HK1161611B - Lubricant for thermoplastic polymers - Google Patents

Description

The invention relates to a polymer composition containing at least one thermoplastic polymer, at least one pigment or at least one filler or a mixture thereof and at least one diester of a linear diol with 2 to 8 C atoms with a linear or branched, saturated or unsaturated monocarbonic acid with 6 to 44 C atoms, where the proportion of diester with different fatty acid residues in a molecule is less than 10% by weight of the total amount of diester, and where the polymer is polyvinyl chloride.

Thermoplastic polymers are very popular in the manufacture of moulds of all kinds. The processing of thermoplastic polymers into such moulds usually takes place in several steps, usually at least one of which involves heating the polymer, often to a temperature at which the thermoplastic polymer has a rheological profile sufficient for further processing. Further processing steps often involve an intensive mixing of thermoplastic polymers and other ingredients and a cutting of the polymer.

In order to improve the machinability of the moulds, a so-called lubricant is often added to such mixtures of thermoplastic polymers and other ingredients, if necessary.

For example, DE 38 12 014 describes the use of ethylene glycol esters in Ca/Zn stabilizers.

It has now been shown that, in particular, thermoplastic polymers contain pigments or fillers which often leave the surface gloss unwanted when using alkyl glycol esters, in particular, partial roughness or matte surfaces which may adversely affect the appearance of a mould made from a corresponding thermoplastic polymer.

There was therefore a need for a thermoplastic polymer lubricant which overcomes the disadvantages of the solutions known from the state of the art. In particular, there was a need for a thermoplastic plastic lubricant which would improve the structure of the thermoplastic polymer. For example, there was a special need for a lubricant which would help a thermoplastic polymer, and in particular a mould made from one of these thermoplastic polymers, to improve its surface structure. In particular, there was a need for a mould which would help a thermoplastic surface to have a rough surface that is less or less matte and in particular an improved gloss.

It has now been found that pigment or filler-containing thermoplastic polymer compositions containing one or more diester of a linear diol with 2 to 8 C atoms with a linear or branched, saturated or unsaturated monocarbon acid with 6 to 44 C atoms can result in moulds with surfaces showing improved gloss or roughness values when in such a polymer composition the proportion of diesels with different fatty acid residues in a molecule is less than 10% by weight of the total amount of diester,

The present invention is therefore a polymer composition containing as constituent elements: Z1at least 15% by weight, in relation to the polymer composition, of at least one thermoplastic polymer;Z20,001 to 15% by weight, in relation to the polymer composition, of a linear diol dister with 2 to 8 C atoms with a linear or branched, saturated or unsaturated monocarbon acid with 6 to 44 C atoms; andZ30,1 to 80% by weight, in relation to the polymer composition, of at least one pigment or at least one filler or a mixture thereof, where the proportion of disters with different fatty acid residues in a diol is less than 10% by weight of the total amount of disters or less than 8% by weight of the total amount of disters and the polymer is polyvinyl chloride.

A polymer composition is a sophisticated additive composition that contains at least one thermoplastic polymer, at least one diester of a linear diol, and at least one pigment or filler, as defined in the present invention. A polymer composition may in principle be in any form, such as powder, granules, or semi-finished products prepared in any form, such as pellets, rods, squares or the like.

In a design according to the invention, the polymer composition according to the invention is thermoplastic and melts not less than 80, preferably at or below 140 and preferably at or below 270°C. In most cases, the thermoplastic polymer compositions according to the invention are preferred to melt at 350° or less. In thermoplastic polymer compositions according to the invention, polymers with equal melting properties are used at more than 50% by weight, preferably at more than 75% by weight and preferably at more than 90% by weight, depending on the polymer or polymers used in the thermoplastic composition.

