Thermoplastic polymer composition

 

(57) Abstract:

Describes a thermoplastic polymer composition for sausage and sausage casings, consisting of one or a mixture of polyamides and technological additives. It differs in that, as the additives used are compatible with the polyamide substance that is selected from a number of higher aliphatic length of the hydrocarbon chain C6-C20and aromatic carboxylic acids, fully and nepolnoglasnyh esters of carboxylic acids and polyhydric alcohols, amides of aliphatic acids, polyhydric alcohols, oligomeric polyamides, lactams, polyalkyleneglycol with molecular weight up to 20,000, their ethers and mixtures of these substances, and has thermal stability up to 300°C in an amount of 0.01-0.5. %. The technical result - described structure allows the processing to ensure the stability of the process orientation of the hood without the introduction of additional process steps and receive on the basis of the tubular film that retains high strength and barrier characteristics of the polyamides. 3 C.p. f-crystals, 1 table.

The invention relates to new thermoplastic polymer composition suitable for extrusion processing in Gowna film may include one or more polyamide layers, or may be made of this composition.

Recently, as the shells of boiled sausage products are increasingly used single-layer and multi-layered biaxially-oriented tubular film containing layers on the basis of synthetic polyamides. These membranes are characterized by a high barrier properties against oxygen, mechanical strength, elasticity, ability to tightly encircle the product without the formation of wrinkles.

Technology of production of biaxially-oriented blown film includes the following operations:

1. Preparation of the granulated polymer composition comprising, as a rule, the granules of a main polymer, poly dimensional additives and masterbatches, and load it into the extruder;

2. The melting of the polymer composition, it punching through the annular die plate and the formation in the form of primary sleeve with a thickness of 250-270 microns;

3. Quenching (hardening) of the primary sleeve water with a temperature of 19-21oC;

4. Heating of the primary sleeve to a temperature of 55 to 75oC;

5. Doconversion hood sleeves with multiplicity 2,5-2,9/a 2.9-3.4 in longitudinal and transverse direction, respectively;

6. Thermofixation of the finished sleeve at a temperature of 155-195oC;

7 the operating hoods and associated with breaks sleeves. They lead to large losses of raw materials and working time. These breaks occur due to the lack of plasticity of the primary sleeve, particularly for films containing polyamide layers red or black dyes.

In the end stage of orientation hood defines industrial production speed blown film.

Therefore, the producers of such films are forced to vary their composition, guided by the need to ensure stability of the process, often to the detriment of the consumer characteristics of the final product, such as strength and barrier properties.

So, to increase the plasticity of the primary sleeve use of multicomponent compositions based on polyamides.

In the Federal Republic of Germany patent N 2850181 (class B 65 D 81/34, A 22 C 13, publ. 29.05.1980, was blown film of shrinkable stretched a mixture of synthetic polymer, which contains at least one aliphatic polyamide, ionomer resin and/or one modified copolymer of ethylene and vinyl acetate. As polyamides it contains the polycaproamide (PA 6), polyaminoamide (PA 7), polyhexamethylenediamine (PA) and/or polyhexamethyleneguanidine (PA Alt (PA 12) as a copolymer of one or more of the above polyamides. Ionomer resin is a copolymer of ethylene, an unsaturated monocarboxylic acid such as (meth)acrylic acid. Introduction ionomer resin contributes to the achievement of greater uniformity exhaust bubble and lack devicenote areas. However, the use of ionomer resin is limited by the tendency of ionomers to destruction, leading to failures of single screw extruders because of the large gap in the melting temperature of the components to the heterogeneity of optical properties (gloss) film and increase the propensity of the film to the adhesion (blocking) in the roll.

Adding certain dyes and pigments, mainly red and black, in a concentration of more than 1% of the total mass of the major difficulties associated with the uneven distribution of pigment in the primary sleeve and increase its rigidity, and therefore its orientation hood often becomes impossible.

In the patent EP 0325151 B1 (class a 22 C 13/00, publ. 26.07.1989,) declared doconversion packaging film is made on the basis of polyamide compositions containing dyes. The composition includes an aliphatic polyamide, a polyester of terephthalic kotchetkova polyamide mostly equal to or greater than the weight fraction of the dye. To ensure the ability of the primary sleeve to the hood in polyamide-polyester mixture of expensive aromatic polyamide, a pre-mixed with the dye.

