DE2236728A1 - PROTECTIVE COVERS AND PROCEDURE FOR THEIR MANUFACTURING - Google Patents

Description

PATENT LAWYERS

DR. IHC. A. VAN DERWERTH DR. FRANZ LEDE RER

21 HAMBURG 90. _ö MONKS 60

WIlSTOSiEB STR. 33 · TEL. «04 I H 77 08 61 LUCILE-GRAHN-STR. 22 ■ TEt. <0β H) - 7 29 47

Munich, July 26, 1972 HL 34 501

Hercules Incqporated, 910 Market Street, Wilmington, Delaware,

United States

Protective coatings and processes for their manufacture

The invention relates to protective coating compositions Water-based and especially those compositions which have a special hydroxyethyl cellulose - hereinafter referred to as HA'C - contain, which imparts a substantially increased bio-stability to the compositions. One embodiment of the invention relates to paints and in particular Latex or emulsion paints,

Although HÄO has been in protective covers as a floating means for many years or anti-settling agents and as thickening agents Has found great application, it would be for such It is even more suitable to use if its susceptibility to biodegradation could be reduced.

209886/1320

DEtJTSCME IANK AO .. HARIlURC 95/201) 11 POSTSCHECKi HAMBUIiG Π73 30 TBLECRAMMEi UEDEiI EH PATENT MÖNCHEN

The biological degradation of HÄC is the result of the hydrolytic cleavage of bonds between anhydroglucose units, which is catalyzed in particular by the enzyme cellulase, ie ß-1,4-glucan-4-glucanohydrolase. This enzyme is found in association with a wide variety of spores and bacteria found in air and water. If an aqueous solution thickened with HIC is contaminated with one of these microorganisms, the cellulase present catalyzes the hydrolysis of HIC, which lowers the viscosity of the solution. The speed at which the viscosity is reduced depends among other things on the enzyme concentration, and as will be explained in more detail below, it is dependent on the number and distribution of unsubstituted anhydroglucose units in the cellulose polymer. This enzyme concentration increases rapidly as the microorganism multiplies; On storage, the viscosities of such contaminated solutions will usually be substantially reduced, and in the case of tarpaulin compositions, e.g. B. paints, these viscosities are sometimes so low that the composition or compositions can no longer be used. Biostability is to be understood as the resistance to this degradation and the resulting reduction in viscosity. The term "biostable" is therefore used to denote the state in which HIC has a substantial proportion of its initial

Retains viscosity over prolonged periods of time / exposure to air or water carried biological substances, the presence of which could significantly reduce the molecular weight of HIC. In contrast to previously known HIC, a low percentage of unsubstituted anhydroglucose units in the HIC molecule is a measure of this biostability.

2 0 9 8 8 6/1 3 2 0

The abbreviation "M.S." used in the following with reference to HA'C has the meaning of the average number of molecules of Ethylene oxide, which with an anhydroglucose unit of Cellulose are linked. The determination is carried out according to the method modified by Zeisal according to Morgan, like them Ind. Eng. Chem. 10 (1946) '500 by P. Vi. Morgan stated became.

The invention is explained in more detail using the following examples, without restricting them. All figures in percentages, Parts and ratios are by weight unless otherwise specified.

In these examples, water-soluble HA'C was used as a thickener in various protective coating compositions (latex paints), and the susceptibility of HA'C to enzymatic degradation in the compositions was determined by the usual method, namely by measuring the decrease in viscosity of the protective coating composition after various times . It is desirable that a latex paint, at the time of use, have a viscosity of at least about 70 Krebs Units, hereinafter referred to as KE. In Examples 1 to M , an enzyme was used which is commercially available under the trade name Cellase 1000 from Wallerstein Co., the main component of this enzyme is Cellulasd or ß-ij ^ - glucan - ^ - glucanohydrolase. In Examples 5 and 6. the samples were inoculated with a living culture of Aspergillus niger, which forms enzymes in it. In each example, the samples were ^{stored in closed containers at 25 °} C. and their viscosities were measured periodically. The components of these formulations are commercially available or they can be easily

-209886 / 1320

conventional working methods from easily accessible chemicals.

