DE1932514A1 - Polyolefin compound suitable as a rust preventive - Google Patents

Description

DA-3281

19325H

Be B ₁ C ₁₁₁₁ Ii re ib u η g in the patent application

the 3? irraa

AIÖELLO CHEMICAL CO. ,, LTD. 18 y 3-Chorae, Fukutplru-cho »

Kita-kUs, Hagoya-shi., Alchi-ken Japan

betraffezid As a Rpstsohutammittel gelgnote Polyolefinmaaae

Priority; 26. 6.1968, ITr ₀ 44030/68, Japan 30 ^_o; .v: ₅ j96S, fe _o 96599/68, Japan

Dia JürfinduJig uses polyolefin tools, esp especially on rust-protecting or corrosion-preventing Polyolefin water-c

An object of the invention is _a new @s rostschütaende and 'corrosion inhibiting Polyolofinmassen for A · = winding BSWA Pausmaterial specify "

A further object of the invention is to provide anti-rust and to indicate corrosion-preventing polyolefinniasaen, die sich. «rar production of films, layered Planar structures and laminates or composites are suitable *

009812/1805

Another object of the invention is to provide a rust preventive and to indicate corrosion-preventing polyolefin compound that is suitable as a molding compound o

Finally, it is an object of the invention to provide anti-rust protection and corrosion-preventing polyolefin compounds to indicate which can be used as coating masses baw "spreadable Suitable material.

On rust-protecting or "corrosion-preventing wrapping or Paokraaterialisn are liable to the extent that these materials are made by Überaishar. are produced, one or more volatile inorganic or organic bases, for example on the surface of paper, cardboard, textiles, cellophane and the like bsw _e these materials are impregnated with the volatile inorganic or organic bases mentioned. The wrapping or packaging materials known here are used to pack metallic objects, in particular those which consist of iron, aluminum or an alloy thereof, which are easily corroded when they come into contact with moist air.

These known packaging materials are generally opaque and have the disadvantage that the wrapped content cannot be seen.

■ - 2 -

009812/1805 _{BAD 0RIQ1NA} u

3 19325U

Another disadvantage of these known materials is that moisture can penetrate the inside of the packaging and thus reduce the rust protection effect of the materials. In order to at least partially overcome these disadvantages, some post-treatments have to be applied to the packaging materials. For example, the penetration of moisture through the wrapping material and the evaporation of the volatile, rust-resistant material can be reduced by laminating a polyethylene film or a polyethylene disc onto the rust-proof paper, but the laminated wrapping materials, as mentioned above, are made of two layers, namely one which contains the volatile anti-rust substance and the other layer which consists of the material through which the anti-rust agent does not just smolder, the anti-rust substance only adhering to the surface of the packaging material and insufficient anti-rust effect and that this effect does not last long enough.

Distinguish the rust-resistant compositions according to the invention differ significantly from the known packaging materials that are manufactured using the rust preventive en paper, cardboard, textiles made to adhere as a coating octer impregnating agent used or that these materials have at least two layers

009812/1805

BATH ORIGINAL

19325 U

sit that either by laminating a resinous Material on the rust-free paper or textile be produced or by die.Rostschutzsubstanz on the resinous material with the paper or Cloth is laminated, made to adhere or applied as a coating or by impregnation. The protective and corrosion-preventing masses are new and are suitable as films, foils, composite material, molded bodies, Coatings and paints.

