WO2002046299A1 - Use of polyether amine derivatives for permanent improvement of the adhesive and/or coating compatibility of polyethylene-based shaped bodies, fibres and films - Google Patents

Abstract

The object of the invention is the use of polyether amine derivatives for permanent improvement of the adhesive and/or coating compatibility of polyethylene-based shaped bodies, fibres and films. A mixture of a) predominantly one or several polyethylenes and b) 0.01 - 20 wt. % - in relation to the polyethylene of one or several derivatives, said polyether amine derivatives being selected from the group of reaction products of di- or polyaminopolyalkylenoxide compounds with organic carboxylic acids containing one or two COOH functions and all together 4 - 22 C atoms, is subjected in a usual manner to a shaping process such as extrusion, calandering, injection moulding or blow moulding or the like at temperatures ranging from 180 to 330 °C.

Description

 Use of polyetheramine derivatives to permanently improve the adhesive and / or coating compatibility of polyethylene-based moldings, fibers and films

Field of the Invention

The invention relates to the use of polyetheramine derivatives for the permanent improvement of the adhesive and / or coating compatibility of polyethylene-based moldings, fibers and films, the polyetheramine derivatives being selected from the group of the reaction products of di- or polyammopolyalkylene oxide - Compounds with organic carboxylic acids that contain one or two COOH functions and a total of 4 to 22 carbon atoms.

State of the art

Shaped workpieces of any spatial shape, including moldings, fibers and foils based on polyolefin, are used in a very wide range today. An important problem area is the improvement of the surface properties of these non-polar hydrocarbon compounds due to their structure. The lack of adhesive strength to coatings and bonds is a central problem, for which numerous proposals have been made for decades.

It is known that the compatibility of the plastic surface with coatings and bonds is achieved, for example, by oxidative aftertreatment processes. drive how corona or plasma treatment can be improved. Here, the plastic is oxidized or chemically modified in the presence of gases and discharges on the surface, which means that certain surface properties of the plastic can be modified. However, these methods always require an additional operation in addition to high energy consumption and lead to ozone emissions in the manufacture of plastic parts. In addition, chemical pretreatment processes, such as treatment with fluorine or chlorine gas, with chromosulfuric acid or fluorosulfonic acid, etc., have long been known.

WO 97/12694 and WO 98/42776 describe the use of amphiphiles for the permanent improvement of the adhesive and or coating compatibility of polyolefin-based molded articles, fibers and films. A mixture comprising (a) predominantly one or more polyolefins, (b) one or more migratable amphiphiles and (c) one or more transition metal compounds are subjected to shaping processing in the customary manner at temperatures in the range from 180 to 320 ° C. , for example extrusion. It is disclosed that dialkanolamides of unsaturated fatty acids, such as oleic acid diethanolamide or linoleic acid diethanolamide, can be used as component b).

EP-A-982 353 describes a method for improving the color adhesion on thermoplastic polyolefins. A thermoplastic polyolefin, which is a polypropylene-containing blend, is treated with maleated polypropylene and amine-terminated polyesters.

EP-A-936 246 describes directly printable thermoplastic polyolefin compositions based on oxidized polyethylene waxes. The complex compositions necessarily contain at least four different components.

EP-A-934 975 describes directly printable thermoplastic polyolefin compositions based on maleic anhydride-modified polymers. The Complex compositions contain at least five different components.

Description of the invention

The object of the present invention was to provide tools with which the adhesive and / or coating compatibility of polyethylene-based moldings, fibers and foils can be sustainably and permanently improved. In other words, it was an object of the present invention to provide work equipment in order to ensure a permanent improvement in the adhesive strength of polyethylene surfaces against adhesions and / or coatings. In particular, the invention aims to enable the setting of high-strength bonds, which preclude the occurrence of undesired adhesion breaks and only ensure destruction of the adhesive joint by way of a cohesive break or a combined cohesion / adhesion break.

The present invention relates to the use of polyetheramine derivatives for the permanent improvement of the adhesive and / or coating compatibility of polyethylene-based moldings, fibers and films, with one containing a mixture

a) predominantly one or more polyethylenes and

b) 0.01 to 20 wt .-% - based on the polyethylenes - one or more polyetheramine derivatives, the polyetheramine derivatives being selected from the group of the reaction products of di- or polyaminopolyalkylene oxide compounds with organic carboxylic acids containing one or contain two COOH functions and a total of 4 to 22 C atoms,

at temperatures in the range of 180 to 330 ° C in a conventional manner, a shaping processing such as extrusion, calendering, injection molding, blow molding and the like. To the pol ethylenes a

In the context of the present invention, all types of ethylene-based polymers and copolymers known today can be used. Polymer types that are particularly suitable for the teaching according to the invention are listed in the following compilation: HDPE (high density polyethylene), LDPE (low density polyethylene), VLDPE (very low density polyethylene), LLDPE (linear low density polyethylene), MDPE (medium density polyethylene) , UHMPE (ultra high molecular polyethylene), VPE (cross-linked polyethylene), HPPE (high pressure polyethylene).

