DE19728997A1 - Aqueous polymer dispersions used for coating paper, textiles and carpets - Google Patents

Abstract

Aq. polymer dispersions are obtained by adding the Zn salt of ricinus acid and/or the Zn salt of abietic acid and/or analogous resin acids and/or a Zn salt of other (un)satd. hydroxylated 16C+ fatty acids, as deodorising agent. Also claimed is a process for deodorising aq. polymer dispersions.

Description

The present invention relates to aqueous polymer dispersions with reduced odor emission as well as methods for desodory tion of aqueous polymer dispersions.

Aqueous polymer dispersions are industrial bulk goods that diverse uses, e.g. B. as the basis of paints, in building and corrosion protection, in paper, textile and tep find coating, etc. A problem with such dispersion NEN is that, due to production, they have different ge odor emitters such as mercaptans, which act as molecular weight regulators serve in the polymerization, ammonia, used for neutralization is used to contain residual monomers etc. The resulting one Smell is perceived as unpleasant by consumers, which is why there is a need for deodorized aqueous polymer dispersions consists.

As is known, deodorization is generally carried out by Be treatment of the dispersions after their production with steam, to remove the volatile components contained. Many disper Sions are not sufficient for this type of deodorization chend stable, so that coagulation occurs, which is an expense filtration before further use. Wu Another type of deodorization, e.g. B. by adding an odor-binding agent to the aqueous bottom polymer dispersions to the aforementioned complex process simplify.

Water-compatible agents with a deodorant effect are available well known from the field of cosmetics and personal care. So describes DE-A-17 92 074 agents with a deodorant effect, the active ingredients are the zinc salt of ricinoleic acid, salts or Esters of other saturated or unsaturated hydroxylated fat acids and zinc salts of abietic acid or other analogues Contain resin acids. These funds are mainly for the Her position of soaps, detergents, room sprays and deodorant sticks turns.

DE-C-37 26 636 also describes deodorants on Ba sis of the zinc salt of ricinoleic acid. the additional solvent and solubilizers included. Be there as a mediator in the hydrolyzed eneducts and Diels-Alder adducts of Ri  cen fatty acids and maleic anhydride used. This means are stable even with a high water content and no longer tend for clouding and precipitation of individual components. So they are also for use in the technical field, such as. B. the Ge elimination of odors in sewage treatment plants. Landfills, households, crane kenhäuser, agriculture, animal breeding, animal utilization as well as in meat and fish farms.

DE-A-38 08 114 also describes agents with deodorization the effect given by the zinc salt of ricinoleic acid as well if the zinc salt of abietic acid and / or zinc salts of others saturated or unsaturated hydroxylated fatty acids with 16 or more carbon atoms and one or more as solubilizers Partial esters of di- or polyhydroxyalkanes, mono- and disaccha riden, polyethylene glycols or alkanolamines with the enadducts from maleic anhydride to at least monounsaturated Contain C₁₀-C₂₅ carboxylic acids. Mixtures of this type can be found in Zu Preparations combined with water in practically all conditions be kidneyed without their durability in any way be is impaired.

DE-A-40 14 055 also describes deodorants Base of zinc ricinoleate, which is an ethoxylated fatty alcohol and a tertiary amine, preferably a tertiary amino alcohol, contain. These agents are characterized by good water tolerance and good flowability, which makes products can be produced, even with a longer storage time and high water content remain stable in solution.

The present invention has for its object aqueous Polymer dispersions with reduced odor emissions available supply. The addition of deodorant may have an effect the agent neither the properties of the polymer dispersions, such as e.g. B. the stability of the dispersive distribution, nor that of affect the products manufactured polymer dispersions.

Surprisingly, it has now been found that this problem has been solved if an agent is added to the polymer dispersions, which contains the zinc salt of ricinoleic acid.

The present invention therefore relates to aqueous poly mer dispersions with reduced odor emissions, obtainable by adding the zinc salt of ricinoleic acid and / or the zinc salt of abietic acid or analogous resin acids and / or a zinc salt of other saturated or unsaturated hydroxy  gated fatty acids with 16 and more carbon atoms as deodorising Medium.

Dispersions in particular can be used as aqueous polymer dispersions based on monomers, such as. B. alkyl acrylates. Alkyl methacryl laten, vinyl esters of C₁-C₁₈ monocarboxylic acids, vinyl aromatics, ethylenically unsaturated nitriles, vinyl halides. C₁-C₁₂-Al alkyl vinyl ethers and aliphatic hydrocarbons with 2 to 8 C atoms and 1 or 2 double bonds, or mixtures of these Mo. nomers are used, which are homo- or copolymers sate can act.

