DE2110472A1 - Masses of wax and polymers - Google Patents

Description

ENTANWlLt. HANS RUSGHKB

AuUUR

Atlantic Richfield Company, New York, New York, V.St.A.

Masses of wax and polymers

Waxes for coating and layering have long been used of materials such as paper, cardboard, corrugated cardboard, regenerated cellulose, wood, keder items, metal foils and the like plate-shaped materials are used to achieve these shielding properties such as, for example, moisture, steam, fat and oil resistance, Protective properties such as hardness and wear resistance as well as a certain appearance, e.g. gloss give «Ideally, the Waohsüberzug should be tough, hard, flexible, sticky and glossy and have a low permeability for water vapor, high fat «and oil resistance as well as good friction properties and have properties that prevent undesired sticking together. Because coatings that only wax exist,: do not have all of the desired properties, modified wax compounds were developed, the polymers such as, for example, various polyethylenes, propylene or butyl Kautfiohuke, Polyisobutylenes, polyterpenes and various mixed

109839/1566

polymers of the ethylene-aryl and ethylene-vinyl families contain. However, the addition of the polymer causes an increase in the melt viscosity of the coating, which makes processing easier is made more difficult. Since the polymers are considerably more expensive than the waxes, is. It is also desired by you, if possible to use low concentrations of the former. For economic and for technical reasons, the extraordinarily favorable properties of wax-polymer compositions have hitherto been possible not be fully exploited.

A polymer that is particularly successful in masses based on wax has been used is ethylene-vinyl acetate copolymer (ÄVA). Wax masses that contain this copolymer, have better tensile strength, elongation, breaking energy, gloss properties and the like than coatings that are exclusive assemble from wax. With increasing amounts of copolymer however, the melt viscosity and cost also increase.

It is known that the addition of an organic acid component to the mixtures of wax and ÄVA copolymer causes a substantial improvement in the physical properties without a major increase in the melt viscosity. By means of the Maasnahrne it is possible to reduce the polymer concentration in a coating without deteriorating its physical properties. This degradation the mixed polymer concentration is determined by a corresponding Accompanied decrease in the viscosity of the coating. It was now found that the addition of a polyamide to these compositions results in coating compositions which have improved hot gel properties, have improved gloss, improved hardness and toughness.

The aim of the invention is to provide improved wax-polymer coatings and compounds * for laminating, which are used to cover any Kind of paper materials are suitable, as well as covering and Layering compounds based on Waohs and ethylene vinyl acetate -Mix polymer, which improves heat sealability,

109839/1566

- 3 - A 123b

oessei'fcen have gloss, improved hardness and toughness.

In general, the compositions according to the invention contain the following Components in parts by weight:

(A) 100 parts of a wax with a melting point above 49 Cj (ß) 5 to 150 parts of an ethylene-vinyl acetate copolymer with a content of polymerized vinyl acetate im Range from 5 to 35 weight-j'j and a melt index im Range from 0.1 to 1000;

(C) a compatible · with wax, non-corrosive carboxylic acid having an acid number üoer 20, to give in an amount sufficient to provide the composition has a total acid number in the range from 5 to; and

(D) 2 Dis 20 parts of a polyamide with the structural formula HO-C-OC-R-CO-NHR ₁ -HH) _n H,

where R contains 13 to 48 carbon atoms and the remainder of a two basic fatty acid is, and viorin R, ~ is an alkylene group having 1 to 10 carbon atoms and η is an integer from 65 to 300.

The wax component used for the compositions according to the invention can be of mineral, vegetable, animal or synthetic origin or a mixture of such waxes. The wax must have a melting point greater than 4yC. The use of petroleum waxes represents a preferred embodiment of the invention. These VJaxles contain paraffin waxes which have a melting point of 4 to 93 ° C, the microcrystalline waxes having a melting point of 0 to 99 ° C. These V / axles can be completely cleaned, whereby they contain only very small amounts of hydrocarbon oils, or they can be semi-refined (raw paraffin) and have a content of hydrocarbon oils of up to about 30 ρ *

109839/1566

~ 4 - »A 1256.