Polvetheramine

In the context of the present invention, component b) uses polyetheramine derivatives. These compounds b) are accessible by derivatization of polyetheramines (PEA).

In the context of the present invention, di- or polyaminopolyalkylene oxide compounds serve as polyetheramines (PEA) and thus as raw materials for the production of the polyetheramine derivatives b) to be used according to the invention. This means that on the one hand these compounds contain two or more amino functions (NH or NH ₂ functions) and on the other hand contain alkylene oxide units. The last-mentioned building blocks are in particular ethylene oxide, propylene oxide and butylene oxide, ethylene oxide and propylene oxide being particularly preferred.

The production of polyetheramines is known from the prior art and includes the reaction of compounds containing hydroxyl groups with alkyl oxides, in addition to subsequent conversion of the resulting terminal hydroxyl groups into amino groups. WO-A-97/03108 (cf. page 8, lines 13-19) refers to the corresponding prior art and states that polyetheramines are usually produced by amination of polyethers with ammonia in the presence of catalysts such as Ni Cu / Cr.

The ethoxylation and propoxylation are of particular importance with regard to the reaction of compounds containing hydroxyl groups with alkylene oxides. The procedure is usually as follows: in a first step, the desired hydroxyl group-containing compounds are brought into contact with ethylene oxide and or propylene oxide and this mixture is reacted in the presence of an alkaline catalyst and at temperatures in the range from 20 to 200.degree. Addition products of ethylene oxide (EO) and / or propylene oxide (PO) are obtained in this way. The addition products are preferably EO adducts or PO adducts or EO / PO adducts with the respective hydroxyl group-containing compound; in the case of the EO / PO adducts, the addition of EO and PO can take place statistically or in blocks.

Suitable polyether blocks of the polyether amines are, for example, polyethylene glycols, polypropylene glycols, copolymers of approximately polyethylene glycols and polypropylene glycols, poly (1,2-butylene) glycols, poly (tetramethylene) glycols.

Diamines and triamines are particularly preferred as polyetheramines. “Diamines and triamines” are understood to mean those polyetheramines which have two or three terminal (terminal) NH ₂ groups per molecule. Very particular preference is given to those in documents EP-B-634 424 and WO-A- The diamines and triamines described in 97/03108 The disclosure of these two publications with regard to the structure of these diamines and triamines is hereby expressly incorporated into the teaching of the present invention.

With regard to EP-B-634 424: page 6, line 23 to page 7, line 36.

• Regarding WO-A-97/03108: page 29, line 1 to page 31, last line. Particularly suitable diamines and triamines (of the PEA type) in the context of the present invention are those which are commercially available from Huntsman Petrochemical Corporation under the trade name “Jeffamine”. The following types are particularly preferred in the context of the present invention:

Jeffamine D-400

Jeffamine D-2000

Jeffamine D-4000

Jeffamine ED-600

Jeffamine ED-900

Jeffamine ED-2001

Jeffamine ED-4000

Jeffamine ED-6000

Jeffamine T-3000

Jeffamine T-5000

Jeffamine ET-3000

These Jeffamine types can be used individually or in a mixture with one another.

The polyetheramines preferably have average molecular weights (number average; Mn) in the range from 400 to 12000, in particular between 400 and 6000.

To the polyetheramine derivatives b

As already stated, the polyetheramine derivatives b) are selected from the group of the reaction products of di- or polyaminopolyalkylene oxide compounds with organic carboxylic acids which contain one or two COOH functions and a total of 4 to 22 carbon atoms. These reaction products are therefore amides which are derived from the above-mentioned polyetheramines and mono- or dibasic organic carboxylic acids with 4 to 22 carbon atoms. In one embodiment, fatty acids having 4 to 22 carbon atoms are used to prepare the polyetheramine derivatives b). Fatty acids with 8 to 18 carbon atoms are preferred. Lauric acid, myristic acid, palmitic acid and stearic acid are particularly suitable.