Examples 1 and 2
Vinyl acetate dibutyl maleate latex paint

In Examples 1 and 2, the viscosity retention of the batches of vinyl acetate-dibutyl maleate copolymer latex paint listed in Table I below is compared, the HAC according to the invention being used as the thickening agent in Example 1 and the previously known HIC in Example 2, with 0.5 ppm of Cellase 1000 as the enzyme were used in each example. Except for the type of used HÄC the approaches and the production were identical.

Table I.

Components

Concentration in parts by weight in Examples 1 and 2 ^

Vinyl acetate-dibutyl maleate copolymer latex (Trade name i'lexbond 800)

Phenylmercury (II) acetate (trade name PMA-18) -

HlC (2 % conc.)

Sodium salt of a polymeric carboxylic acid, anionic dispersant, 25 % conc. (Trade name Tamol 731)

Nonylphenoxypoly (ethyleneoxy) ethanol, surface-active substance ( trade name Igepal CO - 710)

Ethylene glycol

735.0

0.9 597.4

13.0

11.7 73.5

209886/1320

Table I (continued)

Ingredients Concentration in wt. 'of Examples 1 and 2 ^ ^J

Silica containing hydrocarbons, defoaming agents (trade name
Colloid 60) ■ 7.0

Immiscible with water

12-C ester alcohol, coalescing

medium (description of goods

Texanol) 29.4

Ti0 _o pigment (trade name

TiPure R-900) 735.0

Talc extender, pigment

(Trade name Nytal 300) 73.5 "

CaCO, (trade name Atomite) 441.7.

Diatomaceous earth (trade name

Celite 281) 102.7

Water . 763.5

Note (a) “The formulations in Examples 1 and 2 were Identical except for the type of HA'C used. In Example 1, HÄC according to the invention was used, d. H. with 6.9% unsubstituted anhydroglucose units and an M.S. value of 2.5 · - In Example 2 a state-of-the-art HA'C was used, d. i.e., with 11.8% unsubstituted anhydroglucose units and an M.S, value of 2.5

The components of the examples listed in Table I. and 2 with the exception of the first three were together in a Cowles dissolver at 4400 rpm for 10 minutes marry. Then the stirring speed was increased to about 2000 rpm or reduced a little more slowly and slowly incorporated the first three ingredients.

209886/1320

The viscosity data and further details are given in Table II below.

Table II ^

At- HÄC-Art MS viscosity < ^d >

^game after (days) acceptance in KE-V / erten

0 1 8 13 20 30 after 30 days

1 according to the invention W 2.5 90 90 90 90 89 89 1.0

2 State of the _N

Technology W 2.5 86 84 82 81 78.76 10.0

Note (a) »0.5 ppm of the Cellase 1000 enzyme, based on the I make-up and a pH of 8 in each example;

(b) »6.9 % unsubstituted anhydroglucose units;

M.S. = 2.5;

(c) β 11.8% unsubstituted anhydroglucose units;

M.S. - 2.5;

(d) ■ the viscosities were determined with a Krebs-Stormer

Viscometer determined at 25 ⁰ C and expressed as Krebs units (KE).

Examples 3 and 4
Acrylic polymer latex paints

In Examples 3 and 4, the viscosity retention is the Approaches of acrylic polymer latex paints listed in Table III below compared, with HÄC according to the invention as thickening agent in Example 3 and previously known HAC were used in Example 4 and 1.0 ppm of the Cellase 1000 enzyme was used in each example. Kit

209886/1320

Except for the type of HIC used, the approaches and preparation were identical.

Table III.