In the most preferred compositions of the invention, a wax component is used a blend of 20 to 80 wt -.%

rs Q

of a paraffin wax with a melting point of 49 to 82 ° C and 80 to 20 wt .-> o of a microcrystalline wax with a Containing melting point of 60 to 93 ° C, these wax components result in masses that can be used at high temperatures. If you consider the concentration of the microcrystalline wax ■ increased, there is a higher maximum use temperature and an improved physical tensile strength, while the Dimensional stagnation is decreased.

The use of an ethylene-vinyl acetate copolymer is a critical feature of the invention. This ethylene-vinyl acetate copolymer should have a polymerized vinyl acetate content in the range from 5 to about 35% by weight and a melt index in the range from 0.1 to about 1000. Those of ethylene-vinyl acetate copolymers which have a content of polymerized vinyl acetate in the range of 15 to 35 wt. -Fo and a melt index of about 0.1 to I50 are preferred. Those ethylene-vinyl acetate copolymers which have 26 to 29% by weight of polymerized vinyl acetate and a melt index in the range from 0.1 to 25 are most suitable.

The concentration of the ÄVA copolymer should be the minimum amount required to impart the desired physical properties to the composition. Concentrations ranging from about 5 to about 150 parts by weight per 100 parts wax are suitable. The concentration of the copolymer is preferably in the range from about 5 to about 100 parts per 100 parts of wax, in the most favorable case from 15 to 40 parts per 100 parts of wax.

The polyamides that can be used for the inventive compositions are prepared by reaction of dibasic acids with di- or polyamides according to known methods. They are thermoplastic resins with molecular weights ranging from 6,000 to 9,000. They have the general structure-

109839/1566

- 5 - a 1230

formula:

Hb-C-OC-R-CO-NHR _x -NH) _n H,

wherein R contains I3 to 48 carbon atoms and the hydrocarbon radical a dibasic fatty acid, and wherein R is an alkylene group having 1 to 10 carbon atoms and η mean an integer from about 65 to 300 .. R can be saturated or unsaturated and is preferably the remainder of one diraerized fatty acid in which R J4 carbon atoms (in the dimerized form). R is preferably the remainder of oleic or linoleic acid, where R is preferably ethylene. The integer η is preferably in the range from about 100 to 150.

The polyamides can be used in the compositions according to the invention in amounts in the range from about 2 to 20 parts by weight per 100 parts by weight VJachs are introduced. The polyamide concentration is preferably in the range of about 3 to 10 parts.

The fourth critical component of the compositions according to the invention is the acid component. In general, any wax compatible, non-corrosive, acid number greater than 20 can be used Carboxylic acid can be used for the compositions according to the invention. The carboxylic acid must be non-corrosive to the extent that it does not attack the metal parts of machines or containers. In general, the carboxylic acids with lower molecular

z weight, such as formic acid, acetic acid, propionic acid, benzoic acid and the like, very corrosive and also generally not compatible with waxes.

The carboxylic acid should preferably have an acid number greater than about 30, although acids with an acid number lower than about 20 can also be used. Materials with a lower acid number , ie those with a higher molecular weight, are undesirable because they increase the viscosity of the molten mass without bringing about corresponding or comparable improvements in the desired properties. The acid number here corresponds to

109839/1566

usual definition, i.e. it gives the number of milligrams of alcohol Potassium hydroxide, which is used to neutralize 1 g of the tested substance in the presence of methyl orange will. Any aliphatic, alicyclic or aromatic acid with one or more carboxyl groups can be used in the inventive Compounds may be used provided that such acids are wax compatible and non-corrosive and have a Have acid number above about 20. The aliphatic caronic acids can be saturated or unsaturated. Examples of saturated, aliphatic carboxylic acids are nonanoic acid, lauric acid, tetradecanoic acid, Pentacosanoic acid, also naturally occurring acids, such as coconut fatty acid and tall oil fatty acid, sebacic acid, 2-butyl-2-ethylglutaric acid and 2-propyl-1,2,4-pentane tricarboxylic acid. Examples of unsaturated, aliphatic carboxylic acids are oleic acid, linoleic acid, linolenic acid and 5-0etene - ^, 3,6 -tricarboxylic acid. The alicyclic carboxylic acids can also be saturated or unsaturated.