In a further embodiment, dicarboxylic acids having 4 to 22 carbon atoms are used to prepare the polyetheramine derivatives b). Here, α, ω-dicarboxylic acids with 4 to 13 carbon atoms are preferred. Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, maleic acid (cis-2-butene-1, 4-diacid) and fumaric acid (trans-2-butene-1,4-4-) are particularly suitable. dioic). Instead of the dicarboxylic acids, the corresponding dicarboxylic acid anhydrides can also be used in the preparation of the compounds b).

In a preferred embodiment, the above-mentioned diamines and triamines of the Jeffamine type are used to prepare the polyetheramine derivatives b). The di- or triamines are reacted with the organic carboxylic acids such that the equivalent ratio of the NH ₂ : COOH groups is in the range from 1: 0.3 to 1>: 2.0.

The use according to the invention of the polyetheramine derivatives b) mentioned ensures that coatings or bonds can adhere to the plastic permanently and without additional pretreatment. Once set, adhesive and / or coating compatibility values are retained over long periods of time. With regard to the adhesives and coating compositions which can be brought into contact with the surface-modified polyethylenes according to the invention, so that permanent bonding or coating is achieved, there are no restrictions per se according to the invention. With regard to the adhesives, all adhesives familiar to the person skilled in the art, in particular the commercially available adhesives, can be used. With regard to coatings, particular attention should be drawn to the paints. Varnishes are liquid or powdery solid sub- punches, which are applied to objects in a thin layer and which, through chemical reaction and / or physical processes, form a firm film adhering to the surfaces of the objects, which has decorative and / or protective functions. The coatings also include the application of printing inks, since printing inks are applied to substrates to be printed in a binder layer, the adhesion to the shaped body being mediated by the binder which forms a coating.

For shaping processing

The mixture comprising components a) and b) is used by customary shaping processing techniques, such as extrusion, calendering, injection molding and the like, which are well known to those skilled in the art.

The combination of the teaching according to the invention, which leads to the formation of increased coating or bonding compatibility values, with known technologies for improving the coating or bonding compatibility on polyethylene surfaces falls within the scope of the teaching according to the invention. Thus the surfaces of the polyethylenes produced according to the present invention can additionally be treated both mechanically, chemically and / or physically. However, this is usually not necessary.

It may be desirable to use a pre-assembled mixture of components a) and b). Other customary auxiliaries (plastic additives) used, which have proven themselves in general in the processing of plastics and which are known to the person skilled in the art, for example slip agents, antistatic agents, lubricants, mold release agents, UV stabilizers, antioxidants, fillers, fire retardants, mold release agents, nucleating agents and antiblocking agents accordingly pre-assembled in separate form and added during the final mixing of the finished products. Also the technology common in practice, the auxiliary substances mentioned in one The use of the form in which they are already wholly or partly contained in component a) is expressly included in the scope of the present invention.

However, it may also be desirable, for example when using the extrusion technology, to meter all or part of the components b) and, if appropriate, further plastic additives directly into the polyethylene melt on the extruder, so that the mixture of components a) and b) - and, if appropriate, further plastic additives - is not already available as a ready-made product from the start, but is only present in the extruder itself. Such a technique is useful, for example, when the compounds b) to be metered into the polymer melt are in liquid form and injection of this component is easier than pre-assembly.

It may also be desirable - although not necessary to achieve the effect according to the invention - after the use of components a) and b) according to the invention - to carry out a corona or plasma treatment in the customary manner.

The application of coatings or adhesive bonds to the surface-modified polyethylene-based moldings and films obtained by the process according to the invention can be carried out per se by all relevant methods known to the person skilled in the art.

In one embodiment, component a) is HDPE (high density polyethylene) and a temperature in the shaping processing is preferably set in the range from 200 to 300 ° C., in particular 250 to 300 ° C. for HDPE containing carbon black.

In a further embodiment, LDPE (low density polyethylene) is used as component a) and a temperature in the range from 180 to 300 ° C. and in particular 220 to 280 ° C. is preferably set in the shaping processing.

In the case of extrusion processes, the temperature information just given for HDPE and LDPE processing applies in particular to the temperature of the outlet nozzle. If the shaping processing of the mixture of components a) and b) is carried out by extention, the polyethylene mold body is cooled by a maximum of 50.degree. C. within a period of 0.1 to 5.0 seconds immediately after leaving the outlet nozzle. With regard to this temperature difference of 50 ° C - hereinafter also called ΔT50 - the equation applies

A I U 1 outlet nozzle "* polyethylene surface

In this equation, T _Aust ri _t ts _nozzle, the temperature of the exhaust nozzle is to be understood the extruder under Tp _{0] vethy} i _{eno Surface Terminal,} the surface temperature to understand the extruded polyethylene molded article, the non-contact, pertinent known for example using infrared techniques is measured, (for example with an infrared thermometer "IR-TA / Handy 1000" from Chino).