Ingredients Concentration in wt. of Examples 3 and 4- ^v

Group 1 ''

Sodium salt of a polymer
Carboxylic acid, anionic dispersant, 25 % conc.
^ Trade name Tamol 731) 37? 5

Antifoam agent (trade name Nopco NDW) 7.5

Propylene Glycol 228 ₃ O

Ti0 _o pigment (trade name

TiPure R-900) 936.0

Water 291.0

Group 2

Propylene glycol '381 _s 0

Acrylic latex (trade name

Hhoplex AC 4-90) 1791.0

Antifoam agent (trade name Nopco NDW) ~ 7.5

Di (phenylmercury (II) -) -

dodecenyl succinate, - preservative (trade name
Super Ad-It) ■ 3.3

'Butyl Cellosolve 84, 9

Dioctyl sodium sulfοsuccinate,

surfactant

(Trade name Triton GE-7) 7.5

HIC, 2% aqueous solution 161.5

Note (a) “The approaches in Examples 3 and 4 were identical with the exception of the type of HIC used. In example 3, HIC according to the invention was used, namely with 6.9% unsubstituted anhydroglucose ingredients and an MS value of 2.5. In example 4, HIC was used according to the prior art, namely with 11.8 % unsubstituted anhydroglucose ingredients and an MS -Value of 2.5.

209886/1320

BATH ORIGINAL

The first group of ingredients in Examples 3 and K were ground together in a Cowles dissolver at 4000 rpm for 20 minutes. Then the stirring speed was reduced to about 2000 rpm or less and the ingredients of the second group were slowly incorporated.

The viscosity values and other details are given in Table IV below.

Table IV ^

At- HÄC-Art M.S. viscosity

play after (days) acceptance in KE-Verten

· 0 5 13 18 28 after 28 Tap: en

3 according to the invention ^ 2.5 76 74 72 72 72 4

4 State of the

Technology ^ 2.5 76 69 65 63 61 15

Note (a) »1.0 ppm of the enzyme Cellase 1000, based on the color formulation, and a pH value of 8.2 are used in this example;

(b) «6.9% unsubstituted anhydroglucose units;

M.S. »2.5}

(c) - 11.8 % unsubstituted anhydroglucose units;

M.S. - 2.5i

(d) ■ the viscosities were determined with a Krebs-Stormer

Viscometer determined at 25 ⁰ C and expressed as Krebs units (KE).

Example 5 and 6
Ethylene vinyl acetate latex paint

In Examples 5 and 6, the viscosity retention is the in the following Table V listed approaches of

209886/1320

BAD ORiGiNAL

Ethylene-vinyl acetate copolymer latex paint. juxtaposed, with HIC according to the invention as thickening agent in Example 5 and prior art HAC were used in Example 6 and a live culture of Aspergillus niger was used in each example was applied.

Table V

Components

Concentration in parts by weight of Examples 5 and 6 ^K

Sodium salt of a polymeric carboxylic acid, anionic dispersant
(Trade name Tamol 850)

Nonylphenoxypoiy ^ äthylenoxy) ethanol, surface-active substance (trade name igepal CO - 710)

Ethylene glycol

Antifoam agent (trade name Colloid 677) '

3-hydroxy-2 * 2,4-trimethylpentyl isobutyrate (Trade name Texanol)

TiOp pigment (V / arene denomination TiPure Ε-91Ί)

hydrated sodium silico-aluminate, Pigment extender (V / arene designation Zeolex 80)

Calcium carbonate (trade name Carbium) filler

Diatomaceous earth (trade name Gelite 281)

water

Ethylene-vinyl acetate copolymer latex (Trade name Aircoflex 510)

HÄC, 3% aqueous solution 35.0

20.0 125.0

20, Q.

• 50.0 1250.0

125.0 750.0

175.0 1000.0

1250.0 772.0

0 0 0 8 6/13 2

Note (a) “The approaches in Examples 5 and 6 were identical with the exception of the type of HA'C used. Example 5 was used according to the invention HiC, namely with 6.9 % unsubstituted anhydroclucose units and an MS value of 2.5. In example 6, HÄC according to the prior art was used, namely with 11.8 % unsubstituted anhydroglucose units and an MS value of 2.5.