The Masson according to the invention contain essentially

Polyolefins and PicycloheXyiammoniurasalEfc of Aliphatic Carboxylic Acids. In particular, the compositions according to the invention contain, in addition to the polyolefin and dicycloammonium as of aliphatic. Carboxylic acids at least one rust, namely organic monoamine salts of nitrous acid, polyhydric alcohol esters of aliphatic carboxylic acids, rosin amine salts, alley; ejT.:. Ce of aliphatic carboxylic acids or mixtures bv.s urea, alkali nitrite and mono- or Dialcanol the Tiinsalae of benzoic acid,

The term "polyolofins" refers to Horaopolyraere and copolymers of O?: ef; .nen understood in which

009812/1805

BATH ORIGINAL

19325H

the unsaturated bond between the alpha «imd ß-carbon atom is located. Examples of such olefins are: polyethylene, polypropylene, ethylene-propylene mixed polymer, Polybutene, polyisobutylene, polyisoprene, ethylene-vinyl acetate copolymer, Polyvinyl acetate, vinyl chloride-vinyl acetate mixed polymer, polyvinyl chloride, Polyvinylidene chloride, vinylidene chloride-acrylonitrile mixed polymer, Polystyrene, styrene-butadiene mixed polymer, Styrene-itaconic acid !! «mixed polymer, styrene-maleic acid mixed polymer, Styrene monomaleate mixed polymer, polyacrylonitrile , Acrylonitrile-alkyl acrylate ^ mixed polymer, polyalkyl acrylate, Alkyl acrylate acrylic acid styrene terpolymer, Polyalkylraethaorylate, polyacrylamide, acrylonitrile vinyl · = öhloriä - => high-grade polyuier, acrylonitrile-butadiene ~ styj? ol-! per ~ polymer, chlorinated polyethylene, fluorinated polyethylene and the same. The polymers can be in the form of molded particles; Powders, liquids, solutions as paste or emulsion are grounded »

The -Dissycilohexylaaimoniumsalae of aliphatic carboxylic acids may salil · ^ be different from any.c aliphatic see carboxylic acid including straight-chain, branched ;, Derive saturated or unsaturated carboxylic acids. Bobeispiel. ^ For carboxylic acids, which can be used to manufacture are suitable of lUcyoluhexylammoniiunsalzen

009812/1805

BATH ORIGINAL

achieve.

Acetic acid, propionic acid, butyric acid, valeric acid, Isovaleric acid, caproic acid, isocaproic acid, enanthic acid, Caprylic acid, pelargonic acid, capric acid, lauric acid, Myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, Undecylenic acid, oleic acid, linoleic acid, linolenic acid and the same.

Among these carboxylic acids, higher fatty acids are preferred because they "have particularly excellent results."

The amount of dicyclohexylammonium salts to be incorporated into the polyolefin is not decisive as long as the amount is sufficient to give the polyolefins a rust-resistant property and at the same time the mechanical and external surface properties of the polyolefins are significantly impaired. In general, however, the salts are used in an amount of 0.01 to 30 Gav /.- 5 $, in particular from 0.1 to 5 Sew .-? Ä varv / endöt, Sana can generally be said that less than 0, 01 Qsv.-fo ammonium salts are not sufficient to impart rust-splitting and corrosion-preventing properties and that more than 30% by weight of the ammonium salts sometimes have an unfavorable effect on the mechanical surface properties of the polyolefins.

009812/1805

BATH ORIGINAL

The organic monoamine used in the preparation of organic monoamine salts of nitrous acid can be primary, secondary, or tertiary monoamines, whether the amines are saturated or unsaturated. Examples of monoamines are: alkyl amines such as monomethylamine, dimethylamines, triethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, butylamines, pentylamines, hexylamines, hepfcylamines, octylamines, laurylamines, myristyl amines such as oleoethylamines and stearylhanolamines, myristylamines, laurylethanolamines, linanolamines, linanolamines, linoleum ethanolamines, diethylamines, triethylamines, monoisopropylamines, allynsyl amines, linoleum ethanolamines, linanolamines , Triethanolamine, monoisopropanolamine, r, ij.sopropanolarain, tri.isopropanolamine and butanolamine; Amine acids such as glycine, alanine, beta-A ^ .anine, valine, oil, isoleucine and isosuccinic acid; Gyclcalky3.araine. \ 'Ie Oyclohexylamin, Cyclooctylarain, Dicyclohexylamirj. and dicyclooctylamine; Sj? omatic amines such as aniline, MetbA ^r laniline, dirnethylan-jLlin, diphenylamine and naphthyliunir; heterocyclic amines such as ethylene imine, 1,2-propylene imine, 1 _t 3-propylene imine, pyrrole, pyrrolidine, piperidine, Indc3, ohinoline and isoquinoline.