It is particularly preferred to cool the polyethylene molded body by a maximum of 50 ° C. within a period of from 1.0 to 5.0 seconds and in particular from 1.7 to 5.0 seconds immediately after it has left the outlet nozzle of the extruder.

Provided that the molded polyethylene body moves at a constant speed from the exit of the extruder's exit nozzle, the time scale mentioned can be easily transformed into a distance scale. For this, the known equation v = s / t (speed = distance divided by time) is used, from which s = v * t (distance = speed times time) results from transformation, from which it can be seen that distance s (ie distance from the outlet nozzle) and time t are proportional to each other. By definition, the zero point of the distance scale lies directly at the exit point of the nozzle.

In one embodiment, the molding processing of the mixture containing components a) and b) is carried out by an injection molding process. It is preferred to subject the molded polyethylene body obtained to a thermal aftertreatment at elevated temperature. It is particularly preferred to carry out the thermal aftertreatment in such a way that a surface temperature

io temperature of the molded polyethylene body of at least 200 ° C and in particular of about 240 ° C. An IR radiator can be used, for example, to carry out the thermal aftertreatment. The duration of the thermal aftertreatment is preferably at least 4 seconds.

In one embodiment, customary plastic additives are additionally added to the shaping processing of the polyethylenes.

To the plastic additives

The type of plastic additives is not subject to any particular restrictions. In principle, therefore, all plastic additives known to those skilled in the art are suitable. As an example, reference is made to the standard work Gächter / MüIIer "Plastic Additives" (Munich 1989). Suitable plastic additives include:

beta diketones and beta keto esters. 1,3-Dicarbonyl compounds which can be used can be linear or cyclic dicarbonyl compounds. Dicarbonyl compounds of the following formula are preferably used

R ^ CO-CHR ^ CO-R ³ ,

in which mean:

• R ¹ : Ci- a-alkyl, C ₅ -Cι ₀ -Hy <_roxya] __ yl, C ₂ -Cι ₈ alkenyl, phenyl, through OH, C _r C ₄ - alkyl, Cι-C ₄ alkoxy or halogen substituted phenyl, C ₇ -C ₁₀ phenylalkyl, C ₅ - C ₁₂ cycloalkyl, C ₁ -C ₅ -alkyl-substituted C ₂ -Cι cycloalkyl or a group -R ⁵ -SR ⁶ or -R ⁵ -0- R ⁶ ,

R ² : hydrogen, CC ₈ alkyl, C ₂ -C ₁₂ alkenyl, phenyl, C ₇ -C ₁₂ alkylphenyl, C ₇ - cio-phenylalkyl or a group -CO- R ⁴ , 1

R: one of the meanings given for R or Ci-Cig-alkoxy,

n R ⁴ : C ₁ -C ₄ alkyl or phenyl,

R ⁵ : Ci-Cio-alkylene,

• R ⁶ : C Ci ₂ alkyl, phenyl, C ₇ -C ₁₈ alkylphenyl or C ₇ -Cι ₀ phenylalkyl.

These include the hydroxyl group-containing diketones of EP-346 279 and the oxa and thiadiketones of EP-307 358 as well as the isocyanic acid-based keto esters of US Pat. No. 4,339,383.

R ¹ and R ³ as alkyl can in particular be -C ₁₈ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.

R and R as hydroxyalkyl represent in particular a group - (CH ₂ ) _n -OH, where n is 5, 6 or 7.

R ¹ and R ³ as alkenyl can mean, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

1 "

R and R as phenyl substituted by OH, alkyl, alkoxy or halogen can be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichloφhenyl.

1 ^

R and R as phenylalkyl are in particular benzyl.

R ² and R ³ as cycloalkyl or alkyl-cycloalkyl are in particular cyclohexyl or methylcyclohexyl.

R ² as alkyl can in particular be -C ₄ alkyl. R ² as C ₂ -C ₁₂ alkenyl can in particular be allyl. R as alkylphenyl can in particular be tolyl. R as phenylalkyl can in particular be benzyl. R is preferably hydrogen. R as alkoxy can be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R ⁵ as Ci-Cio-alkylene is in particular C ₂ -C alkylene. R ⁶ as alkyl is in particular C ₄ -C ₁₂ -alkyl, such as butyl, hexyl, octyl, decylyll ooddeerr DDooddeeccyyll .. R ⁶ as alkylphenyl is in particular tolyl. R ⁶ as phenylalkyl is especially benzyl.