All ingredients in Examples 5 and 6 except for the latter three are included in a Cowles dissolver Mill together at 4000 rpm for 20 minutes. Then became the agitation speed is reduced to about 2000 rpm or less and slowly incorporated the last three ingredients.

Proportions of these paints were 900 g of the same amount of 2 cc of the same, living culture of Aspergillus niger seeded, stored in closed containers at 25 ⁰ C, and the viscosity was measured periodically.

The viscosity values and further details will emerge from the following Table VI.

(a)

At- HÄC-Art

game

5 according to the invention ^

6 State of
Technology ^ ⁰ '

Table VI

M.S. viscosity

_Λ after (days) acceptance in KE-V / erter

^{0 4} 26 3 * '42 60 95 after 95 Taeen

2.5 90 90 90 86 87 86

2.5 90 88 86 84 83 82 79

2098 8 6/1320

BATH ORIGINAL

223672a

Note (a) “2 cc of the live culture of Aspergillus niger and a pH of 7i9 were used in each example; _r

Cb) β 6.3% "unsubstituted anhydro glucose units; M.S. -2.5; -

(c) β 10.3 % unsubstituted anhydroglucose units;

M.S. β 2.5; .

(d) β the viscosities were determined with a Krebs-Stormer

Viscometer determined "at 25 ⁰ C" and expressed as Krebs units (KE).

These investigations give the real conditions under which the organism in the paint. Lives and with its growth forms enzyme.

From the examples given above it can be seen that in two different types of paint formulations practically no loss of viscosity after about a month when using HIC according to the invention as a thickening agent occurred, while when using HÄC according to the prior art in the same paint formulations, a loss of viscosity occurred from about 10 to 15 KE.

The type of hydroxyethyl cellulose that can be used in accordance with the invention is essential. In order to characterize the HÄC 'according to the invention in more detail, the structure factors are discussed below, which influence the enzymatic degradation of water-soluble cellulose derivatives. Cellulose consists of straight chains of ß-anhydroglucose units, which by glucosidic. Ties are held together. ' It is believed that at cellulose derivatives soluble in water cause cleavage as a result of enzymatic hydrolysis at bonds between two anhydrous

/WHERE

glucose units occurs / of at least one unsubstituted

209886/1320

is; see HGH Sui in Ott and Spurlin "Cellulose and Cellulose Derivatives", p. 183, Interscience, New York (1954). From another side it is assumed that the chain break occurs more quickly at bonds between two unsubstituted glucose units, see MG Wirick, J. Polymer Science A-16 (1968), p. 1705. The change in intrinsic flow behavior, Ä ß0j, das According to LF McBurney in Ott and Spurlin, "Cellulose and Cellulose Derivatives" pp. 109-111 Interscience, New York (1954) represents a measure of the number of chain fractions, is directly proportional to the content of unsubstituted anhydroglucose units. if the weight of enzyme per anhydroglucose unit the HEC is kept constant. The following Table VII shows this for conventionally produced, water-soluble HÄC with various MS values.

Table VII

Conventional HÄC Example 7 8 9 10 11

M.S. 1.47 1.82 2.44 2.96 5.15

% unsubstituted glucose ^ 22.8 13.15 11.9 7.3 5.8 Δ [W after 24 h at 25 ^° C. ^ 1.34 0.85 0.69 0.47 0.23

Note (a) ■ unsubstituted glucose units per 100 glucose units;

(b) alteration of the intrinsic Pließverhaltens after 24 h at 25 ⁰ C for 0.0055 g mol / l of HÄC and 0.008 g / 1 enzyme (Cellase 1000).