Examples of saturated, alicyclic carboxylic acids are naphthenic acids (cycloparaffinic acids) including those having one or more alkyl side chains of different Be long, e.g. cyclohexane pelargonic acid. Examples of unsaturated, alicyclic carboxylic acids are abietic acid and acids produced by dimerization or trimerization from higher molecular weight, unsaturated fatty acids such as oleic acid or linoleic acid. Aromatic acids, e.g. Naphthoic acid, anthronic acid, alkyl-substituted phthalic acid and alkyl-substituted naphthalic acid can also be used according to the invention be used.

Carboxylic acids which have other functional groups than the caroxyl groups, e.g., aldehyde, keto or hydroxyl groups, can also be used in the compositions of the invention, provided that the functional group is the carboxy moiety not disabled. Accordingly, acids such as 12-hydroxystearic acid and oxidized petroleum waxes with an acid number of more than 20 can also be used in the compositions according to the invention

109839/1566

- γ - A 1236

be used. Acids containing small amounts of other elements, e.g. containing nitrogen, sulfur, oxygen, phosphorus, etc. may also be used provided the additional Elements do not interfere with the carboxy unit.

A carboxylic acid-oevorzugte is abietic acid, inter alia, in HoIz- Hurz occur containing melu- or less abietic acid, depending on how it chemically modified 1st. The products of the resin, which have been subjected to chemical treatments such as isomerization, oxidation in air, hydrogenation, disproportionation or dimerization, are also suitable as the carboxylic acid component. By subjecting the wood resin of a similar to the above treatments, the relative proportions of the acids that make up the wood resin composed, changed! accordingly, the properties of the HoIzhai * :; can be varied as desired. By oxidizing the wood resin it is possible, for example, to obtain a product with a higher softening point. Hydrogenation of the wood hare leads to a product with improved color stability. Disproportionation of the wood resin gives a product with improved resistance to oxidation. The dimerization of the wood resin gives a product with a higher softening point. The methods of modifying the wood resin by the above chemical processes are known to those skilled in the art, and the products thereby obtained are commercially available. '

Superior properties result from the use of an acid component, which is both an acid and a liquid contains. This can be achieved either by using a liquid acid or by using a solid acid (e.g. wood resin ) used in combination with a liquid acid or non-acid. This combination should be at least 35 wt .-, j one organic acid with an acid number greater than 20. Second, it should be at least 5% by weight of an organic liquid contain. Both the organic acid and the organic liquid should have a boiling point above 149 ° C at 7 mm Hg, and both should be treated with your wax, the ethylene vinyl

109839/1568

- 8 - a 1236

acetate copolymer and the polyamide at the temperature at which the coating is applied as a hot melt, be compatible. In the most favorable case, the organic acid has an acid number above 30 and is present in the acid component in an amount of more than 50% by weight. The organic liquid is preferably present in the acid component in an amount greater than 20 % by weight.

While a preferred acid component must contain both an acid and a liquid, both requirements can be met by using an organic carboxylic acid that is a liquid at 21 ° C. On the other hand, both liquid organic acids and liquid organic non-acids can be used to the same extent if desired. For example, liquid acids such as the oligomers of fatty acids can be used alone or together with a solid organic acid or a liquid organic non-acid. When a liquid organic carboxylic acid is used, it must have to 8OO a melting point below 21 ° C, a viscosity at 38 ⁰ C in the range of 500 to 10,000 SSU (Saybolt seconds) and a molecular weight in the range of 400th Preferred liquid acids are the dimerized and trimerized fatty acids which contain from 16 to 22 carbon atoms; for example dimerized or trimerized oleic acid, arachidonic acid, sorbic acid or eicosenoic acid. Most preferred are the dimerized and trimerized fatty acids having 18 carbon atoms, for example dimerized or trimerized oleic acid or linolenic acid.