A polymer composition according to the invention contains at least 15% by weight, in relation to the total polymer composition, of at least one thermoplastic polymer which is polyvinyl chloride. The upper limit for the content of thermoplastic polymers may be, for example, 99,899% by weight, in relation to the total polymer composition, or less, for example, 98%, 96%, 94%, 92%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, or 50%, or less. It is also possible that a polymer according to the invention may contain less than or equal to 20% by weight, in relation to the total polymer composition, or less than or equal to 20%, 17%, 45%, 25% or less, or less, or less than or equal to 20% or less, in relation to the total polymer composition, or less than or equal to 20% or less, for example, or less than or equal to 20% or less, in relation to the total polymer composition, or less than or equal to 20% or less, in relation to the total polymer composition, or less than or equal to 16,5% or less, in relation to the total polymer composition, or less than or equal to 20% or less, for example, or less than or equal to 20% or equal to 20% or less, or less, in relation to the total polymer composition, or less than or less than or less than or equal to 20% or equal to 20% or less, for example, or less, or less, or less than or equal to or equal to 20% or equal to or equal to or equal to or equal to or equal to or equal to or equal to, or less, or less, or less, or to or less than or less than or equal to or equal to or equal to or equal to or equal to or equal to or equal to or equal to or equal to or equal to or equal to or less than or equal to or equal to or less than or equal to or equal to or equal to or equal to or less than or equal to or equal to or to or less than or equal to or equal to or less than or equal to or equal to or equal to or less than or equal to or equal to or equal to or less than or equal to or equal to or to or less than or equal to or to or less than or less than

A polymer composition in accordance with the invention is intended to exhibit thermoplastic properties, but this does not preclude a polymer composition in accordance with the invention from having a proportion of non-thermoplastic polymer components, such as a proportion of duromers (often referred to in the literature as duroplasts), which is, however, at most such a quantity that the thermoplastic properties of the entire polymer composition are not so adversely affected that thermoplastic processing is not possible or only serious adverse effects are absorbed.

In addition to at least one thermoplastic polymer according to component Z1, a polymer composition of the invention has as component Z2 between 0.001 and 15% by weight of the total polymer composition of a linear diol dister with 2 to 8 C atoms with a linear or branched, saturated or unsaturated monocarbon acid with 6 to 44 C atoms.

Linear diols with 2 to 8 C atoms are suitable as the basis for the diester to be used in accordance with the invention. Linear diols are, for example, ethylene glycol, n-propylene glycol, n-butylene glycol, n-pentamethylene glycol, n-hexamethylene glycol, n-heptamethylene glycol or n-octamethylene glycol. In a preferred embodiment of the invention, the diester is a diester of ethylene glycol, propylene glycol, butylene glycol, pentamethylene glycol or hexamethylene glycol, in particular of ethylene glycol, propylene glycol or butylene glycol, in which case the esters of ethylene glycol in many cases have excellent properties.

Err1:Expecting ',' delimiter: line 1 column 259 (char 258)

The invention has been shown to be particularly effective when the diester is a diester of a linear, saturated or unsaturated monocarbonic acid with 8 to 22 C atoms, particularly 10 to 20 or 12 to 18 C atoms.

In principle, caproic acid, onic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidonic acid, benzoic acid, lignoceric acid, cerotinic acid, montanoic acid, melissic acid, undecylic acid, myristolic acid, palmitoleic acid, petricic acid, oleic acid, elacidic acid, vaccinic acid, gadolinium acid, icosic acid, cetic acid, erucic acid, caproic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, cerodic acid, α-linolenic acid, lauric acid, lauric acid, lauric acid, butyl acetic acid, unidecylic acid, unidecylic acid, unidecylic acid, or clenic acid are suitable for use as a food additive, especially in the formulation of a mixture of up to 22 amino acids, such as clenic acid or clenic acid, which is obtained by dissolving or dissolving the amino acid, in the presence of a solution of a phenol or a phenol.

A polymer composition according to the invention may contain a diester or a mixture of two or more disters. However, it is important in this context that the above limit for non-symmetrically substituted diester, i.e. diester with different acidic constituents, is respected. A polymer composition according to the invention may then contain, for example, a mixture of two different disters or a mixture of three different disters or a mixture of four or more different disters.