The content of unsubstituted glucose units is determined by first hydrolyzing the cellulose derivative in aqueous HoSO ^

209886/1320

see standard ASTM Method D1915-65, Vol. 15, p. 651. The unsubstituted glucose in the hydrolyzate is determined by enzymatically oxidizing the unsubstituted glucose to gluconic acid and H ₀ O ₀ . In the presence of horseradish peroxidase, H ₀ O ₀ o -dianisidine oxidizes to a colored form. The developed coloring strength is a measure of the unsubstituted glucose, see RR Barton "Analytical Biochemistry" 19, (1966), 258-60. Since the change in the intrinsic flow behavior (a good measure of the number of chain fractions) is approximately proportional to the content of unsubstituted glucose It follows that the susceptibility of the cellulose derivative to enzymatic degradation is determined by the amount of unsubstituted glucose units present.

The type of HAC usable in the present invention is as follows Table VIII and defined in Figure 1 of the drawing and the prior art HIC in terms of the approximate percentage of unsubstituted anhydroglucose units for the given M.S. values compared. ·

Table VIII

% unsubstituted anhydroglucose units

Invention state of the art

M.S. -Area ^v values between 1.5 and maximum 2.0 ' 11 '. Hinimum , 5. 1.5 and Everyone ' If Il 2.0 and 2.5 9 · 12th 2.0 Il Il Il Il 2.5 and 3.0 7th • 10 2.5 Il Il Il Il 5 and J-, , 5 5.5 8th , 5 3.0 Il Il Il Il 3.5 and 4.0 4th 6th 3.5 Il Il Il Il 4.0 and 5.0 2 5 4.0 Il Il Il Il 5.0 and 10 1 3 5.0 Il H '2

209 886/1320

Note (1) a Each area including the first value closes however the last mentioned value, e.g. B. 1.5 and all values up to but not including are included in the first area.

The special one. HAO, which are used according to the invention can has already been made, so the HAG and the manufacture of which are known and not covered by the invention fall. However, for ease of understanding and completeness, preferred modes of manufacture are by HÄC described in more detail below. Two such modes of operation are the HA'C methods, which are described in US patents 3,131,176 and 3,131,177 are described. One essential condition for the production of suitable HIC is that the greater part of the hydroxyethylation is carried out using a low alkali / cellulose ratio will. As a result of the crystalline structure of the cellulose, however, it is necessary to have an alkali / cellulose ratio of to use at least about 0.2 / 1 and preferably from about 0.3 / 1 to 0.4 / 1 in order to reduce the crystallinity and to produce a HA'C with the desired good solubility in water in the reaction with ethylene oxide; this is on known. These two conditions are met by a hydroxyethylation in two stages, one being conventional Alkali / cellulose ratio in the first stage and a much lower alkali / cellulose ratio is applied in the second stage. The alkali / cellulose ratio in the first stage is at least about 0.2 / 1 and it can be about 0.8 / 1 or even higher as is known in the art, but preferably it is 0.3 / 1 to 0.4 / 1, especially if the product is according to the invention

209886/1320

should be used. That is in the second stage The alkali / cellulose ratio does not exceed about 0.1 / 1, and is preferably about. 0.03 / 1 to 0.08 / 1, however, ratios as low as about 0.01 / 1 and even about 0.005 / 1 can also be used. The first stage can.as hydroxyethylation to an M.S, value not above about 1.0 and preferably not above about 0.8, - with the second stage the remainder Part of the hydroxyethylation to the final, desired M.S.-value 'includes, the "about 1.5 to · 10 but often too 1.5 to 3. The alkali quantities given here refer to NaOH. ·