In the case of the carboxylic acids used for the production of polyhydric alcohol esters of garbene acids it can be the same carboxylic acids that

- 1 ~

009812/1805

"19325H

also for the production of Dicyclohexylaramoniumsalae are used, examples of polyhydric alcohols are: Äthylenglj'kol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, 1,3-propylene glycol, 1,3-butylene glycols, 1,4-butylene glycols, glycerine, Erythr.it, pentaerythritol, pentitol, hexitol and the like » The polyhydric alcohols react with the carboxylic acids to form mono-, di-, tri- or higher esters esterified. Natural fatty oils such as | Soybean oil, loin seed oil and castor oil, also epoxidizeda natural fatty oils such as epoxidized soybean oil and eporydated flaxseed oil as polyhydric alcohol esters uses v / earth «

In the Kollophciium amine salts ice are salts of inorganic acids such as hydrochloric acid _t boric acid and silicic acid, Salsen of aliphatic Monooarbonsäuren Salsen and aliphatic dicarboxylic acids such as succinic acid, Haieinsäure, fumaric acid. Adipic acid, itaconic acid and citraconic acid and also iun aromatic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, heraimellitic acid, trimellitic acid, pyromellitic acid, naphthoic acid and pt-butylbenzoic acid.

009812/1805

BATH ORIGINAL

The carboxylic acids used for the preparation of the alkylamides of aliphatic carboxylic acids can be are the same aliphatic carboxylic acids with the exception of acetic acid, propionic acid and acrylic acid, dl ?, »for the production of Dlcyclohexylamrioniumsalze be used. Preferred acids are higher carboxylic acids. The amines used to prepare the amides can be the same allyl amines as they are used for the production of nitrous acid salts is used »

The alkali metal nitrite component of the mixture of urea, Alkallnitrit and Alkanolarainbenzeat can Lrlthiumnitrlt, sodium - _'s ärit rCaliumnitrlt or Oäsiumnitrit. Examples of mono- or Malkanolamines are: Monoäthanolanu.n, Diethanolamin, Monoisopropanolamin, Diisopropanol-? amine, monylsutanolamine and dibutanalamine,

If one or more of these roat protection additives are incorporated into the iiaasfen, dia polyolefins and bicyclohexyl ammonium a Is; a contain organic carboxylic acids, as revealed this "RostschutzzusätS3 not only special effects _f these additional admixtures are typical ρ but surrendered masses with an excluded

BATH

distinguished rust and corrosion resistance due to a synergistic effect of the additives with the dicyclohexylamraonium salsa. For example, the organic monoarainnit.rite serve as a dispersion accelerator for the dicyclohexylanuKoniuniBalze in the polyolefi: masse, which leads to a :. ' uniform mixture results. Furthermore, the organic .HoTioaminnitrite act not only as sehlupfverhindernde substances between polyolefins and the screw in Ii ¹ Ilmextrudern, the Sohlupf the polyolefin would make it difficult ine extrusion, but wirkan also synergistically as -losSschutzstibstanzen together, ammonium salts with Dicyclohaxy!,

Improve nishrwertigeii Alkoholester of aliphatii3chan carboxylic acids not only the 'üriermische stability of polyolefins, but also serve DAAU, 3ixcht the entry of J ": igkelt push back.' The effects of the added E £ - ^r; he circadian indirakt cer for Yerstärkung the Rostsohtttξeigenschaften Kaas » _s

The hydrochloric acids salts of KollcphoMiumamiiien give the Polyolefins not only have thermal stability, but rather also an excellent anti-rust Elgonschafto

The alkylamides of carboxylic acids make the polyolefins water repellent and also improve lightfastness of the masses.