Examples of 1,3-dicarbonyl compounds of the above formula are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoyl-benzoyl methylbenzoylmethane-5-yloyl methane-benzoyl methane-5-yloyl methane-benzoyl methane-5-yloyl methane-benzoyl methane-5-benzoyl methane-5-benzoyl methane-tri-benzoyl methane-5-benzoyl methane-benzoyl methane-benzoyl methane-5-benzoyl methane-tri-benzoyl methane-tri-benzoyl methane - benzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetyl -phenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoyl-phenylacetylmethane, bis-cyclohexanoyl-methane, dipivaloyl-methane, 2-acetylcyclopentanone, 2-benzessonyl acetic acid -, -ethyl- and - allyl esters, benzoyl, propionyl and butyryl-acetoacetic acid methyl and - ethyl esters, triacetyl methane, acetoacetic acid methyl, -ethyl, -hexyl-, -octyl-, -dodecyl- or -octadecylester, benzoylessi gsäuremethyl-, -ethyl-, -butyl-, -2-ethylhexyl-, - dodecyl- or - octadecyl ester, as well as propionyl and butyrylacetic acid -C-Ci ₈ - alkyl ester. Stearoylacetic acid, ethyl, propyl, butyl, hexyl or octyl esters and multinuclear jS keto esters as described in EP 433.230 and dehydroacetic acid and its zinc, magnesium or alkali metal salts.

Preferred are 1,3-diketo compounds of the above formula, wherein R ^{1 is} Ci-Cig-alkyl, phenyl, phenyl substituted by OH, methyl or methoxy, C ₇ -C ₁₀ -phenylalkyl or cyclohexyl, R is hydrogen and R is one of the for R has given meanings. The 1,3-dicarbonyl compounds of the above formula can be used as mixtures, and / or as their alkali metal, alkaline earth metal and zinc chelates.

Polyols and polyol derivatives. Particularly suitable as polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trismethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, hydroxylate, leucyl), trisethyl (THEIC), Palatinit, Tetramethylolcyclohexanol, Tetramethylolcyclopentanol, Tetramethylolcyclopyranol, Glycerin, Diglycerin, Polyglycerin or Thiodiglycerin as well as reaction products of these polyols with ethylene oxide and / or propylene oxide.

If desired, the polyols can be esterified or etherified on one or more OH groups. Preferred polyol derivatives which are esters of polyols with carboxylic acids, for example glycerol partial esters of fatty acids, for example glycerol monooleate, glycerol dioleate, glycerol monostearate, glycerol distearate, pentaerytrite or TMP partial esters or esters of dicarboxylic acids (for example adipic acid, maleic acid) with polyols Glycerin or trismethylolpropane. The polyols or polyol derivatives can be used alone or as a mixture with one another.

Amides. For this purpose, expressly refer to page 7, line 22 to page 25, line 21 of EP-A-768 336. The sterically hindered amines mentioned there are expressly included in the disclosure of the present invention. Also suitable are erucic acid amide, oleic acid amide and other amides based on fatty acids.

Antioxidants. For this purpose, expressly refer to page 31, line 34 to page 33, line 4 of EP-A-768 336 cited above. The antioxidants mentioned there are expressly included in the disclosure of the present invention. Lubricants and release agents. In this context, it should be expressly stated that both lubricants and release agents, as well as mixtures of lubricants and release agents, can be used. According to the usual use of the expert, products are called release agents that reduce the frictional resistance mainly between the polymer melt and the steel surface of the machine used in the shaping process; the reduction of the frictional resistance has the consequence that the melt mass pressure is reduced. In contrast, lubricants predominantly act in the polymer melt and reduce the internal frictional forces, which means that the melt maintains a good plastic flow even at high filler contents, which is important for filling the shaping tool.

In one embodiment of the present invention, solid or liquid calcium salts and / or magnesium salts and / or aluminum salts are used as lubricants or release agents at 20 ° C., which are selected from

Calcium salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms,

Calcium salts of unsubstituted benzoic acid or benzoic acid substituted with C ₄ alkyl radicals,

Magnesium salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms,

Magnesium salts of saturated or unsaturated dicarboxylic acids with 6 to 10 carbon atoms,

• Aluminum salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms

It applies to the above-mentioned calcium, magnesium and aluminum salts that they could be used both alone and in a mixture.