Various other working conditions for the production of HACs that are useful in the present invention are not essential and are well known in the art, so none Difficulty arises due to the description given above with regard to the essential influence of the area the values of the alkali / cellulose ratio to obtain a suitable HEC for carrying out the invention. The others. Working conditions are also not essential and on known z. B. whether the HÄC between the first and the second stage by removing practically all of the alkali and the other impurities are cleaned from it, the type of alkali, the optionally present diluent, the water / cellulose ratio, the type of cellulosic Material, etc. A preferred mode of operation for making HÄC useful in the present invention includes the implementation of ethylene oxide with cotton linters to one Hydroxyethyl M.S. of no more than about 0.8 in the presence of sodium hydroxide within the aforementioned ranges of the alkali / cellulose ratio, tert. Butanol, water, Neutralize the required amount of sodium hydroxide, continue the hydroxyethylation to the desired H.S. value

without purification of the HÄC intermediate and then the Cleaning of the finished HÄC product, such as Cleaning preferred but not required. Without in any way describing the invention to the details Restricting a typical procedure for the production of HÄC that can be used according to the invention is one of the following Embodiment explained in more detail.

A reaction mixture of:

1.0 TIn. Cellulose

0.8 TIn. Isopropanol

9.4 TIn. tert. Butyl alcohol 0.3 TIn. acetone

1.6 TIn. water

0.325 tin. NaOH and

0.43 TIn. Ethylene oxide

was stirred in a pressure vessel from which air had been displaced by nitrogen. The temperature was increased to 70 ^° C. in 0.5 h and held at 70 ^° C. for 2.5 h. The temperature was then lowered to 50 ° C. and a sufficient amount of HNO 2 was added to reduce the NaOH / cellulose ratio from 0.315 to 0.06. At this point the MS value was approximately 1.0. 0.86 TIe. Ethylene oxide was added and the reaction was completed ^{at 70 ° C. in a further 3 h.} The product was made by neutralizing the remaining alkali and washing with 80% acetone until no salts or by-product glycols were present. The product had excellent water solubility and an MS value of 2.9. Another HÄC product with a MS value of 2.9 was produced according to previously known procedures, the total ethylene oxide being added at the beginning. On each of these HÄC products in 1% aqueous solution,

209886/1320

BATH ORIGINAL

which was buffered to a pH of 5.5, investigations of the enzymatic degradation were carried out. The enzyme concentration (Cellase 1000) was 400 ppm, based on the HÄC, and this large amount of enzyme accelerated the investigations. The degradation took place at 25 ⁰ G for 4 h in closed containers. A comparison of the properties is given in Table IX below.

Table IX

HA'C HÄC invention state of the art

M.S. value,. 2.9. 2.9

Brookfield Viscosity (cP),

on 1% aqueous solutions at 25 ^° C. 800 790

% unsubstituted anhydroglucose

units' 5 »1 8» 5

Viscosity after 4 h 120 10

% remaining viscosity after

accelerated, enzymatic

Dismantling 15 1.2

In general, a water-based latex paint comprises fine divided pigment material and a finely divided film-former, both of which are dispersed in a liquid carrier consisting essentially of water. In the liquid Carrier is dissolved in a suspending aid.

The finely divided pigment material essentially consists from at least one pigment. It can comprise a mixture of pigments and extenders, examples of which are Titanium dioxide, potassium carbonate, bauxite, etc.

2 0 9 8 " ¹ BB / 13 2 0

BATH ORIGINAL

- 13 -

The finely divided .Filmbildner or the binder consists consisting essentially of at least one film-forming, organic substance, generally it is in a liquid medium Delivered in dispersed form, which usually contains water, this dispersion is often also available as an emulsion or latex designated. When the liquid medium is practically removed, e.g. B. by evaporation when applying the dispersion as coating on a surface, the film former coalesces under Formation of a resinous or polymeric film.

The suspension aid increases the consistency and / or the Viscosity of the liquid carrier and thereby sets the settling of those dispersed or suspended in the liquid carrier Particles to a minimum and makes the job easier.