Preferred monomers are e.g. B. methyl methacrylate, methyl acrylate, n-butyl methacrylate, n-butyl acrylate, ethyl methacrylate, ethyl acrylate lat, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, vinyl laurate. Vinyl stearate, vinyl propionate, vinyl acetate, vinyl formate, vinyl bu tyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, styrene, α-methylstyrene, α-butylstyrene, o-chlorostyrene, Vinyl toluenes, acrylonitrile, methacrylonitrile, vinyl chloride, vinyli denchloride, methyl. Ethyl, n-propyl, i-propyl, n-butyl, i- Butyl, 2-ethylhexyl vinyl ether, butadiene, isoprene etc., or de ren mixtures.

According to a preferred embodiment of the invention the aqueous polymer dispersions are styrene / butadiene Dispersions.

According to another preferred embodiment of the invention the aqueous polymer dispersions are alkyl acrylate / styrene dispersions and alkyl methacrylate / styrene dispersers sions, especially around butyl acrylate / styrene dispersions.

The zinc salt of ricinoleic acid can be used as a deodorant and / or the zinc salt of abietic acid or the zinc salts of others analog resin acids, such as. B. Neoabietic acid, Levopimar acid, pimaric acid, palustric acid etc. can be used. As well the deodorant can sow other zinc salts of others saturated or unsaturated hydroxylated fatty acids with 16 and more carbon atoms, e.g. B. the trihydroxystearic acid, contain. The latter compounds reinforce the desodo effect of zinc ricinoleate.

An aqueous dispersion of Zinc ricinoleate and other of the aforementioned zinc salts are used be the Lö compatible with the aqueous polymer dispersion contains solubilizers and possibly solvents.  

Suitable solubilizers are e.g. B. from DE-C-37 26 632, DE-A-38 08 114 and DE-C-40 14 055 known and include hydroly based enadducts and Diels-Alder adducts of ricen fatty acids and Maleic anhydride, the adducts first hydrolyzed with water siert and then with a base such as caustic soda, potash lye, ammonia and / or triethanolamine are neutralized. Other suitable solubilizers are partial esters of di or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycol kolen or alkanolamines with the enadducts of maleic acid drid on at least monounsaturated C₁₀-C₂₅ carboxylic acids, such as e.g. B. ricinoleic acid, oleic acid, linoleic acid and linolenic acid, wherein in particular partial esters are used, which then with Amines implemented or with amino acid esters, such as the glycol esters of aspartic acid and / or glutamic acid combined will. Likewise, ethoxylated as solubilizers C₁₀-C₁₈ fatty alcohols with straight or branched alkyl chain and less than 30 ethylene oxide units per molecule in combination with a tertiary amine, preferably a tertiary amino alcohol, such as B. triethanolamine or N, N, N ', N'-tetrakis (2-hydroxypro pyl) ethylenediamine can be used.

Suitable solvents are e.g. B. monohydric and polyhydric alcohols and glycol ethers, in particular ethanol, isopropanol, propylene glycol, dipropylene glycol, glycerin and trimethylolpropane.

To reduce odor emissions, the aqueous polymer disperse the deodorant in one to reduce effective amount of the smell, especially in an amount of up to 5% by weight, preferably up to 1% by weight, based on the solid substance content of the aqueous polymer dispersion and the solid matter hold the deodorant added.

According to a preferred embodiment of the invention, the deodorant in an amount of 0.01 to 1 wt .-%, bezo conditions on the solids content of the aqueous polymer dispersion and the solids content of the deodorant added.

According to a further preferred embodiment of the invention an aqueous dispersion of zinc ricino is used for deodorization leats with a density of about 1.00 g / cm³ are used. The water content is 50 to 100%, especially 80 to 90%. Of the The pH of the added aqueous dispersion is about 6 to 8 and the zinc content is about 0.5 to 1.5%.

For the preparation of the aqueous polymer dispersion according to the invention NEN z. B. an aqueous dispersion of the zinc salt of Rici nolic acid stirred into an aqueous polymer dispersion, the  pH of these polymer dispersions beforehand, if appropriate, with a inorganic or organic base, such as. B. NaOH, on a ge suitable value can be set.

In contrast to those, aqueous polymer dispersions are simulated treat the prior art with the zinc salt of ricinoleic acid systems two-phase systems from an aqueous phase and a polymer phase, in which the odor emitters both in the aqueous phase as well as contained in the dispersed polymer are. It was not to be expected and therefore surprising that too deodorization of those in the polymer particles Odorant carried out with zinc ricinoleate. Beyond that it was Surprisingly, the smell of residual monomers, such as Al kyl (meth) acrylates and vinyl aromatic compounds, e.g. B. Sty rol, can be effectively reduced. Advantageously enough nevertheless small amounts of zinc ricinoleate for a desodo rier effect, so that the application technology own the aqueous polymer dispersions by adding in generally not be affected. Likewise, the Stabili the dispersive distribution is not impaired.