Introduction aromatic polyamides in the composition in substantial amounts significantly increases the cost and price of biaxially-oriented bag polyamideimide films.

In the patent US 3632728 (class B 29 D 7/24, publ. 04.01.1972,) it is shown that a uniform thickness and uniformity simultaneously zvukosnimateli flat polyamide film is achieved by using the workpiece polyamide film with a water content of more than 1% by weight of the polyamide. However, using this method associated with mutually exclusive requirements rather long exposure of the workpiece in the water and maintain the amorphous state of a polyamide as the water accelerates the crystallization of the polyamide. In addition, it is technologically very difficult to ensure uniform wetting of the workpiece, without which it is impossible to obtain a uniform film thickness.

In the patent EP 0062820 B1 (class C 08 J 5/18, publ. 28.05.1987, was very thin polyamide film obtained molded by extrusion. In the polyamide raw materials, including the RA education centers of crystallization and liquid organic dispersant, selected from the group of polyalkylene glycols, paraffin oils, esters of carbocyclic acids, organopolysiloxanes, alkoxycarbonyl ALKYLPHENOLS, alkoxycarbonyl fatty acids, alkoxycarbonyl amines and fatty acid amides. The initiators of crystallization are barium sulfate, trehzameshchenny calcium phosphate, calcium chloride and talc. The advantages achieved by introducing into the polymer composition of the initiators of centers of crystallization during injection molding extrusion, are an obstacle when the orientation of the polyamide film obtained from the amorphous state. The disadvantages of this method includes an additional step of obtaining a dispersion, which is then mixed with the polyamide granulate.

The closest technical solution to the invention is described in U.S. patent 5534277 (class a 22 C 13/00, publ. 09.07.1996 g), which claimed at least three-layer film, the outer layers which are composed of a mixture of crystalline polyamide and additives that violate the crystallinity of the latter.

As such additives, a mixture of the second crystalline polyamide, different from the first crystalline polyamide and olefinic material. The first crystalline polyamide crystallinity first polyamide, most preferably the use of polyamide materials, such as PA 11, PA 12, PA 610, PA 612 (polyhexamethylenediamine), the copolymer PA 6/66 (copolyamide caprolactam, diamine and adipic acid) and the copolymer PA 66/610 (copolymer obtained from a mixture of monomers for PA 66, PA 610). In the same as can be used and olefinic materials, such as copolymers of ethylene and an unsaturated acid, ethylene ester of unsaturated acid-modified polymers and ionomers. However, the use of such a thermoplastic polymer composition does not solve all problems arising in the process of orientation, especially when the film thickness less than 50 microns. The introduction of such additives mainly in the amount of 20 - 40% impact on consumer properties of the produced film, including its strength, and water permeability. To overcome these disadvantages it is necessary to make a multilayer film instead of a single layer.

The problem to be solved in the present invention is to develop a new thermoplastic polymer composition on the basis of one or a mixture of several polyamides, allowing for processing on conventional extrusion equipment (single screw extruder) the walkie-talkies and receive on the basis of the tubular film, retaining high strength and barrier characteristics of the polyamides.

The next task of the invention is to reduce production costs and obtain intensively and uniformly colored products improved the presentation.

The solution of this problem is achieved by thermoplastic polymer composition consisting of one or a mixture of polyamides and technological additive, an additive used is compatible with the polyamide substance that is selected from a number of higher aliphatic length of the hydrocarbon chain C6-C20and aromatic carboxylic acids, sulphonic acids, fully and nepolnoglasnyh esters of carboxylic acids and polyhydric alcohols, amides of aliphatic and aromatic acids, sulfonamides, or higher polyhydric saturated alcohols, oligomeric polyamides, lactams, polyalkyleneglycol with molecular weight up to 20,000, their ethers and mixtures of these substances, and has thermal stability up to 300oC in an amount of 0.01 to 0.5 mass %.

Suitable as polyamides, first of all, to use the polyamides 6, 12, 66, 612 or copolymers of polyamides or mixtures thereof.

It is preferable to use an additive, Osment, filler up to 10% by mass.