In addition to the aforementioned ingredients, such latex paints also usually comprise a surfactant Substance that has a dispersion function and a wetting agent function. One of the main purposes of the Disper; sLons function is the flocculation or coagulation of the dispersed particles prior to application to a surface to be painted Minimum, while the main purpose of the wetting agent function is to increase the adhesion of the paint to facilitate oily surfaces. Usually, but not necessarily, the surfactant comprises two or two more substances, at least one of which is mainly than Dispersing agents and at least one other act mainly as wetting agents. Part of the surfactant

Substance or all of the surfactant can be used in the dispersion of the film former, as he / the manufacturers for Paint is delivered.

2 f) I) B 8 6 / I 3 2 Q

BATH ORIGINAL

The invention provides a protective coating composition which (1) a. Film former included in (2) a and (J) dissolved in said liquid carrier a suspending agent consisting essentially of hydroxyethyl cellulose, which is certain improved and very has advantageous properties for use in this composition. These three components are the main ingredients the basic composition according to the invention. This means that no further components are required. A preferred general embodiment of the base composition comprises (4-) one dispersed in the liquid carrier Pigment material. In addition, preferred specific embodiments include (5) surfactants, polygamy at least a dispersion function and preferably a wetting agent function own. Additives such as a preservative, a suds suppressor and the like can also be present.

The film former, as previously described, is at least a film-forming, organic substance. Examples of a fuming organic substances include polymeric substances, especially rubber-like or elastomeric materials, which are available in stable, aqueous latex form and to bleed (coalesce) into a film, preferably one pigmented film, capable, when brushed, sprayed onto a surface under normal ambient conditions, rolled up or otherwise applied.

In particular, natural rubber latexes, polymers, materials produced by emulsion polymerization and

dispersed polymers. .

in water / for example by emulsifying a solution of a Polymers in. A solvent, followed by partial or

20988 6/1320

BATH ORIGINAL

complete removal of the solvent by evaporation applicable. These include B .: vinyl polymers, in particular the homopolymers and copolymers of vinyl acetate, vinyl chloride, vinylidene chloride and copolymers with others unsaturated monomers e.g. B. ethylene, propylene, maleate and Fumarate esters and acrylic esters; Homopolymers and copolymers of olefin hydrocarbon, e.g. B. ethylene, propylene, 1-butene, styrene, butadiene, isoprene and the like, wherein Examples of such polymers are polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene, butadiene-styrene copolymer, Butadiene-vinyltoluene copolymer, isoprene-styrene copolymer, etc. as well as oxidized and halogenated derivatives these include homopolymers and copolymers such as oxidized polyethylene, chlorinated polyisoprene, etc .; Acrylic homopolymers and copolymers, which are repeating Containing units of acrylic acid ester, methacrylic acid ester, acrylonitrile and similar units, alkyd resins, Nitrocellulose, etc. Preferred film formers include e.g. B. vinyl acetate homopolymer, vinyl acetate copolymers with Dibutyl and dioctyl maleate and fumarate, vinyl acetate-ethylene copolymer, Vinyl acetate-acrylic and methacrylic ester copolymers, Homopolymers and copolymers of methyl, ethyl and butyl acrylates and methacrylates and butylene-styrene copolymers.

The amounts of HEC, film former and water, calculated as the weight of the total protective coating composition, which can be used vary widely. General amounts of HAC from about 0.03 % to 3.0 %, preferably from about 0.2 % to 0.7 % are suitable. General amounts of film former from about 10 % to 35%> preferably from 15% up to 25 % are suitable.General amounts of water / water of about

209 886/1 320

30 ° / o to 65%, preferably from about 35% 'to 50% are suitable''

To achieve the advantages possible according to the invention is it is only necessary to inform the HÄG according to the status of To replace technology by EIC according to the invention in protective coating compositions, according to the prior art the manufacture and use of protective coating compositions at the expense of previously known EaG for many Has been carried out on a large scale over the years and has also been described. Therefore, further explanations regarding the Ingredients, amounts, protective coating compositions, their preparation and application are not required.