Organic carboxylic acids which are liquids at 21 ° C may be used if they are at least 5 wt -% of an organic liquid combined.. This solid organic carboxylic acid must have an average molecular weight in the range from 150 to 1200 and an acid number greater than 20. Preferably; this acid has an average molecular weight of 400 to 100 and a melting point in the range of 49 to 93 ° C. A preferred solid organic acid

109839/1566

- 9 - A 1236

is abietic acid, which is commonly found in wood resins.

The organic liquids suitable for practicing the invention must be liquids at 21 ° C and boiling above 1 ^ 9 ° C at J mm Hg. As previously indicated, the acid component must contain at least 5 % of a liquid organic acid or a liquid non-organic acid. If a liquid organic non-acid is used, it must be a hydrocarbon compound, which can be an oil or a styrene, butene or propene polymer.

The oil which can be used as organic liquid may be any hydrocarbon oil having a viscosity at 38 ⁰ C in the range of JX) O to 3ooo SSU. The oil preferably has a viscosity at 38 ° C. in the range of 500 to 150 CFU. The most preferred oil is a refined white oil.

The styrene polymers which can be used as organic liquids according to the invention must have a viscosity at 38 ° C. in the range from 800 to 100,000 SSU and an average molecular weight in the range from 300 to 3,000. The viscosity at 38 ° C. is preferably in the range from 800 to 3500 SSU and the average molecular weight in the range from d 300 to 1300. These polymers can be prepared by polymerizing various styrene monomers to give low molecular weight polymers. A mixture of styrene monomers can also be polymerized. For example, suitable polymers can be derived from styrene, OC-methylstyrene, or alkylated styrene such as, for example, alkylated oC-methylstyrene, alkylated oC-methyl-methylstyrene or alkylated p-methylstyrene and mixtures thereof. A particularly suitable polymer of this type is made by simultaneous alkylation and polymerization of monomeric! Styrene, OC -methylstyrene, OC-methyl-p-methylstyrene, p-methylstyrene or a mixture of these monomers.

109839/1666

- 10 - A 1236

The liquid Butenpolymerisate which can be used as organic liquids according to the invention have at least 90 wt -. Contain% butene and having a viscosity in the range 1000 to 1,000,000 SSU at 38 ⁰ C and an average molecular weight from 300 to 12,000 . Copolymers containing butene and up to 10% by weight of other, lower monoolefins can also be used. The butene polymer is preferably a homopolymer with a viscosity of 800 to 3,000 SSU at 38 ° C the average molecular weight of Bireich I6OO to 25OO the most preferred Butenpolymerisat W is a by Polymeric -. ^ z ion produced from butene-1 or isobutylene polymer.

The Propenpolymerisat, which can be used as the organic liquid according to the invention, has a viscosity at 38 ⁰ C in the range from 10,000 to 1,000,000 SSU and an average molecular weight in the range of 8OO to 3500. This polymer preferably has a viscosity oei 38 ⁰ C from 20,000 to 50,000 SSU and an average molecular weight from 1000 to 2000.

Preferred compositions can be produced by using, as acid component used m a mixture of wood rosin and dimerislerten fatty acids or a mixture of wood resin and styrene polymer. This acid component can contain, for example, 70 to 95% by weight of resin acid and 5 to 30 % by weight evi- / o of a dimer of 9jl2-octadecadienoic acid or a styrene homopolymer.