Other lubricants or release agents that can be used alone or in combination with one another are the relevant ones known from the prior art. substances. The following types of compounds are preferably suitable: hydrocarbon waxes which melt in the temperature range from 70 to 130 ° C., oxidized polyethylene waxes, free fatty acids with 8 to 22 carbon atoms and their branched chain isomers, for example stearic acid or also hydroxystearic acid, α-olefins, wax esters , ie esters of longer-chain monocarboxylic acids and monoalcohols, primary and secondary, saturated and unsaturated higher alcohols with preferably 16 to 44 carbon atoms in the molecule, ethylenediamine distearate, montanic acid esters of diols, for example ethanediol, 1,3-butanediol and glycerol, mixtures such montanic acid esters with unesterified montanic acids, partial esters of fatty acids with 8 to 22 carbon atoms and polyols with 2 to 6 carbon atoms and 2 to 6 hydroxyl groups, which contain on average at least one free polyol hydroxyl group per molecule. The mixed esters described in DE-C-19 07 768 with hydroxyl or acid numbers in the range from 0 to 6 and consisting of aliphatic, cycloaliphatic or aromatic dicarboxylic acids having 2 to 22 C atoms in the molecule, aliphatic polyols having 2 to 6 can also be used Hydroxyl groups in the molecule and aliphatic monocarboxylic acids with 12 to 30 C atoms in the molecule. Examples include mixed esters of maleic acid-pentaerythritol-behenic acid, mixed esters of adipic acid-pentaerythritol-oleic acid and mixed esters of adipic acid-pentaerythritol-stearic acid. Such lubricants or release agents can be used in the context of the present invention both individually and in combination with one another, and also in combination with the calcium, magnesium or aluminum salts mentioned above.

Plasticizers. With regard to plasticizers, express reference is made to page 29, line 20 to page 30, line 26 of EP-A-768 336 cited above. The plasticizers mentioned there are expressly included in the disclosure of the present invention.

Epoxidized fatty acid esters. With regard to examples of suitable compounds of this class, expressly on page 31, line 27 to page 31, line 32, the above cited EP-A-768 336. The epoxidized fatty acid esters mentioned there are expressly included in the disclosure of the present invention.

UV absorbers and light stabilizers. With regard to examples of suitable compounds of this class, reference is expressly made to page 33, line 6 to page 34, line 7 of EP-A-768 336 cited above. The UV absorbers and light stabilizers mentioned there are expressly included in the disclosure of the present invention.

Another object of the present invention is a process for the production of molded polyethylene articles, fibers and films, wherein a mixture containing

a) predominantly one or more polyethylene and

b) 0.01 to 20 wt .-% - based on the polyethylenes - one or more polyetheramine derivatives, the polyetheramine derivatives being selected from the group of the reaction products of di- or polyaminopolyalkylene oxide compounds with organic carboxylic acids containing one or contain two COOH functions and a total of 4 to 22 C atoms,

at temperatures in the range of 180 to 330 ° C in a conventional manner, a shaping processing such as extrusion, calendering, injection molding, blow molding and the like.

The molded polyethylene articles obtainable using the polyetheramines b), in particular the granules accessible by extrusion, can in turn be used to be used as so-called masterbatches in the processing of bulk plastics. Another object of the present invention is therefore the use of molded polyethylene articles, in particular granules, which are obtainable by containing a mixture

a) predominantly one or more polyethylene and

b) 0.01 to 20 wt .-% - based on the polyethylenes - one or more polyetheramine derivatives, the polyetheramine derivatives being selected from the group of reaction products of di- or polyaminopolyalkylene oxide compounds with organic carboxylic acids containing one or contain two COOH functions and a total of 4 to 22 C atoms,

at temperatures in the range from 180 to 330 ° C. in a customary manner to shaping processing such as extrusion, calendering, injection molding, blow molding and the like, as additives for masterbatches in the processing of bulk plastics.

B e i s p i e l e

1. Materials used

1.1. Polyethylene (a)

Lupo: low-density polyethylene (commercial product "Lupolen 1800 H" commercial product from Elenac

1.2. Polyetheramines (PEA)

Jeffamine D-2000: Commercial polyetheramine from Huntsman Petrochemical Corporation (MG = 2000)

Jeffamine D-4000: Commercial polyetheramine from Huntsman Petrochemical Corporation (MG = 4000)

Jeffamine T-3000: Commercial polyetheramine from Huntsman Petrochemical Corporation (MG = 3000)

1.3. Production of polyetheramine derivatives b)

In the following, the abbreviation "AZ" means amine number, a product code number familiar to the person skilled in the art, which indicates the number mg KOH which is necessary to neutralize the amount of hydrochloric acid bound by 1 g of amine. Example 1 (Bl):