201886/1320

Claims (1)

- 22 ~
Claims 1 »Protective coating composition increases significantly Biostability, which consists of a film former dispersed in water and one made from a hydroxyethyl cellulase existing anti-sedimentation agent contains »thereby marked that the hydroxylathyI cellulose a represented by the following diagram, low content of unsubstituted anhydroglucose units having. o _o ΟΙΟ ο _o .ι ι ι ι — ι ι 9686/1320 IAD ORIGINAL where .on the abscissa the average number of ethylene oxide molecules with an anhydroglucoεe of the cellulose are combined, and on the ordinate in percent the unsubstituted anhydroglucose units are specified. 2. Protective coating composition according to claim 1, characterized marked that the hydroxyethyl cellulose an M.S. fourth in the range from 1.5 to 10 and a maximum percentage of unsubstituted Anhydroglucose units according to the following list, with the M.S "area the first Value includes, but does not include the second value: maximum% unsubstituted M. .S. Area Il Il values between Anhydroglucose units 2.0 11 1.5 and Everyone Il > ■ Il 1.5 and 2.5 9 2.0 Il Il Il Il Il 2.0 and 3.0 " 7th 2.5 Il Il Il Il 2.5 and , 5 5.5 3.0 3! I! Il 3 and 3i 4.0 4th 3.5 Il H It 3.5 and 5 _? O 2 4.0 Il Il Il 4.0 and .10 1 5.0 Il 5.0 and Protective coating composition according to claim 1 or 2, marked by the fact that the protective coating composition Hydroxyethyl cellulose, film former and water in amounts of 0.03 wt.% - 3.0 wt.%, 10% by weight - 35% by weight or 30% by weight - 55% by weight of the total Contains protective coating composition. 209886/1320 4. Protective coating composition according to one of claims 1, 2 or 3, characterized in that the The hydroxyethyl cellulose component of the composition is prepared by performing the hydroxylation in two stages with the first stage at an alkali / cellulose ratio of at least 0.2 / 1 and the ratio / of the second stage was not more than 0.1 / 1. 5. Protective coating composition according to any one of the preceding Claims, characterized in that the hydroxyethyl cellulose has an M.S. value between 2.5 and 3 »0 and the maximum percentage of unsubstituted Anhydroglucose units is 7. 6. Methods of increasing the bio-stability of a protective coating composition water-based, wherein the composition comprises a water-dispersed film former and comprises a suspending agent consisting of a hydroxyethyl cellulose, thereby marked, that a hydroxyethyl cellulose is used as a suspending agent, which has a low content of unsubstituted Has anhydroglucose units according to the diagram of claim 1. 7. The method according to claim 6, characterized in "e" t that a hydroxyethyl cellulose is used which has an M.S. value in the range from 1.5 to 10, The maximum percentage of unsubstituted anhydroglucose units is defined by the following list, in which each M.S. area includes the first V / ert but does not include the last V / ert: 209886/1 320 M-. S. ..-Area values see between V U 1.5 and maximum % unsubstituted 11 Il It Il 2.0 and Anhydrogglucose units 9 1.5 and Everyone . Il U 2.5 and 2.0 7th 2.0 Il Il Il U 3 and 3, 2.5 5 * 5 2.5 Il Il 11 3.5 and 3.0 4th 3.0 U H Il 4.0 and 5. 2 3.5 ti M. Il 5.0. and 4.0 1 4.0 Il Il 5.0 5.0 Il M. 10 8. Verfahr s according to claim 6 or 7 ,. characterized in that a hydraethyl oil is used which has an M.S. value between 2.5 and 3.0, being the maximum percentage of unsubstituted anhydroglucose units. 7 is 9, method according to one of claims 6, 7 or 8, characterized gelsennz, shows that a hydroxyethyl cellulose component is used in the composition which is prepared by carrying out the hydroxylation in two stages was carried out, the first stage being carried out at an alkali / cellulose ratio γοη at least 0.2 / 1. was, and in the second stage the ratio is not over 0.1 / 1 read * 209886/132 BATH 2ί Blank page