As a component, Z3 of the invention contains at least one pigment or at least one filler or a mixture of one or more fillers and one or more pigments.

Pigments are generally any inorganic or organic pigment which is compatible with the polymer composition as such and in particular with the polymer composition in the context of the intended processing. Pigments may give a colour to the polymer composition, but pigments which colour the polymer composition white or black are also suitable. Pigments which are particularly suitable are, for example, titanium dioxide, pigments based on zirconium oxide, barium sulphate, zinc oxide (zinc white) and lithone (zinc sulphate/barium sulphate), sulphur, mixtures of sulphur dioxide and titanium, iron oxide pigments, antimony oxide, chromium oxide, spinal blue and cadmium, cobalt oxide, azithromycin, cobalt blue or pigments such as cadmium, cadmium, cadmium, cadmium or anthracene, or pigments such as pigments such as cadmium, cadmium, cadmium, cadmium, cadmium, cadmium, or anthracene.

Fillers are in particular calcium carbonate, dolomite, gypsum, wolastonite, magnesium oxide, magnesium hydroxide, silicates, china clay, tallow, glass fibres, glass balls, wood balls, mica, metal oxides or metal hydroxides, soot, graphite, rock flour, heavy spatter, glass fibres, tallow, kaolin or chalk or metal sulphates, such as heavy metal sulphates, which may have a stabilising effect on the polymer composition in addition to a filling or pigmenting effect.

The proportion of pigments or fillers or mixtures of one or more pigments and one or more fillers in the total polymer composition is between 0.1% and 80% by weight, depending on the polymer composition. The invention provides that a polymer composition contains only small amounts of pigments or fillers, for example, between 0.5 and about 10 or between 1 and about 5%, by weight. However, it is also possible that a polymer composition according to the invention contains larger amounts of pigments or fillers or their mixtures, for example, between 10 and about 20 or between 70 and about 75 or between 25 and about 60 or between 30 and about 55 or between 35 and about 50 or between 40 and about 45% by weight, respectively, of the total polymer composition.

In other embodiments of the invention, the polymer composition includes as a constituent additional additives selected from the group consisting of stabilizers, other lubricants, plasticizers, anti-lock agents, anti-sealing agents, antistatic agents, flame retardants, dyes, pigments, fuels, fillers, fats, oils, antioxidants and solvents or a mixture of two or more of these additives.

Stabilizers prevent plastics such as PVC from decomposing or changing chemically at high temperatures, thus improving weather resistance.

Other lubricants are used to facilitate polymer processing by reducing friction between polymer chains and reducing the adhesion of the melt to the walls.

Many plasticizers belong to the group of phthalates (DEHP, DINP and DIDP), as well as the adipate and citrate groups.

Anti-fouling agents are used to prevent precipitation on the surface, for example, they are published in DE 10 2004 038 980 A1 and Plastics Additives Handbook, 5th Edition, Hanser Verlag, pp. 609 to 626, and are available from Cognis Oleochemicals GmbH.

Err1:Expecting ',' delimiter: line 1 column 93 (char 92)

Water or organic solvents such as alcohols, such as polyglycol, in particular polyethylene glycol or polypropylene glycol, or a mixture of the above, may be used as solvents.

Err1:Expecting ',' delimiter: line 1 column 97 (char 96)

Stabilizers prevent plastics such as PVC from decomposing or changing chemically at high temperatures and improve weather resistance.

Water or organic solvents such as alcohols may be used as solvents.

In a preferred embodiment of the invention, the polymer composition is a thermoplastic polymer composition. Thermoplastic polymer compositions are reversible from a certain temperature range. In further embodiments of the invention, the polymer composition is an unlinked, linkable polymer composition, for example for the production of elastomers.

Err1:Expecting ',' delimiter: line 1 column 225 (char 224)

The invention also relates to a mould containing or produced from a polymer composition of the invention.

