat ® WE Cloudy/without Viscous/ Viscous/ Slightly cloudy/ 3488 trapped air trapped air trapped air without air bubbles bubbles bubbles bubbles Hydropalat ® WE Readily mobile, Readily mobile, Readily mobile, Readily mobile, 3488/ clear liquid clear liquid clear liquid clear liquid Hydropalat ® 3162 (1:1) premixture