The acid component is introduced into the composition according to the invention, both to impart improved properties and to make the polyamides soluble. The amount of acid should therefore be high enough be to achieve these goals iu. The concentration should be sufficient to achieve an acid number in the range from 5 to 200. In the best case it is available in an amount which is sufficient to achieve an acid number of 10 to 75.

109839/1566

- 11 - A I256

The concentration of the acid component that is required to achieve the necessary acid number, of course, depends on the specific acid used, but it is usually in the range from 10 to 150 parts by weight per 100 parts of wax.

Ingredients that usually result in waxes or ethylene-vinyl acetate copolymers are added, can be introduced into the compositions according to the invention in effective amounts, - without deviating from their scope. Examples of such components are: heat and UV stabilizers, inert fillers, secondary plasticizers, lubricants, pigments and colorants, antioxidants, gloss stabilizers, agents that improve the viscosity index, solvents, Agents that improve wear properties, etc. Special can use agents such as the solid glycol esters of wood resin acids can be added to improve color, odor and heat stability.

The production of the compositions according to the invention is not a critical feature for their execution. These masses can be produced, for example, by heating the wax to a temperature above its melting point, adding the ethylene-vinyl acetate copolymer, the acid component, the polyamide and other additives and stirring vigorously until a homogeneous hot λ melt is obtained. It has been found, however, that the acid component facilitates the dispersion of the polymers. When this method is used, it is therefore preferred to introduce the acid component into the molten wax prior to the addition of the polymers. A special manufacturing process is as follows: the waxes are melted together, any antioxidants or heat stabilizers are added, and the melt is then brought to a temperature above 55 ° C. The acid compartments are heated to above about 135 ° C. and added to the hot melt. The ethylene-vinyl acetate copolymer and the polyamide are then added to the melt with vigorous stirring, a temperature above 55 ° C. being maintained. After all

109839/1568

- 12 - A I236

Copolymer has been added to the melt, the temperature of the melt is increased to about 154 ° C, and it is stirred until the mass is homogeneous. The polymers can also first be mixed with the acid component by they are combined at a temperature above 121 C. When this mixture is homogeneous, it becomes the melted wax added.

The following examples are intended to provide specific embodiments of the Explain the invention. All parts and percentages are based on weight.

Examples

The mixtures in the table were prepared as follows:

Half of the amount of wax and the acids were heated to 135 ° C. The ÄVA copolymer then became this mixture added, and it was stirred until a uniform dispersion was obtained. The remaining portion of the wax was heated to 104 ° C and the polyamide and polystyrene (if used) were added. The two mixes were then combined and stirred until homogeneous.

109839/1566

Tabel

A 1236

Mixture No.

Parts by weight

Petroleum wax (l) 100 AYa copolymer (2) 30

Polyamide (3)
Polyamide (4)
Wood resin (5) 60 Dimerized fatty acid (6) 10

Trimerized Fatty Acid (7)

Polystyrene (8)

exams
Acid number

viscosity
(Cp)

120 ⁰ C

Penetration hardness (9) ^ * 3 C

Yield strength to break (10) kg / cm ²

% Elongation (10) breaking energy (10) mkg / on

neg

56

I37I 16

420

22.0 110

0.397

180 ° bending value (ll) 534 initial gloss (13) 71

00 100 100 100 · 100 30th 30th 30th 30- 10 10 10 - - ■ - - - 10 10 60 50 50 50 40 - - 10 - 10 10 10

46

1350 15

387 20.9 95 10

39 1298

16

379 20.4 92

49 1277

17th

384 21.0 90

49

I307

16

389 21.7 95

0.270 0.262 0.257 0.278

491 482

98 97

89

94

Wear-resistant-

ability (13) massive marks excellent. excellent excellent, Pick / Block @ ° C 54/61 64/66 + 64/66 + 64/66 + 64/66 +

Bond strength (12) g / cm sulfite paper

Sulphite paper T.S. (13) T.S. Aluminum 4 ^, 0 T.S.