The thermoplastic polymer compositions of the invention can generally be converted into the moulds of the invention by known methods. The polymer preparations can be first processed by known methods, for example by incorporating additives or by converting the polymer composition into a suitable form, such as granules, powders, pastes or solutions. If necessary, the polymer compositions are treated mechanically, i.e. dispersed, kneaded or granulated. The processing into moulds takes place, for example, by spraying or extruding. If necessary, the surface parts are further processed, i.e. molded, cut, pressed or welded. Polymers must be hardened or pressed to harden after molding.

A further subject of the processes used to produce a mould, including the process steps: (ii) heating the thermoplastic polymer composition to the glass transition temperature of the thermoplastic polymer or to a temperature above the glass transition temperature of the thermoplastic polymer; (iii) manufacture of a mould from the thermoplastic polymer composition produced in step II)

In step I of the process of manufacture of a mould, a thermoplastic composition of the invention is first provided, preferably by a process according to the first variant of the process of the invention.

In this context, it is again preferable to heat the thermoplastic composition to a temperature in the range of 5° below the glass transition temperature (Tg) to 100°C above the glass transition temperature of the thermoplastic polymer used, preferably to a temperature in the range of 1° above the glass transition temperature (Tg) to 50° above the glass transition temperature (Tg), with most thermoplastic polymers being heated to a temperature in the range of 1° below the glass transition temperature (Tg) to 20°C, but also to a temperature in the range of 1° above the glass transition temperature (Tg) to 50°C above the glass transition temperature (Tg), whereby the thermoplastic polymer is inserted and the temperature is in the range of 1° below the glass transition temperature (Tg) to 20°C, but also within the thermoplastic polymer's upper boundary, but not exceeding the thermoplastic transition temperature (Tg).

In principle, the steps I and II can be performed simultaneously or in succession. For example, it is useful to perform steps I and II simultaneously if the thermoplastic composition is produced by a melt-blending process. In this case, it may be advantageous to transfer the composition produced by the melt-blending process directly into a mould. For example, it is useful to perform steps I and II successively if the thermoplastic composition is produced by a dry-blending process or if the thermoplastic composition is produced by a melt-blending process but not immediately after the formation of a mould, although much of the mould is removed according to the procedure.

In step III of the method of manufacturing a mould according to the invention, a mould is produced from the heated thermoplastic composition produced in step II. The methods of manufacturing a mould include, in particular, injection moulding, extrusion moulding, compression moulding, layer moulding, lamination moulding, hollow moulding, vacuum moulding and transfer moulding, with particular preference to injection moulding.

In a preferred embodiment of the invention, at a further process step (IV), at least one part of the body obtained in process step (III) is reduced in its cross-sectional area compared to process step (III).

The invention also relates to a process for the manufacture of a packaging product, which involves the process steps of providing a product and a body of the invention and of at least partially surrounding the product with the body of the product.

Furthermore, it is consistent with the design of the method of manufacture of a thermoplastic mould according to the invention that at least one further process step (IV) at least a part of the mould obtained in process step (III) is used as mould grout and is reduced in its cross-section. The cross-section of the mould is the cross-section of a region of the mould consisting in the main of the thermoplastic mould mass according to the invention. For example, in the case of containers or assemblies, the cross-section of the mould represents the thickness of a transformation of these containers or assemblies. In the case of moulds shaped more like strands or strands, the cross-section represents the thickness of these strands or assemblies, which are more like layers, plates, sheets, plates, etc.The cross-section of the mass is the strength of the flat structure. In principle, all methods known to the skilled person and suitable for this purpose are used to reduce the cross-section. These include, for example, stretching in one or two directions, pulling in one or two directions, slinging or bubbling, preferably at elevated temperatures, where the thermoplastic composition of the invention is so soft or even fluidized that stretching, pulling, slinging or bubbling can be carried out. The part of the body in which the cross-section is reduced must preferably be at least 50% and at least 80% of the shape in the form of a pre-form.In the case of the production of films, the drawing or stretching can be carried out in one or more dimensions. For example, the track running from an extruder can be drawn on a roller at a higher speed than the exit speed from the extruder.The thermoplastic composition of the mould obtained in step III, which is usually heated to at least glass transition temperature, can be stretched; the stretching is usually limited by the use of a mould which has the final shape of the mould; it is still possible for two or more of the steps I to IV to be supplemented by further steps and/or at least overlap in time; this is particularly the case for steps III and IV.