In a 250 ml four-necked flask equipped with a stirrer, thermometer and distillation bridge, a mixture of 100 g Jeffamin D-4000 (AZ: 27.6) with 2.46 g succinic anhydride was reacted at 120 ° C. for 2 hours with stirring. The product obtained had an AZ of 11.0

Example 2 (B2):

In a 250 ml four-necked flask equipped with a stirrer, thermometer and distillation bridge, a mixture of 100 g Jeffamin D-4000 (AZ: 27.6) with 4.92 g succinic anhydride was reacted at 120 ° C. for 2 hours with stirring. The product obtained had an AZ of 0.0

Example 3 (B3):

In a 250 ml four-necked flask equipped with a stirrer, thermometer and distillation bridge, a mixture of 100 g Jeffamin D-4000 (AZ: 27.6) with 4.82 g maleic anhydride was reacted with stirring at room temperature. After the slight exotherm subsided, the product obtained was filled. The product had an AZ of 0.0.

Example 4 (B4):

In a 250 ml four-necked flask equipped with water separator, reflux condenser and thermometer, a mixture of 100 g Jeffamin D-4000 (AZ: 27.6) with 7.19 g adipic acid and 50 ml xylene was heated under reflux with stirring until no more water of reaction was separated (6h). The remaining solvent was then removed in vacuo (5 mbar). The product obtained had an AZ of 0.6.

Example 5 (B5)

In a 250 ml four-necked flask equipped with water separator, reflux condenser and thermometer, a mixture of 100 g Jeffamin D-2000 (AZ: 56.1) with 3.65 g of adipic acid and 50 ml of xylene on a water separator under reflux until no more water of reaction has been separated (6 h). The remaining solvent was then removed in vacuo (5 mbar). The product obtained had an AZ of 32.3

Example 6 (B6)

In a 250 ml four-necked flask equipped with water separator, reflux condenser and thermometer, a mixture of 100 g Jeffamin D-4000 (AZ: 27.6) with 1.79 g adipic acid and 50 ml xylene was heated under reflux with stirring until no more water of reaction was separated off (6h). The remaining solvent was then removed in vacuo (5 mbar). The product obtained had an AZ of 10.7

Examples 7 (B7):

In a 250 ml four-necked flask equipped with a water separator, reflux condenser and thermometer, a mixture of 100 g Jeffamin D-4000 (AZ: 27.6) with 2.39 g adipic acid and 50 ml xylene was heated under reflux with stirring until no more water of reaction was separated off (6h). The remaining solvent was then removed in vacuo (5 mbar). The product obtained had an AZ of 8.7.

Example 8 (B8):

In a 250 ml four-necked flask equipped with water separator, reflux condenser and thermometer, a mixture of 100 g Jeffamin T-3000 (AZ:

52.2) with 2.26 g of adipic acid and 50 ml of xylene on a water separator under reflux until no more water of reaction has been separated (6 h). The remaining solvent was then removed in vacuo (5 mbar). The product obtained had an AZ of 31.1. 2. Production of surface-modified polyethylene

according to the method of the invention

To check the adhesive compatibility properties of surface-modified polyethylene, polyethylene tapes were first produced. To do this, each

- 600 g of polyethylene granules a) and

Additive b) (or in the comparative tests also of other test substances)

mixed. The type and amount of component b) used in each case can be found in Table 1. These mixtures were fed into an extruder through a hopper. A twin screw extruder DSK 42/7 from Brabender OHG (Duisburg) was used. An extruder is - as is well known to the person skilled in the art

- A plastic processing machine, which is suitable for the continuous mixing and plasticizing of both powder and granular thermoplastics. In addition to water cooling, which is intended to prevent premature melting of the granules or powder, there is also a counter-rotating twin screw, which is divided lengthways into three heating zones. The temperature of the heating zones and the speed of the twin screw can be controlled via a PL 2000 data processing plast corder, which is connected to the extruder via a PC interface. The following temperatures were set for the production of the polyethylene tapes: Heating zones I-III each 240 ° C., the three heating zones being air-cooled in order to keep the temperatures constant.

The polyethylene granules including the respective component b) were automatically drawn into the extruder by the twin screw running counter to one another and conveyed along the screw. The speed was 50 revolutions per minute. This ensured a relatively long residence time in the extruder and, accordingly, good mixing and homogenization. This homogeneous and bubble-free mixture finally came into a nozzle, which is a fourth heating zone. The temperature of this outlet nozzle is shown in Table 1.