In distinction from the usual, and on the "structural" plasticizers, drastically reducing the softening temperature and viscosity of polymer melts, the proposed additives practically do not change the conditions of extrusion and do not impair strength and barrier characteristics of the polymers. This makes possible their use in a conventional single screw extruder without introducing additional process steps of mixing. When using these additives in the declared amount is achieved technologically necessary plasticity of the primary sleeve, which is manifested in the stability of the process, especially when obtaining films, painted in the "problem" of color. Reducing the number of breaks during orientation extraction, leads to an increase of industrial production speed of the claimed film, as well as decrease waste polyamide raw materials. In the inventive composition is a valid introduction of dyes, pigments or fillers to 10% by weight, while the tubular film obtained uniformly and intensely colored, while maintaining flexibility and barrier characteristics of the polyamide film. This fact and the advantages obtained films from the point of consumer characteristics is B4 BASF) and additive - the product of transesterification of sunflower oil with glycerin (hydroxyl number 298-305 mg KOH/g) is stirred in a mixer of the type "drunken barrel is loaded into the hopper of the extruder. The weight percent of the polyamide and the additive in the mixture is at 99.95:0.05 per cent, respectively. From the melt with a temperature 256-262oC form the primary sleeve with a diameter of 26.5 mm and a thickness of 250-270 μm, which is at a temperature of 60oC pneumatic method is subjected to biaxial orientation of the hood with coefficients of longitudinal stretching is 2.6, transverse to 3.0. Then oriented sleeve is subjected to relaxation annealing at a temperature of 160-180oC for 15 seconds, accompanied by longitudinal shrinkage factor of 1.2, cooled to 20oC and wound into a roll. The finished film turns glossy, has a thickness 39-41 μm and the diameter 79-81 mm

For 48 hours the line was observed two cases of rupture orientation when the hood.

The results of studies of the mechanical and barrier characteristics are shown in the table.

The mechanical characteristics of the blown film was determined using a bursting machine brand "Hecker" at the speed of sliding clamps 110 mm/min Permeability to water vapor of opredelyalas and 65% relative humidity according to DIN 53 380-69.

Example No. 2.

Tubular film manufactured according to example No. 1 with the use of polyamide PA 66 (mark A4 BASF), extrusion was carried out at the temperature has reached 270-290oC, extractor fan is at 75oC, annealing is at 170-190oC.

For 48 hours the line was observed three cases of rupture orientation when the hood.

Example No. 3.

Tubular film manufactured according to the technology described in example N1 of a mixture of polyamides PA 6 and PA 612 and iron oxide pigment in the form of a 20% aqueous superconcentrate based on PA 6. The content of PA 6, PA 612, pigment, additive - 77,93:20,00:2,00:0,07% by weight, respectively. Extrusion was carried out at temperatures 245-260oC, hood - with 72oC, annealing is at 160-170oC.

For 48 hours the line was observed two cases of rupture orientation when the hood.

Example N 4.

Tubular film manufactured according to example No. 1 with the addition of the dye - perimenopause red as 25% superconcentrate. The weight percent of the polyamide, dye, additives - 99,43:0,50:0,07%, respectively.

For 48 hours the line was observed three cases of rupture orientation when the hood.

Example No. 5.

the ATA and polyethylene glycol with a molecular weight of 10,000 as an additive. The weight percent of the polyamide, pigment and additives in the mixture is 98,92:1,00:0,08%.

For 48 hours the line was observed four cases of rupture orientation when the hood.

Example No. 6.

Tubular film manufactured according to example No. 1 with the use of oleic acid as an additive and with the addition of brown iron oxide pigment in the form of a 20% aqueous superconcentrate based on PA 6. The weight percent of the polyamide, pigment and additives in the mixture is 97,94: 2,00: 0,06%.

For 48 hours the line was observed one case of rupture orientation when the hood.

Example # 7.

Tubular film manufactured according to example No. 2 using glycerol as an additive and with the addition of brown iron oxide pigment in the form of a 20% aqueous superconcentrate based on PA 6. The weight percent of the polyamide, pigment and additives in the mixture is 97,95:2,00:0,05 %.

For 48 hours the line was observed two cases of rupture orientation when the hood.

Example N 8.

Tubular film manufactured according to example No. 3 with the use of triacetate glycerol as an additive. The weight percent of the polyamide, the tear film when the orientation of the hood.

Example 9 N.