Glassine 13.8 43.8

50

1268 21

360 21.0 91

0.253 462

90, excellent,

T.S. T.S. T .S. T .S. T.S. T.S. T .S. T .S. 63.5
(FP) (13) o9.5
(FP) T .S. T .S.

109839 / 1B68

labe 11 e (continued)

A 1236

Mixture No. 1 2 5 3 4th Parts 51, 8th 5 6th 4th Weight , 0 94, 0 Polypropylene 9.8 29 7th 49 , 0 47, 2 54.9 59 (FP) "Aluminum on
aluminum 31.5 71 6th 91 , 5 23, 2 97.5 109 Aluminum on
Polypropylene ■ lA 23, 0 43 ,1 39 0 51.8 54.9 Glassine on
Pergairiv-in 11.8 15, 20th , 5 26.5 37.3 Glassine on
aluminum 15.8 24, 37 42.5 46.0 Notes on Tabel:

(1) Mixture containing 75 parts of completely purified paraffin wax with a melting point of 66 ° C (ASTM D-87) and 25 parts of a wax based on microcrystalline wax with a melting point of 80 ° C (ASTM D-IkJ).

(2) ¹¹ ELVAX 360 "- an ethylene-vinyl acetate mixed polymer with a bound vinyl acetate content of 28 wt .- ^ and a melt index of 0.1.

(3) Polyamide, made by reacting a dimerized oleic acid with an ethylenediamine. The molecular weight of the polymer was about 6000. It had a softening point (ASTM-E28-58T) of 110 ° C and a viscosity at 160 ° C of 25 poise (ASTM D 445-64).

(4) "VERSAMID 940" - a polyamide produced by the reaction of a dimerized linoleic acid with atnylenediamine. The molecular weight of the polymer was about '( 000, its softening point 110 ° C (ASTM-E2Ö-58T) and its viscosity at 10 ° C.

109839/1568

- 15 - A I236

20 poise (ASTM D 445-64).

(5) Disproportionated wood rosin having a melting point of 83 ⁰ C (Ring and Ball), an acid number of 154, a saponification number of ungs I89 and an average molecular weight of from 45O.

(6) Dimerized 9,12-octadecadienoic acid with a melting point of 1.7 ° C, a Si
38 ° C from 1000 SSU.

of 1.7 ° C, an acid number of 190 and a viscosity

(7) 9,12-octadecadienoic acid Trimerized having an acid number of 190, a melting point of 10 ° C and a viscosity at 38 ⁰ C of 6OOO SSU.

(8) A viscous, liquid polystyrene with an initial boiling point at I54 ⁰ C at 7 mm Hg, an average molecular weight of 325-350, a specific gravity of about 1.03 and a viscosity at 38 ⁰ C. of about I500 SSU.

(9) - ASTM 1321

(10) Tensile strength, elongation and fracture energy were determined according to ASTM

D 1708 -59T using non-milled samples produced by injection molding.

(11) The 180 ° bending values were determined according to that in the USA patent 3 417 040, column 7, lines 10-73 determined.

(12) The strength of the bond was determined by coating the first of two substrates with a wax compound. That The coated substrate and the second substrate were then pressed together with a hot iron with the coating between them found. After the coating had cooled, the substrates were separated. The strength of the bond is indicated than the force in g / cm width that is required to achieve the

109839/1566

- 16 - * A 1236

Tons of substrates. "T.S." means "tear seal", which indicates that the coating did not yield, but rather the substrate itself tore. "f.P." means "fiber pull" which indicates that though the substrates could be separated without tearing, but leaving fibers in the coating.

(13) The gloss tests were carried out as follows:

The gloss was measured under two conditions, i.e. initially after cooling in air and after wearing and aging the Sample for 12 days.

The devices used were as follows:

1. Scraper Bars - Two stainless steel bars with diameters of 9.525 mm are made with steel wire of 0.305 mm in diameter wrapped in such a way that each turn of the wire is in continuous contact with the previous one Turn stands. These two wrapped rods are then placed parallel to each other in an adjustable clamp through which the distance between them can be varied from 0 to 6.35 mm.