A process for the manufacture of a packaging product, including as process steps: (b) at least partly enclosing the good with the body.

The goods supplied in step (a) are, for example, a pharmaceutical, personal care product or foodstuff, and the goods at least partially enclosed may be, for example, provided by the procedure described in DE-A-103 56 769.

The use of the materials and their use as lubricants in accordance with the invention solves the problems underlying the invention.

One use of the invention is to use a linear or branched diol dister of 2 to 8 C atoms with a linear or branched, saturated or unsaturated monocarbon acid of 6 to 44 C atoms, in a thermoplastic polymer composition containing a pigment or filler containing polyvinyl chloride, to improve the surface structure of a mould made from the polymer composition, where the proportion of diesels with different fatty acids in a polymer composition is less than 10% by volume of the total amount of disters, and where the improvement of the surface structure is a reduction in roughness or an improvement in the sheen.

In a preferred use, the proportion of diesters with different fatty acid residues in a diol is less than 8% by weight of the total amount of diesters.

Experimental part Manufacture of lubricants according to the invention: Example 1:

Distearylphthalate, Loxiol G 60, Fa. Cognis-Oleochemicals Other

Example 2: Ethylene glycol and ipalmitate

90 g ethylene glycol (Fluca), 571 g palmitic acid (Edenol C16 98-100, Fa Cognis-Oleochemicals) and 0.3 g tin-II oxalate (Goldschmidt) were heated under nitrogen. The esterification reaction started at about 170 °C with the formation of water. After 3 h, the reaction water was further withdrawn by applying a vacuum and the vacuum was reduced to about 15 mbar within 4 h. The final temperature was 230 °C. At a SZ < 6, the reaction was completed. It was cooled and filtered to 90 °C. Yield 568 g, S = 3.9, drop point 70.5 °C.

Example 2:

Rilanite AGS, an ethylene glycol ester with a stearic acid/palmitic acid mixture (approximately 50%:50%) from Fa. Cognis

Manufacture of dry blends

The following table shows the composition of PVC powder and the various additives used in a Henschel blender to produce a dry blend (material quantity = 3 kg, heating temperature = 120 °C, subsequent cooling).

Beispiel:	B1	B2	B3
PVC Evipol SH 6520	100	100	100
Pb-Sulfat, 3-basisch	2	2	2
Bleistearat 28 %	0,5	0,5	0,5
Calciumstearat	0,5	0,5	0,5
Distearylphthalat	1	-	-
Ethylenglykoldipalmitat	-	1	-
Rilanit AGS	-	-	1

Manufacture of flat-rolled strip

The dryblends were extruded onto a flat strip on a Weber double-slotted extruder (extrusion parameters: speed = 15 UpM; temperature = 190 °C). The gloss of the finished flat strip was determined according to DIN 67530. Other

Glanz %	B1	B2	B3
55,1	65,7	40,0
55,2	63,6	44,1
54,3	59,3	48,0
48,5	62,1	39,3
50,9	61,8	43,3
Mittelwerte:	52,8	62,5	44,36

The lubricant of the invention (B2) results in a very smooth surface and a very high gloss. Distearylphthalate (B1) is a lubricant that is commonly used in such applications and is listed for comparison. The worst surface is achieved with a lubricant containing asymmetric ethylene glycol ester (B3).