Another object of the invention is the use of Zinc salt of ricinoleic acid and / or the zinc salt of abietin acid or analogous resin acids and / or other zinc salts and others rer saturated or unsaturated hydroxylated fatty acids with 16 and more carbon atoms as deodorants or the use of the agents described above based on the Zn salt of Ricinoleic acid for deodorization of aqueous polymer dispersions.

The polymer dispersions according to the invention with reduced Ge odor emissions can in the usual manner known to the person skilled in the art technical products, such as B. binders for paints, Coatings in building and corrosion protection. Coatings for paper, textiles. Carpets, leather, etc. are processed.

The examples listed below are intended to ver the invention vividly, but without restricting them.

EXAMPLES Example 1 a) Preparation of a butadiene / styrene dispersion

Template:
0.25 kg sodium lauryl sulfate (10% by weight in water)
3.88 kg inlet 1
1.05 kg inlet 2
19.40 kg of fully deionized water
Inlet 1:
2.75 kg sodium lauryl sulfate (10% by weight in water)
0.50 kg of tert-dodecyl mercaptan
1.50 kg acrylic acid
17.50 kg butadiene
31.00 kg styrene
24.25 kg of fully deionized water
Inlet 2:
0.40 kg sodium peroxodisulfate
4.85 kg of fully deionized water.

The mixture introduced was polymerized at 85 ° C. for 15 minutes. On the remaining feed 1 was then closed for 5 hours and, starting simultaneously with inlet 1, inlet 2 for 5.5 hours admitted.

Particle size: 170 nm
Solids content: 50% by weight
Tg (DSC measurement): 17 ° C
pH: 2.1.

b) preparation of the mixture of aqueous polymer dispersion and deodorant

The butadiene / styrene dispersion from stage a) was by Zu administration of 25% NaOH to a pH of 7.5. Then an aqueous dispersion of the Zinc salt of ricinoleic acid with a solids content of 15 % added, so that mixtures were obtained which desodo resources with a share of

• a) 0.03%
• b) 0.15%
• c) 0.3%

based on the solids content of the aqueous butadiene / sty rol dispersion from stage a) and the solids content of the odorant.  

c) Evaluation of the smell of dispersion films

The films are prepared by diluting the step b) prepared aqueous polymer dispersion with water approx. 25% dispersion. Serves as a reference substance a 25% dispersion from stage a) without the addition of Zinkri cinoleat.

The blends are used to create films on a sili cast rubber plate and then 24 hours at 40 ° C dried. The films thus obtained in the format of approx. 12.5 cm × 8 cm are preheated in a glass bottle at 80 ° C. 250 ml volume filled with screw cap and 5 minutes in a drying cabinet heated to 80 ° C. On finally allowed to cool to room temperature and the Ge six test persons on a scale from 1 to 6 Assess (intensity). The results of the smell test shows Table 1.

Table 1

Example 2 a) Preparation of an n-butyl acrylate / styrene dispersion

Template:
14.00 g sodium lauryl sulfate (10% in water)
2.222 g of C₁₂ alkyl diphenyl ether disulfate Na salt (45% in water)
82.10 g of feed 1
6.25 g of feed 2
296.00 g of fully deionized water
Inlet 1:
2.00 g Na pyrophosphate 16.00 g sodium lauryl sulfate (10% in water)
11.11 g of C₁₂ alkyl diphenyl ether disulfate sodium salt (45% in water)
30.93 g acrylic acid
900.00 g of n-butyl acrylate
100.00 g styrene
4.000 g of tert-dodecyl mercaptan
100.00 g of fully deionized water
Inlet 2:
5.000 g sodium peroxodisulfate
120.00 g of fully deionized water
Inlet 3:
10.00 g tert-butyl hydroperoxide (10% in water)
Inlet 4:
10.00 g of hydroxymethylsulfinic acid sodium salt (10% in water).

