DE1205656B - Self-sterilizing packaging material - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

A611

German class: 30 i - 3

1 205 656
A 36100IV a / 30 i
November 23, 1960
November 25, 1965

The invention relates to self-sterilizing material for the manufacture of packaging material and Packaging for food and pharmaceutical products. The material consists of one high molecular weight thermoplastic hydrocarbon polymer that can be halogenated.

In the pharmaceutical and food industries it is necessary that the packaging itself is sterile even though the contents are enclosed therein. The desired sterility is usually achieved by subjecting the package to a sterilization treatment immediately before filling, which for thermo-plastic resins is a regular treatment with ethylene oxide. By such a However, treatment, which is also very time consuming and requires expensive equipment, becomes proportionate has achieved questionable results, and only certain thermoplastic resins can act on this Way to be sterilized. Other common sterilization methods, such as autoclaving or the like, are ao not useful for most thermoplastic resins because of the temperature required for this treatment is so high that there is a risk of deformation or melting of the material.

It has also been proposed to sterilize the surfaces of thermoplastics by they are immersed in a sterilizing liquid. If at the same time a porous surface layer is formed it is actually possible to have a limited, self-sterilizing effect. It has however, it has been found that the self-sterilizing effect achieved in this way is only a relatively short one Time lasts.

It has been proposed to produce masses with a certain disinfecting effect by that one incorporates various additives, but all of these have been found to be unsuitable because they even at low concentrations, which are effective in themselves, the development of toxic side effects result and / or are tissue-irritating, or at concentrations that are useful per se are too weak an effect.

There is thus a need in the food industry and pharmacy for a self-sterilizing one Packaging material that does not affect the contents and always during manufacture is sterile and remains sterile during storage so that further sterilization prior to shipment and packaging is not necessary. The ingredients that give the self-sterilizing effect may not be extracted into the product packed therein at the concentrations used or Self-sterilizing packaging material

Applicant:
Aktiebolaget Astra,
Apotekarnes Kemiska Fabriker,
Södertälje (Sweden)

Representative:

Dr. H.-H. Willrath, patent attorney,

Wiesbaden, Hildastr. 18th

Named as inventor:

Bertil Järnhäll,

Erik Lennart Wikander, Södertälje (Sweden)

Claimed priority:

Sweden of November 24, 1959 (11055) -

migrate into it, at least not to such an extent that toxic or tissue-irritating secondary effects be evoked. Furthermore, of course, the sterilizing ingredient must not be included in the contents Give taste or smell.

This object is achieved by the invention, which provides a self-sterilizing packaging material, that fully meets the requirements mentioned.

The novel feature of the invention is that a packaging material consists of a high molecular weight hydrocarbon polymer which can be halogenated and contains 4-n-hexylresorcinol and / or 4-n-octylresorcinol as an antimicrobial component, the active ingredient being uniformly distributed in the material and its content is more than 2 ° / _0, preferably at most I ⁰ I ₀ is. The uniform distribution of these compounds is achieved by mechanically mixing the granulated polymer and the active substance and then homogenizing the blend in the molten state by heating it to the setting temperature, whereupon the mass is converted into granulated form. The granulate obtained in this way is then used for the production of films or packaging of various types by injection molding, blow molding, compression molding or casting. The material can of course be used directly for finished packaging,

509 739/376

such as vials, jars or containers, bottles or ampoules. Also layered foils can be made that on at least one side of the self-sterilizing material after Invention included, preferably on that film surface when the Package made of the self-sterilizing material according to the invention in contact with the package contents should come. These finished packs and the packaging material can of course be per se known methods are produced.

The invention is further illustrated by the following examples, but is not intended to be restricted thereto be.

example 1

10 kg of polyethylene granules of the LD type were continuously mixed in a drum or by hand 10 g of 4-n-hexylresorcinol cut off. The homogeneous mixture was then transferred to an extrusion mold, in the cylinder of which the polyethylene was converted into a molten mass. Through this the hexylresorcinol was evenly distributed throughout the mass. The homogeneous cut was squeezed out and then immediately converted into granule form. These self-sterilizing granules were then in brought a mold, in the cylinder of which it was again melted and thereby further homogenized, and the molten mass was converted into 100 ml vials or ampoules. On the same Ampoules or vials made of polyethylene with an addition of 0.5% (50 g / kg) were also used. 4-n-hexylresorcinol. Controls, d. H. Polyethylene ampoules without any additives for sterilization of hexylresorcinol, were also made.

So three types of ampoules were made, viz

Table 1

concentration Staph. 100 Candida P.nota- At the of the sterilizer albus 0 albicans tum pulp by means of 100 0 100 100 A. 0 0 0 0 B. 0.1 0 0 0 C. 0.5

From the numbers in this table it can be seen that 100% growth of microorganisms at All controls occurred, while the test tubes with ampoules that were made from the sterilant in question containing resin were prepared, no growth of microorganisms was observed.