Claims (17)

1. A polymer composition comprising, as composition components

   Z1 at least 15% by weight, based on the polymer composition, of at least one thermoplastic polymer;

   Z2 from 0.001 to 15% by weight, based on the polymer composition, of a diester of a linear diol having from 2 to 8 carbon atoms with a linear or branched, saturated or unsaturated monocarboxylic acid having from 6 to 44 carbon atoms; and

   Z3 from 0.1 to 80% by weight, based on the polymer composition, of at least one pigment or of at least one filler or of a mixture thereof,

   wherein the amount of diesters having different fatty acid residues on a diol is less than 10% by weight, based on the total amount of diester, or less than 8% by weight, based on the total amount of diester, and where the polymer is polyvinyl chloride.
2. The polymer composition according to Claim 1, where the symmetrical diester is a diester of ethylene glycol, propylene glycol, butylene glycol, pentaethylene glycol or hexaethylene glycol.
3. The polymer composition according to Claim 1 or 2, where the symmetrical diester is a diester of a linear saturated or unsaturated monocarboxylic acid having from 8 to 22 carbon atoms.
4. The polymer composition according to any of the preceding claims, where the symmetrical diester is a diester of ethylene glycol with a fatty acid selected from the group consisting of myristic acid, palmitic acid, margaric acid, stearic acid, arachic acid or behenic acid.
5. The polymer composition according to any of the preceding claims, where the polymer composition comprises a diester or a mixture of two or more diesters.
6. The polymer composition according to any of the preceding claims, where the polymer composition comprises an amount of from about 0.01 to about 10% by weight or from about 0.1 to about 5% by weight of a diester or of a mixture of two or more diesters.
7. The polymer composition according to any of the preceding claims, where the amount of diesters having different fatty acid moieties on a diol is at least 0.1% by weight, or 0.01% by weight, or 0.001% by weight, based in each case on the total amount of diester.
8. The polymer composition according to any of the preceding claims, where the amount present of the filler or two or more fillers or the pigment or at least two or two or more pigments or a mixture of filler and pigment is comprised from 0.05 to 60% by weight or from 1 to 50% by weight, based on the entire polymer composition.
9. The polymer composition according to any of the preceding claims, where the polymer composition comprises at least one or several additives.
10. The polymer composition according to any of the preceding claims, wherein as additive at least one additive selected from the group consisting of stabilizers, other lubricants, plasticizers, antiblocking agents, antifogging agents, antistatic agents, flame retardants, dyes, propellants, fats, oils, antioxidants, acid traps, nucleating agents and solvents, or a mixture of at least two thereof is comprised.
11. A process for producing a moulded article, comprising the following steps:

    I) providing a thermoplastic polymer composition according to any of Claims 1 to 10,

    II) heating the thermoplastic composition to the glass transition temperature of the thermoplastic polymer, or to a temperature above the glass transition temperature of the thermoplastic polymer;

    III) producing a moulded article from the thermoplastic composition produced and heated in step II).
12. The process according to Claim 11, where, in a further step IV), the mass cross section of at least one portion of the moulded article obtained in step III) is reduced with respect to step III).
13. The process according to Claim 11 or 12, where the moulded article is one selected from a group consisting of a container, a film, a fibre.
14. A method for producing a packaged product comprising as method steps:

    a) providing a product and a moulded article obtainable according to a process according to any of Claims 11 to 13;

    b) at least to some extent surrounding the product with the moulded article.
15. Use of a diester of a linear or branched diol having from 2 to 8 carbon atoms with a linear or branched, saturated or unsaturated monocarboxylic acid having from 6 to 44 carbon atoms, in a pigment- or filler-containing thermoplastic polymer composition which comprises polyvinyl chloride, for improving the surface structure of a moulded article made from the polymer composition, wherein the amount of diesters with different fatty acid residues in a molecule is less than 10% by weight in the polymer composition, based on the total amount of diester, and wherein the improvement of the surface structure is a roughness reduction or a gloss improvement.
16. Use according to Claim 15, wherein the amount of diesters with different fatty acid residues on a diol is less than 8% by weight, based on the total amount of diester.
17. Use according to Claim 15 or 16, wherein the polymer composition is a polymer composition according to any of claims 1 to 10.