The mixture introduced was polymerized at 85 ° C. for 15 minutes. Then was at 85 ° C for a while span of 2 hours the remaining feed 1 and, simultaneously starting with inlet 1, for a period of 2.5 Hours, the remaining feed 2 added. The reaction ge Mixing was then continued for one hour at 85 ° C stirred, cooled to 25 ° C and then ver with feed 3 and 4 puts. A dispersion with a solids content was obtained of 51.3% by weight and a pH of 2.4. Particle size (Malvern Autosizer): 151 nm.

b) preparation of the mixture of aqueous polymer dispersion and deodorant

The n-butyl acrylate / styrene dispersion from stage a) was by Addition of 25% NaOH to a pH of 7.2 poses. An aqueous dis persion of the zinc salt of ricinoleic acid with a solid content of 15% was added, so that mixtures were obtained which the deodorant with a share of

• a) 0.01%
• b) 0.03%
• c) 0.05%

based on the solids content of the aqueous n-butyl acrylate / Styrene dispersion from stage a) and the solids content of the deodorant contained.

c) Evaluation of the smell of dispersion films

For making the films and for evaluating the smell the procedure described in Example 1c was used. The results of the odor test are shown in Table 2.

Table 2

Comparative Example 1

• a) The n-butyl acrylate / styrene dispersion was used Example 2a.
• b) preparation of the mixture of aqueous polymer dispersion and ZnO.

The n-butyl acrylate / styrene dispersion from Example 2a was by adding 25% NaOH to a pH of 7.2 posed. Zinc was then added with vigorous stirring pure oxide according to DAB (Merck, Darmstadt) added, so that mixtures were obtained which contained the zinc oxide in a proportion of

• a) 0.01%
• b) 0.03%
• c) 0.05%

based on the solids content of the aqueous n-butyl acrylate / Styrene dispersion from stage a contained.

• c) Evaluation of the smell of dispersion films
  The procedure described in Example 1c was used to prepare the films and to assess the smell. The results of the odor test are shown in Table 3.

Table 3

As the results of the odor tests of the invention Let examples 1 and 2 (Tables 1 and 2) clearly prove aqueous polymer dispersions with reduced odor emis sion by adding the deodorant agents described Make the base of the zinc salt of ricinoleic acid. Here are before in some cases, very small amounts are effective. The Ver same example 1 (Table 3). at the ZnO as a reference substance was used for the deodorant agents according to the invention, showed no reduction in odor emis on the odor test sion.

Claims (10)

1. Aqueous polymer dispersions with reduced odor emis sion, obtainable by addition the zinc salt of ricinoleic acid and / or the zinc salt of Abietic acid or analogous resin acids and / or a zinc salt zes other saturated or unsaturated hydroxylated Fatty acids with 16 and more carbon atoms as a deodorant tel. 2. Aqueous polymer dispersions according to claim 1, wherein the des odorant in an amount of up to 5% by weight before adds up to 1 wt .-%, based on the solids content of the aqueous polymer dispersion is added. 3. Aqueous polymer dispersions according to claim 1, wherein the des odorant in an amount of 0.01 to 1 wt .-%, be drew on the solids content of the aqueous polymer disper sion, is added. 4. Aqueous polymer dispersions according to one of claims 1 to 3, the deodorant as an aqueous dispersion. optionally with the addition of a solubilizer is set. 5. Aqueous polymer dispersions according to claim 4, wherein the solubilizer is hydrolyzed enadducts and Diels-Alder adducts of ricin fatty acids and maleic anhydride;
Partial esters of di- or polyhydroxyalkanes, mono- and di-saccharides, polyethylene glycols or alkanolamines with the enadducts of maleic anhydride on at least mon and unsaturated C₁₀-C₂₅ carboxylic acids;
ethoxylated C₁₀-C₁₈ fatty alcohols with straight or branched alkyl chain and less than 30 ethylene oxide units per mole cool in combination with a tertiary amine, preferably a tertiary amino alcohol;
acts. 6. Aqueous polymer dispersions according to claim 1, wherein as a nono mere alkyl (meth) acrylates. Vinyl esters of C₁-C₁₈ nonocarboxylic acid ren, vinyl aromatics. ethylenically unsaturated nitriles, vinyl halides, C₁-C₁₂ alkyl vinyl ethers and aliphatic coal water substances with 2 to 8 carbon atoms and 1 or 2 double  bindings are used and it is homo- or copoly merisate acts. 7. Aqueous polymer dispersions according to claim 6, wherein it is are styrene / butadiene dispersions. 8. Aqueous polymer dispersions according to claim 6, wherein it is around alkyl (meth) acrylate / styrene dispersions, in particular around Butyl acrylate / styrene dispersions. 9. Process for deodorization of aqueous polymer dispersions, characterized in that to the aqueous polymer disper sion the deodorant, according to one of claims 1 to 5, is given. 10. Use of the zinc salt of ricinoleic acid and / or zinc salt of abietic acid or analogous resin acids and / or further zinc salts of other saturated or unsaturated hy droxylated fatty acids with 16 and more carbon atoms, given if together with a solubilizer, as in claim 4 or 5, for deodorization of aqueous polymer dispersers sions.