- 10 -

009812/1805

BATH ORIGINAL

19325H

The mixtures of urea, alkali nitrite and mono- or dialkanolamine benzoates also improve the rust resistance the dicyclohexylammonium salts

The efficiency of the anti-rust effect can be explained as follows, for example:

Cyclohexylarainnitr.lt e.g. has an excellent rust protection effect, when used in effective concentration. The rust resistance decreases rapidly when it is used in a concentration less than the effective concentration range. In contrast to this have the dicyclohexylaramoniura salts of aliphatic carbonic acids, for example dicyclohexylammonium caprylate no such critical focus. Thus, when a polyolefin film such as a polyethylene film which has both which contains nitrite as well as an ammonium caprylate, is used for wrapping metal objects sublime the ammonium salt over a longer period of time and the closed space formed between the film and the metal object with the ammonium salt vapor fill in and there would be an absorbed layer of the Amsioniura salt on the surface of the metal object form that prevents rust and corrosion. The other rust inhibitors according to the invention deploy also their anti-rust effect according to the same mechanism.

0098 12/180 5

BATH ORIGINAL

19325H

The additions- can be used in any amount * !; Provided that it is sufficient for the polyolefin, it has a rust protection effect on the surface and at the same time the mechanical properties and surface properties. the polyolefin "In general, these are influenced Susätse, together with the Bicyclohexylammoniumsalzen in a total amount of 0.01." not ungünntig ° to 30 wt -..% _t insbescndpre of 0.1 to 5 wt ~ $ applied. One can generally say that less than 01 percent by _p 0 ~% of the mixture is insufficient to rust ™ and Korrosionsschiitzwirkung £ -;. U unfold and AASS more than 30 UEW .- / »the mixture roar.chma '.. the mechanical -.;. nd have a positive effect on the surface properties of the polyolefin _o

"iisät & e kcnr..i: n in d;, e Polyolerfinc in ai \ e.'se GingeK.rljeJ.tfit are well-known. If the Pclyolefin as molded parts (pellets) or powder is present _r . the Susätse with the polyolefins while heating in a mixer, a "B. E ^ räurjr mixer, Mifjchwalzen processed who known Veise pelletized or pulverized. If the polyolefins are in the form of a powder or paste, the additives can simply be mixed in or stirred in. In polyol - -

009812/1805

⁰ AD OBlGlNAL

19325H

Fine, which are available as a liquid or emulsion, the additives can be added and the mixture can then be stirred.

In the polyolefin compositions according to the invention other additives such as pigments, antioxidants, stabilizers, Antistatic substances, anti-corrosion agents against salt water, lubricants, fillers and solvents have been incorporated, if necessary ο

The charge-designed Pülyülefinraassen can form articles such as films; layered materials, sacks, tubes, sheets, hollow bodies, bottles and the like are processed ;

The polyolefin compositions according to the invention can be peeled off the surface of synthetic resin filaments or layers that do not contain the rust protection substances mentioned, as well as from cellophane films, aluminum foil or paper (e.g. (Hasslnpap. | Ar, Kraft paper, qualitative}>. och \ / ^ erti it 'is laugh. Eb several methods>' white shiny paper and the like) to form the laminated Filns or laminated! 'ÜR manufacturing

- 15 -

009812/1805 βΑΟ ORIGINAL

19325H

such Vsrbundf lines or composite panels. A procedure for the construction of composite or laminated panels Pollen is as follows:

The anti-rust polyolefin film according to the invention is made from an organic solution of a synthetic thermoplastic. Resin such as a polyvinyl chloride, polyvinyl acetate or vinyl chloride-vinyl acetate mixed polymer, a latex or emulsion of natural or synthetic rubber or an adhesive based on sines saturated polyester applied, the solvent evaporated from the coating and derm the other layer or the other film on the coated Polyolefin film applied with the help of the adhesive force of the coated layer. In this way, layer zigon -SiR stage can -stjiiG ■ j.amini sr ' «e of three or four layers in a prepared and one must only the layers ₁ Lr remove such a manner that the polyolefin layer gamäS c; sr invention di-3 first layer of Iamiiii ^ rt .- 'n layer v / ircL