Tubular film made from a mixture of PA 6, brown iron oxide pigment in the form of a 20% aqueous superconcentrate based on PA 6, copolymer PA 6/66 (mark C35 BASF), copolymer PA 6T/61 (mark "SELAR" company "Du Pont"), oleic acid and chalk as antiblocking of additive with the mass content of the component, respectively, 77,24: 7,87:3,94:9,38:0,07: 1,50%. Modes extrusion, drawing and annealing as described in example No. 1.

For 48 hours the line was observed one case of rupture orientation when the hood.

Example N 10.

Tubular film is produced by coextruding five layers:

PA (5 μm)/ adhesive (3 μm)/PP (10 μm)/adhesive (3 μm)/PA (23 μm), where PA is a polyamide layer according to example No. 1;

the adhesive layer grafted maleic anhydride (1,5-2%) polyethylene, (mark "Bynel - SHOE" company "Du Pont");

PP - polypropylene layer brand "Kaplan-35" manufactured by LLC "Moscow oil refinery".

Polypropylene layer was abstrogirovalsya at a temperature of 260-270oC, the adhesive layer at a temperature of 240-260oC.

The layers were joined in a special co-extrusion head at a temperature of 260oC.

Modes extrusion Polyamid the th gap film orientation when the hood.

Example No. 11.

Tubular film manufactured according to example N4 with the addition of the Ethylenediamine N,N'-stearylamine (mark "Loxamid" the company "Henkel") as an additive. The weight percent of the polyamide, pigment and additives in the mixture is 98,94:1,00:0,06%.

For 48 hours the line was observed two cases of rupture orientation when the hood.

Example N 12

Tubular film manufactured according to example No. 6 with the addition of distearate of polyethylene glycol-400 (Aldrich) as an additive. The weight percent of the polyamide, pigment and additives in the mixture is 98,92:1,00:0,08%.

For 48 hours the line was observed four cases of rupture orientation when the hood.

Example N 13

Tubular film manufactured according to example No. 6 with the addition of polyethylenepolypropylene with molecular weight of 5000 (mark "Aquazol-5" firm "Polymer Chemical Innovators Co.") as an additive. The weight percent of the polyamide, pigment and additives in the mixture is 98,95:1,00:0,05%.

For 48 hours the line was observed three cases of rupture orientation when the hood.

Example No. 14.

Tubular film manufactured according to example 9 N using anise (p-methoxybenzoyl) to the S="ptx2">

For 48 hours the line was observed two cases of rupture orientation when the hood.

Example N 15.

Tubular film manufactured according to example 10 using butyrolactam (mark "2-PYROL" company "ISP") as an additive in the outer layer of polyamide. The weight percent of the polyamide, pigment and additives in the outer layer is to 97.91:2,00:0,09%.

For 48 hours the line was observed three cases of rupture orientation when the hood.

Example # 16 (comparative).

Tubular film manufactured according to example No. 1, but without additives.

2 hour line was observed eleven cases of rupture orientation when the hood.

Example N 17 (comparative).

Blown film was produced according to example No. 2, but without additives.

2 hour line was observed fifteen cases of rupture orientation when the hood.

Example N 18 (comparative).

Tubular film tried to manufacture according to examples No. 3 and No. 4, but without additives. Primary sleeve to inflate impossible.

Example No. 19 (comparative).

Tubular film manufactured according to example 8 without add the LASS="ptx2">

Example N 20 (comparative).

Multilayer tubular film manufactured according to example No. 8, and a layer of PA - as in the example No. 11.

For 48 hours the line was observed four cases of rupture when the orientation of the hood.

1. Thermoplastic polymer composition for sausage and sausage casings, consisting of one or a mixture of polyamides and technological additive, wherein the additive used is compatible with the polyamide substance that is selected from a number of higher aliphatic length of the hydrocarbon chain C6-C20and aromatic carboxylic acids, fully and nepolnoglasnyh esters of carboxylic acids and polyhydric alcohols, amides of aliphatic acids, polyhydric alcohols, oligomeric polyamides, lactams, polyalkyleneglycol with molecular weight up to 20,000, their ethers and mixtures of these substances and has thermal stability up to 300oC in an amount of 0.01 - 0.5 wt.%.

2. Thermoplastic polymer composition under item 1, characterized in that the polyamides are primarily used polyamides 6, 12, 612, 66 or copolymers of polyamides or mixtures thereof.

3. Thermoplastic polymer composition under item 1, characterized in that use is different because it contains a dye, pigment or filler to 10% by weight.

 

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