After exiting the nozzle (dimensions of the nozzle = 50 x 0.5 mm), the hot mixture flowed onto a conveyor belt, the speed of which was adjusted in such a way that a smooth and uniformly thick and wide belt was formed when cooling in air. In the work described here, the speed was set so that the polyethylene tape was about 45 mm wide and about 0.5 mm thick. Square test specimens (25 x 20 mm) were punched out of this material and used for the adhesive tests described in more detail below.

3. Glue and tear tests

3.1. Production of the test specimens

The extruded tapes produced according to 2) were stored for 24 hours at room temperature (20 ° C.). Then square polyethylene pieces of 25 x 20 mm were glued between two wooden boards measuring 100 x 25 mm. The bond had a thickness of 2 mm. The adhesive surface was exactly 25 x 20 = 500 mm. It should be noted that the experimental setup is analogous to that outlined on p. 21 of WO 98/42776 mentioned above.

A two-component adhesive was used as the adhesive ("Makroplast" polyurethane adhesive from Henkel KGaA / Düsseldorf). For this purpose, the two reactive components (resin = UK 8109; hardener = UK 5400) were mixed in a ratio of resin: hardener of 5: 1 in an aluminum dish. The pot life was about 1 hour.

After appropriate storage, strips with a width of 25 mm were cut from each band and glued on both sides using a template between two wooden boards. 5 bonds were made from each plastic tape. The use of a template guaranteed compliance with the desired adhesive surface between the modified plastic and the board. Wooden clips were used to fix the test specimen. Excess glue has been removed.

3.2. Tensile Tests

The test specimens produced according to 3.L) were stored at 20 ° C. for 5 days to ensure that the two-component adhesive had completely hardened. A universal testing machine from Zwick was then used to measure the tensile shear forces. The speed at which the test specimen was subjected to tension was 15 mm / min. The glued wooden spatulas (= test specimens) were clamped into the clamping jaws of the universal testing machine and pulled apart at the specified test speed. It was ensured that the test objects were always positioned vertically and exactly in the middle of the test device. The test results obtained are summarized in Table 1. All results are mean values from 5 experiments each.

Table 1:

About the columns in Table 1:

No. test number (B = according to the invention; V = comparison) a) component a) (polyethylene) additive either a comparison compound or a compound b) according to the invention was used here; The column "%" indicates the amount in which the particular compound -% by weight based on component a) - was used

T / nozzle Temperature of the outlet nozzle of the extruder in ° C ZSG Value of the tensile shear strength, determined during the tensile tests. The figures are in Newtons per square millimeter.

Claims

Patent claims

1. Use of polyetheramine derivatives for the permanent improvement of the adhesive and / or coating compatibility of polyethylene-based moldings, fibers and films, with a mixture containing

a) predominantly one or more polyethylenes and

b) 0.01 to 20 wt .-% - based on the polyethylenes - one or more polyetheramine derivatives, the polyetheramine derivatives being selected from the group of the reaction products of di- or polyaminopolyalkylene oxide compounds with organic carboxylic acids containing one or contain two COOH functions and a total of 4 to 22 C atoms,

at temperatures in the range of 180 to 330 ° C in a conventional manner, a shaping processing such as extrusion, calendering, injection molding, blow molding and the like.

2. Process for the production of Polyemylenformköφern, fibers and films, wherein one containing a mixture

a) predominantly one or more polyethylenes

b) 0.01 to 20 wt .-% - based on the polyethylenes - one or more polyetheramine derivatives, the polyetheramine derivatives being selected from the group of the reaction products of di- or polyaminopolyalkylene oxide compounds with organic carboxylic acids containing one or contain two COOH functions and a total of 4 to 22 C atoms,

at temperatures in the range of 180 to 330 ° C in a conventional manner, a shaping processing such as extrusion, calendering, injection molding, blow molding and the like.

3. The method according to claim 2, wherein the polyethylene used is low density polyethylene.

4. The method according to claim 3, wherein a temperature in the range from 200 to 270 ° C is set in the shaping processing.

5. Use of polyethylene moldings, in particular polyethylene granules, which are obtainable by containing a mixture

a) predominantly one or more polyethylenes and

b) 0.01 to 20 wt .-% - based on the polyethylenes - one or more polyetheramine derivatives, the polyetheramine derivatives being selected from the group of the reaction products of di- or polyaminopolyalkylene oxide compounds with organic carboxylic acids containing one or contain two COOH functions and a total of 4 to 22 C atoms,

at temperatures in the range from 180 to 330 ° C. in a customary manner to shaping processing such as extrusion, calendering, injection molding, blow molding and the like, as additives for masterbatches in the processing of bulk plastics.