2. A source of heat, which the wax mass and the doctor sticks able to hold at I07 + 1 ° C.

3. Thickness gauges in the range from 0 to 0.76 mm.

4. Water bath of about 300 ml. '

5. Test paper - an unbleached kraft paper weighing 3.37 kg / m (69 lbs / 1000 ft ² ) (other papers can be used if desired).

6. Glossmeter - A Hunter DIb Specular Glossmeter, such as it is described in TAPPI standard rc 653 ts-63. The scale ranges from 0 to 100. Zero is registered when a black-lined cavity is placed over the sample opening. A reading of 100 is obtained on polished black glass with an index of refraction of 1.5 ^. 7 Wear device: Any friction machine such as one "Testing Machines Inc.", which enables a power of

109839/1566

.J " 211 (H 7 |

-.17. - A 1236 "~~

1000 g on the sample while it is pulled at a speed of 91 ¹ l-cm per minute 7 > 62 cm over an abrasion surface.
8. Abrasion Surface - Scott OHA-I5O Industrial Paper Towel

The following procedure is used:

1. About 500 g of the wax mass to be examined are set to 107 + 1 ° C heated.

2. The doctor bars are adjusted so that when a sample is coated, its thickness increases by 0.076 mm + 0.005 (0.038 + 0.0025 mm coating on each side). The stripper bars are then heated to IO7 ⁰ C.

3. Test plates are cut from the kraft paper. The samples have dimensions of 69 * 85 mm X 184.15 mm. » whereby the longer dimension extends in the machine direction of the paper.

4. One of the narrow ends of the test plate is then inserted between the scraper bars so that about 25.4 mm of the paper protrudes from the other side of the bars. The waste \ roaming rods are then held directly over the reservoir with the hot coating mass and then lowered mm immersed in the coating composition to the long, narrow end of the sample about the 127th By pulling on the part of the sample protruding by 25.4 mm, it is removed from both the coating material and the stripping rods by pulling the paper through the rods. The molten coating is then immediately cooled by placing it in air at 23 ° C and 50 % relative humidity. Moisture is swirled vigorously until the coatings have solidified. This procedure is repeated until five air-cooled samples are obtained which have the required coatings of 0.076 ± 0.005 mm. The measurement of the coating wix'd 50 .mu.m away from the neschLeiteten end along the Io4.15 mm-R: Lchtuui (j v .-. R ^

109839/1586

- 18 - A 125t

5. The gloss of the five samples is then determined on the gloss rnesser, the average value is calculated and used as the initial

- reproduced rather gloss.

6. The five samples are then prepared for a wear test. A hole is punched in the center of the uncoated end. An industrial embossed paper towel (Scott OHA-150) is attached to one end of a Testing Machine Inc. rubbing machine with the embossed side up. A sample is placed "sieve side" down on the paper towel. The term "wire side" relates to the designation of wire and mushroom sides of papers placed on Fourdrinier machines L.,., Which is customary in the paper industry. A square pine wood panel measuring 50.3 50.8 6.55 mm is placed over the center of the test area, which is 50.8 mm from the coated end. A weight of 1000 g is placed on the square wooden plate and the hook of the TMI friction machine is passed through the punched hole of the sample. The sample, along with the wood and weight on it, is drawn across the embossed paper towel over a distance of 7c.2 mm at a rate of 91.44 cm per minute. The sample is then removed and aged for 12 days at 23 ° C and 50 % relative humidity. The gloss after "wear and tear" is determined on the gloss meter.

Preparations 2 to 6 are embodiments of the invention. Preparation 1 is a control that does not contain polyamide. In all cases the preparations according to the invention had better gloss and sealing properties compared to Control.