Bsi play for F. ^! ,:, me, which can be ninated with the inventive polyolefin composition r, rf.; Non-stretched polypropylene film, biaxial, stretched polypropylene film, Polysster?;. Lm, Nylonfilra, Polycarbpnatfilra, Poly-Tinylidenchlorllill.m, Polyäthyleiä.nim, Aluminum foil,

- -14 -

0098 12/180 5

BATH ORIGINAL

19325U

Cellophane film, vinylonfilra, water resistant Cellophane, glossy white paper, drawing paper, glassine paper, and the like. If a two-layer film industry you want: unstretched polypropylene filra / vinylon filra, biaxially stretched polypropylene film / vinylon film, polyesterfum / unstretched polypropylene film, polyester film / biaxially stretched polypropylene film, Cellophane film / aluminum foil, paper / aluminum foil and the same. If a three-layer film laminate is desired: Unstretched or biaxially stretched Polypropylene film / Polyäthylenfi.Im / Vinylonfilra, Polyäthylenfilm / Papi.er / Polyesterfilm and the like when a multi-layer laminate is desired

As already mentioned, the polyolefin can according to of the invention directly or indirectly on the metallic product al.3 color in the form of a liquid, solution or Emulsion to be used *, wöbe :, one excellent Uostprotective effect achieved.

When ran down the metallic products easily corroded be, with the masses according to the invention, which Manufactured in various forms, wrapped or packaged, you can use permanent anti-rust protection and before Achieve corrosion-preventing effects without the transparency, Moisture resistance, printability, airtightness of the mass au influence.

- 15 - _

009812/1805 bathroom ORIGINAL

193251 A

The following examples serve to illustrate preferred embodiments of the invention without , however, restricting it. In the following examples, percentages are percentages by weight »

example 1

In a high-pressure polyethylene from Sshmelzindex 1.8 and a Dicbta of 0.923 'were 1} $ Dicyclohexy .ammonium ~ caprylate, ei.ngeinlacht 0.2F> f ° Cyclohexylaminetrit and 0.5 ° f monoglyceride of a higher fatty acid and verknete- the mixture. :. ^..? The "kneaded Semisch was a blow to ex '; ausgeprei3t rowing against 40 mm Lurchmesser a FiIm _r ÜR the production of this film were applied following cond> \% <in:

Extrudsrtei ^ r nature: Cylinder change C,
C. 110 ° C. cylinder 1'5 ° C. cylinder D. 120 ° O Dog 135 ° C. Uradr a hungB ζ ah 1
Screw: the 30 from left p.m. L / D 20th Compre ssi ons ve ratio: 3o5 Add extrudes • 10 kg / hr Folding diameter r »; 100 mm Thickness of the film I ** ·
O · 0.05 mm.

- 16 -

00981 2/1805

BATH ORIGINAL

19325H

The rust preventive film thus prepared is excellent Transparency, water resistance and separability. In the single-layer polyethylene film was that anti-rust mixture evenly dispersed.

Examples 2 to 8

A polyethylene hose (120 mm 280 mm; 0.05 mm thick) was produced as in Example 1, but the compounds given in Table 1 were incorporated as rust-preventing substances. In all © Polyäthylenschläuche, acid-treated iron test pieces were of rust freed (100 mm χ 200 ram χ 1 mm) and "closed the mouth of the hoses, the wet strength of the samples thus prepared was according to JIS Z-0228 Standardtsst at a temperature of 49 ° * - ¹ ° ° and a relative humidity of 95 + 5? ' checked for more than 720 hours.

For comparison, the same experiment was used of a Po? .yäthyXensehlauchs, which does not contain any rust protection substance contained. The iron test pieces were already kicking. 48 hours of rust.