The results compiled in Table 2 below were obtained when testing Receive ampoules that had been inoculated after a storage time of 4 months. Some ampoules had been washed before vaccination. These ampoules have been bacteriologically tested after they were exposed to incubation conditions for 1 day (Table 2) and for 2 days (Table 3) was. The numbers in Tables 2 and 3 have the same meaning as in Table 1.

Table 2
(1 day incubation conditions before breeding)

40

A. Controls, d. H. Ampoules made of polyethylene resin without any addition of hexylresorcinol,

B. Ampoules made of polyethylene resin with 0.1%
4-n-hexylresorcinol and

C. Ampoules made of polyethylene resin with 0.5%
4-n-hexylresorcinol.

45

Some ampoules of these three types were immediately inoculated with one of the following test organisms: Staph. albus, E. coli, Candida albicans, Pen. notatum, and were then exposed to incubation conditions. It there may be technical reasons for making vaccination very difficult and in practice only a fraction of the vaccination level actually used is given.

Some other ampoules were tested with the same test organisms after a longer or shorter period of storage inoculates. On this occasion, ampoules that were prepared in accordance with the washing instructions for the pharmaceutical industry had been washed, also inoculated.

The ampoule set that comes first, i.e. H. was inoculated immediately after manufacture a bacteriological test 3 days after vaccination, d. H. after them the for growth of microorganisms were subjected to suitable conditions for 3 days. the Test results are compiled in Table 1 below. The numbers mean the growth of the test organisms in percent.

At the
pulp Concentration of
Sterilizing agent
° / o Staph.
albus Exoli Can
dida
albi
cans P.no-
date A.
B.
C. 0:
washed
not washed ..
0.1:
washed
not washed ..
0.5:
washed
not washed .. 100
100
30th
0
0
0 100
100
30th
30th
0
0 100
100
0
0
0
0 100
100
0
0
0
0

Table 3

At the
pulp Concentration of
Sterilizing agent
° / o Staph.
albus E. coli Can
dida
albi
cans P.no-
date A.
B.
C. 0:
washed
not washed ..
0.1:
washed
not washed ..
0.5:
washed
not washed .. 100
100
0
0
0
0 100
100
0
0
0
0 100
100
0
0
0
0 100
100
0
0
0
0

From the above Tables 2 and 3 it can be seen that in the ampoules C all test organisms were destroyed after just one day, while in some of the ampoules B the surviving microorganisms still after 1 day, but no longer after

2 days could be determined. The controls, i.e. H. the ampoules A did not prevent in any case the growth of one of the test organisms.

Example2

10 kg of polyethylene were added to a drum with 50 g of 4-n-hexylresorcinol and 50 g of 4-n-octylresorcinol blended into an even mixture. The granulate was then transferred into an extrusion mold, in the cylinder of which the molten mass is further homogenized at the merging temperature of the resin became. Immediately after pressing, the product was ground into granules, and from this self-sterilizing base packs were manufactured by injection molding.

Example 3

10 kg of rubber hydrochloride were combined with 150 g of 4-n-octylresorcinol in a calender. After homogenization, the mixture was dissolved in a suitable solvent and the solution cast into foils in a manner known per se, whereupon the solvent was evaporated. the thus produced film has self-sterilizing properties and has been used as a material for production of various kinds Packaging, such as bags, used. The slide was also considered to be at least one Layer used in layered sheets, and as a result, such sheets did not need to be customary Methods to be sterilized that already entail the risk of deformation.

It is also possible, as resins, to use mixtures of polymers and / or copolymers, block copolymers and to use, for example, graft polymers. However, the invention does not encompass thermosets Resins and vulcanized products.

The self-sterilizing packaging materials made according to the invention are merely intended for export from the Federal Republic of Germany, as long as the addition to their manufacture substances used for food in accordance with the Food Act and the related ordinances is not permitted.

Claims (4)

Patent claims: 1. Use of a 4-n-hexylresorcinol and / or 4-n-octylresorcinol in an even distribution in a concentration of not more than 2%, preferably not more than 1% by weight, containing high molecular weight thermo-plastic hydrocarbon polymer, in particular polyethylene, as self-sterilizing packaging material for food and pharmaceuticals Products. 2. Use according to claim 1, characterized in that the polymer is 0.1 to 0.5 percent by weight 4-n-hexylresorcinol and / or 4-n-octylresorcinol contains. 3. Use according to claim 1, characterized in that the polymer consists of at least one of the resins polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinylidene chloride and Rubber hydrochloride. 4. Use according to any one of claims 1 to 3, characterized in that in one of packaging material consisting of several layers only with the packaging material The layer to be brought into contact with food or pharmaceutical product is 4-n-hexylresorcinol and / or 4-n-octylresorcinol. Considered publications: French Patent No. 790669; British Patent No. 555,907; U.S. Patent No. 2,758,032; Food Engineering, 27 (1955), No. 4, pp. 57 to 59; Reddish, »Antiseptics, Disinfectants, Fungicides, and Chemical and Physical Sterilization ", 1957, pp. 537-542. 509 739/376 11.65 © Bundesdruckerei Berlin