- patent claims -

1Q983S / 1566

Claims (10)

- 19 - A 1236 claims: 1. mass, characterized in that it contains the following components in parts by weight contains: (A) 100 parts of a wax having a melting point above 49 ° C; (B) 5 to 150 parts of an ethylene-vinyl acetate copolymer with a content of polymerized vinyl acetate of 5 to 35 percent by weight and a melt index in the range from 0.1 to 1000j - (C) a non-corrosive carboxylic acid compatible with wax having an acid number greater than about 20 in an amount sufficient to give the mass a total acid number award in the range of 5 to 200; | (D) 2 to 20 parts of a polyamide with the structural formula HQ ^ -OC-R-CO-NHR ₁ -NH) _n H, wherein R 1 contains 5 to 48 carbon atoms and the Is a residue of a dibasic fatty acid, wherein R 1 is an alleylene group having 1 to 10 carbon atoms, and where η is an integer from about 65-300. 2. A composition according to claim 1, characterized in that the ethylene-vinyl acetate copolymer I5 to 35 wt -% containing polymerized vinyl acetate.. 3. Composition according to claim 1 or 2, characterized in that the ethylene-vinyl acetate copolymer has a melt index 109839/1566 - 20 - A 1236 in the range 0.1-25. 4. Masse.nach one of claims Ij 2 or J5, characterized in that that the concentration of the ethylene-vinyl acetate copolymer is in the range from about 15 to about 40 parts per 100 parts of wax. 5 »mass according to claim 1, characterized in that R in (D) a dimerized fatty acid residue with J4 carbon atoms is. 6. Composition according to one of claims 1 - 5 * characterized in that that the polyamide in an amount ranging from 3 to There is 10 parts per 100 parts of wax. 7. Composition according to one of claims 1-6, characterized in that the acid component (C) is a non-corrosive acid component which, in the case of oils for applying the coating, is compatible with the wax and the ethylene-vinyl acetate copolymer * where this component contains at least 35% by weight of acid and at least 5 % by weight of liquid, all of which have boiling points above 149 ° C at 7 mm Hg, whereby the acid can be one of the following compounds: 1), comprising an organic carboxylic acid, the C is a liquid at 21 °, a viscosity at 38 ⁰ C in the range from 500 to 10,000 SSU, an average molecular weight in the range 400 to 2500 and an acid number above; .._...-_.__-._ 2) an organic carboxylic acid that has a melting point above 21 ° C, an average molecular weight in the range of 150 to 1500 and an acid number greater than 20 has i and 5) a mixture of 1) and S | i the liquid being one of the following compounds can: \ 10,9,839 / $ 1 66 - 21 - A I23O 1), having a viscosity at 38 ⁰ C in the "range 500-10000 SSU, an average molecular weight of from 400 ° to 2" 5ÖQ and an acid number of more than 20, an organic carboxylic acid ° at 21 ° C. a liquid; 2) a liquid hydrocarbon at 21 ° C, the one ^ the following connections can be: (a) an oil with a viscosity at 3d ⁰ C of 300 to 3,000 SSU; (b) a styrene polymer with a viscosity at 30 ° C from BOO to 100,000 SSU and an average molecular weight from 300 to 3,000; Ä (C) a butene polymer which is at least y0 wt .-,.> Contains butene, with a viscosity at 30 ° C of 1,000 to 1,000,000 SSU and an average Molecular weight in the range of 300 to 12,000; (d) a propene polymer with a viscosity at 3oC from 10,000 to 1,000,000 SSU and one average Molecular weight from 300 to 3500; 3) a mixture of 1) and 2). 8. Composition according to claim Y, characterized in that the acid component is a mixture of liquid and non-liquid organic carboxylic acids. 9. Composition according to claim Y, characterized in that aa.ss the Acid component a mixture of wood resin acids and dimerized or trimerize fatty acids is wooei the fatty _ _s acid_16 to_ contains 22 carbon atoms. 10. Composition according to claim <Y_, characterized in that the Acid component is a mixture which is a styrene polymer and contains wood resin acids. Me./Br. 109839/1566