0098 12/180 5

BATH

example

fit

Table 1 Anti-rust agents

Dicyclohexylammonium caprylate 0.1? 6

19325U

Look after trying

No rust

3 Il 1 4th Dicylohexylamroo-
nium acetate 5 5 Dicyclohexyl
ammonium butyrate 3 6th Dicyelohexyl
ammonium laurate 0 7th Bicyclohexyl
• ammonium te arat 1 8th Dicyclohexyl
ammonitimoleate 1

Bei piele 9 to 20

Polyethylene hoses were canaer with anti-rust subs. produced _s which are given in Table 2. The wet strength values were determined in the same way as in Example 2, with the difference that the test was carried out for more than 960 hours. The results were as follows:

18th

0 09812/1805

BATH ORIGINAL

19325U

Table 2

Example host protection agent looks like - - ; - the attempt

Dicyclohexylammonium caprylate Q.5 $ No rust + laurylamine nitrite O ₀ 5 $ Dicyclohexylammoniuracaprylate 0.5 $ " + diisopropanolamine nitrite 0" 5 / £ Dicyclohexylammonium caprylate 1? '"■ * - Giyoinnitrite Oo2jS

Dicyclohexyl aramonium caprylate 1% "+ aniline nitrite 0.2 ??

Dicyclohexyl aramonium caprylate "/ '" -f- piperazine nitrite 0 »3 / S

Dicyclohexylaramoniuracaprylate 0 = 7? ' "

-} - Soybean Oil 0 _a 355 ^

Dicyclohexylamnioniumcaprylat 1 $ "I'onoglycerid of Lauririoäure 0.2 $ Dicyclohexylaramoniumcaprylat 1 5""opoxydiertes soy O.25S 'Dicyclohexylammoniumcaprylat 0.5 / °" Kollophoniumaminhydrochlorid 0.55 ^ Dicyclohexylammoniumcaprylat 1 55 "Laurinsäuremonoäthylamid O ₀ 3? ^ Dicyclohexylammoniumcaprylat 1 $"

+ a mixture of urea, sodium uranium nitrite and monoethanolamine benzoate O ₀ 55 »

, Dicyclohexylammonium caprylate 1 5 »■ _" ■ <- Dicyc / .ohexylarainnitrite Οο25δ

- 19 -

0 0 9812/1805

Examples 21-23

Polyethylene hoses were made with anti-rust substances » which are listed in Table 3. The wet strength values were determined as in Example 2, with the difference that the duration of the experiment was longer than 1o200 hours. The results were as follows:

Table 5

Example rust preventive looks like

- · * the attempt

21 Dicyclohexylammoniuracaprylate 1 % No rust ■ f Cyclohexylamine _{nitrite O 0} 25? '<~ Monoglyceride of a higher

Fatty acid 0.25a

22 dicyclohexylammonium caprylate $ 0.5 "

+ Rosin amine hydro ™

. chloria O ₀ 5 ^C A

- Monoglyceride of a higher fatty acid 0.

£ 3 Dicyclc'hexylammOiiiuEil & ur & t 1 -f aniline nitrite O ₀ -

• f- it epoxidizes soybean oil O ₀ ¹

Examples 24 to 29

Polypropylene tubing (120mm by 250mm; 0.05mm thick) was made manufactured using rust inhibitors, which are listed in Table 4. The wet strength

- 20 -

009812/1805

BATH ORIGINAL

was carried out in the same manner as in Example 2, but over a period of more than 1500 hours.

For comparison, the same test was carried out using a polypropylene hose that did not contain any rust inhibitor. There was already rust on the ironwork after 36 hours,

Table 4

Example rust preventive appearance

after trying

24 Dicyclohexylammonium caprylate O ₀ 5 $ No rust

25 dicylohexylammonium acetate 5% "

26 dicyclohexylammonium palmitate 1 ? ° "

27 Dicyclohexylammoniuralinolate 2 "/> "

28 Dicyclohexylammonium caprylate 1 # "+ dicyclohexylamine nitrate O ₀ 5 $>

29 Dicyclohexylammonium aurate 0 "5 i ° " ■ τ Cyclohexylamine nitrite 0 "5 5 ^ ■ f Pentaerythritol monooleate 0", 5 %

Examples 30 to 34

Polyvinyl chloride tubing (120 ram χ 250 mm; 0.1 mra thick) were made with the following anti-rust substances,

- 21 -

0 0 9 8 12/1805 BAD ORIGINAL

'. Si 19325U

The wet strength tests were as in Example 2 carried out over a period of more than 5,000 hours. The results are shown in the table below

For comparison, the same test was carried out with the aid of polyvinyl chloride, which did not contain any rust protection substance. Rust appeared on the Bisenstüeken after 120 hours & n £ _a

l'abelle 5

example

30 31 32 33

34

Anti-rust agents

Look after trying

Dicyclohexylammonium propionate 3 i ^a No rust Dicyclohiexylaramoniumisccaproate 1.5 $ "DicycloLexylammoniummyxNlstat 1" 5% "Bicyclohexylammoniumcap ^ ylate 1 $" + pyrrole nitrite 1

Dicyclohexylammonium isooaproate 1 + Cyclohexylamine nitrate 0 + sorbitol monooleate 0

Examples 35 to 36

Polyvinyl acetate tubes (120 mm: t 250 mm; 0.6 mm thick) were made »by the following · anti-rust sub = punching were added. The wet strength tests

- 22 -

009812/1805

ÖAD ORlGfNAL

19325K

were as in Example 2 for a period of more than Performed 10,200 hours. The results are in the Table 6 given.

For comparison, the same test was carried out with polyvinyl acetate carried out, which did not contain any anti-rust substance. Rust appeared on the biscuit pieces after just 48 hours on.

Table 6

Example rust preventive looks like

______ . - _{i r} . ^. _{< i} ', - - the attempt

35 Dicyclohexylararaonium Pelargonate 1 »5 $ No rust

36 Dicyclohexylammoniuracaprate 1 $> "

• f mixture of urea, potassium nitrite and diisopropanol araine benzoate 1 %

Examples 37 to '59

In a mixture of 15 wt. Parts of vinyl chloride-vinyl acetate Hischpolyraer and 85 parts by weight of a Löaungsmittelgeraisches consisting of 30 i> benzene, 60 ^ methanol and 1Q $ water were incorporated the anti-rust agent listed in Table 7 in the preparation of coating compositions. These coating compositions were applied to a thickness of 0.1 mm on the surface of an iron plate that had been freed from rust and treated with acid.

009812/1805

19325 U

After drying, measurements were made on the coating layer the wet strength as in Example 2 carried out over a period of more than 500 hours. The results are compiled in Table 7.

The same experiment was used for comparison carried out a coating composition that did not contain any rust protection substance. There was already rust on the iron plate after 12 hours.

example

37

38 39

Table 7 Anti-rust agents *

Dicyclohexylammonium caprylate $ 5

Dicyclchexylammoniuralaurate 2 fo

+ Colloplionium Acetate $ 2

Dicyclchexylammonium caprate 1 ₀ 5 ^

+ Capric acid diisopropylamide 1 %

Look after trying

No rust

* The amount of residual protective substances would be calculated on the base of solid components in the coating mass.

Examples 40 and 41

In a coating emulsion that was prepared by stirring in a mixture of 15 i ° vinyl chloride-vinyl acetate

- 24 -

0098 12/1805

Bathroom original

19325U

Mixed polymer, $ 5 emulsifier, and $ 80 water were the ones Anti-rust substances are given, which are listed in Table 8. The emulsion thus obtained was used as a coating Applied in a thickness of 0.5 mm to the surface of a rust-free iron plate treated with acid. After the coating layer had dried, the wet strength was tested as in Example 2. The results can be found in the following table »

For comparison, the same test was carried out with a coating compound carried out, which did not contain any rust preventive substance. Rust appeared on the surface of the iron plate after only 18 hours.

Table 8

Example of anti-rust agent * Appearance

after the "_______________________ .. ^^ attempt

40 Dicyclohexylainmonium valeriate $ 5> No rust

41 DicyclohexylaraiHonium aprylate 0.5 $ " Pentaerythritol monostearate 0.5 $

+ Mixture of urea, sodium nitrite and di ~
ethanolamine benzoate $ 1

* The amount of anti-rust substances was calculated on the basis of pesticides in the coating compound.

- 25 -

009812/1805 _BA D ORIGINAL

ifc 19325U

Examples 42 to 46

The rust inhibitors listed in the table below were incorporated into polyethylene (SahmeIzindex 0.8; density 0.923) and the resulting mixture was kneaded in a Banbury mixer. The kneaded mixtures were extruded from a film with the aid of a T-extruder with a 60 mm diameter nozzle. The films were then coated using an adhesive. The adhesive consisted of 35 parts by weight of a polyester varnish saturated to 70 ° , 15 parts by weight of 65% strength isocyanate, 25 parts by weight of ethyl acetate and 25 parts by weight of toluene. These films were laminated with various films to form a film laminate of 0.05 mm thick. Tubes were made from the films thus prepared. The wet strength of the hoses was tested, as in Example 2, over a period of more than 1,500 hours. The results are shown in Table 9 below.

- 26th

009812/1805

91

19325U

Tabel

example

Anti-rust agent for lamination Appearance after the attempt Film ___

Dicyelohexylammoniura caprylate 1

Dicyclohexylammonium caprylate 0.5

+ Cyclohexylamine nitrite 0.5

+ Monoglyceride

of Lauic acid 0.5

Dicyclohexylammonium caprylate 0.5

+ Kollophoniura * -
amine benzoate 0.5

lauric acid βhexyl arid 0.5

5 Mcyclohexylaramonium palmitate 1

Bicyclohexy ammonium

not stretched polypropylene

Gellophane

PolycarTjonat

Polyester and biaxially _stretched l _poly

propylene polyethylene ge

s SS ¹¹ * -

polyester

Claims

-

009812/1805 BAD

Claims (6)

. T9325U claims 1. Against rust protective polyolefin, characterized in that it contains Bioyclqjamnoniumealge of aliphatic carboxylic acids. 2nd polyolefin composition according to claim 1, characterized in that it is also organic Monoamine nitrites, polyhydric alcohol esters of aliphatic carboxylic acids, rosin amine salts, Alkyl amides of aliphatic carboxylic acids and / or a mixture of urea, alkali nitrite and mono- or dialkylamine benzoate. 3 «polyolefin composition according to claim 1 or 2, characterized ge ke η η ζ e Lehn et that it contains as polyolefin, polyethylene, polypropylene, polybutene, polyisobutene, polyisoprene, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, fluorinated polyethylene, polystyrene, polyacrylonitrile, polyacrylamide, polyacrylic acid, Contains polymethacrylic acid, alkyl polyacrylate and / or alkyl polymethacrylate or their mixed polymers. 4. Polyolefin composition according to claim 1 to 3%, characterized in that it contains, as organic monoamine nitrite, alkylamine nitrites, in particular cycloalkylate nitrites. 0098 1 2 / 1.805 BATH ORIGINAL 19325U 5. polyolefin composition according to claim 1 to 4 »characterized in that they are polyvalent Alcohol esters of aliphatic carboxylic acids, polyhydric alcohol monoesters of higher fatty acids, in particular of fatty acids with more than 6 carbon atoms, preferably with more than 12 carbon atoms. 6. Polyolefinraasse according to claim 1 to 5, characterized in that they are used as rosin amine salts Contains rosin amine hydrochloride or the Salt® of organic acids. That it 7 · polyolefin composition according to claim 1 to 6, characterized in that the dicyclohexylammonium of aliphatic carboxylic acids and the optionally added antirust additives in an amount of 0.01 to 30 percent by _e - contains $, preferably from 0.1 to 5 wt .- ^ . - 29 - 0098 12 / 18öS _BAD original