CS272090B1 - Polymer composite material on base of spliced foils and method of their preparation - Google Patents

Abstract

An aq. or alcoholic extract of Luffa cylindrica, in amount of 1-99 wt.% based on total wt. of the formulation, is added to a conventional cosmetic formulation contg. softening or moistening agents, etc

Description

Polymer composite material based on cleavable foils and process for its preparation

57) The present invention relates to polymar composite materials based on non-refillable films and to a process for their preparation.

The essence of the pleats is a polymeric kg-composite material based on Stp-foil sheets; consisting of at least one fibrillated cleavable polyolefin film as reinforcement and at least one _{/ non-} fibrillated matrix polyolefin film, wherein both the reinforced fibrillated film and the unfibrillated matrix film optionally comprise particulate or fibrous filler.

A process for preparing the above composite is to laminate the sheets at a temperature at the melting point of the unfiltered matrix foil and below the temperature at which the initial structure of the fibrillated cleavable foil is canceled at a pressure in the range of 1 to 100 kPa.

272 090 (11), (13) Bl (51) Int. Cl.®

32 B 27/32 B 32 B 27/02

CS 272 090 Bl

The invention ββ relates to polymer composite materials based on cleavable foil and to a process for their preparation.

The composites of the present invention have substantially higher toughness, crack propagation resistance and transverse cohesion than a self-oriented film prepared from a single polymeric component.

When cold-drawing a film of aemicryetallic polymers, their strength and stiffness increase in the drawing direction, but they stick together in their transverse direction. Due to the mechanical stress, the stretched film of some seaicrystalline polymers is less easily pinched to a system of parallel flbrils, never to microscopic dimensions. This phenomenon aa is called fibrillation. Isotactic polypropylene is the most fibrillated fibril; jrilaej. decreases in order: high-density polyethylene, polyamides, polyethylene terephthalate (Polymer Teating 6, 1986, 447), Fibers prepared by fibrillation are used for the production of woven and non-woven fabrics, * Insulating boards and as reinforcement and building materials (asbestos replacement).

The tendency of isotactic polypropylene to ee fibrillation is also utilized in the preparation of composite materials. According to USSR Authentication Certificate No. 103 804 ee, the polyethylene alloy e is first stretched in the solid state and then heated to a temperature that lies between the melting point of the polyethylene and the polypropylene. The result is a material comprising fine and strong polypropylene fibers embedded in a polyethylene matrix. The siny poatup (Vyeokomol. Sojed, 29, 1987, p. 778) uses high-density polyethylene drawing in a liquid monomer medium (styrene, butylaathacrylate and the like) which, upon completion of polyethylene fibrillation, leads to polymerization to form a composite matrix. It has also been described to prepare composite films by laminating extreme rigid polyethylene fibers between films of high or low density polyethylene. "Because the reinforcing fibers of such co-cozils have an approximate 100-fold strength than the matrices, even a small volume percent of the fibers has a significant effect. The disadvantage of these films in some applications, however, may be the low adhesion between the matrix and the reinforcement, the high cost of the extreme rigid polyethylene fibers used and the problems of uniform placement of the reinforcement, and? even at random or unidirectional fiber deposition.

SUMMARY OF THE INVENTION The present invention provides a polymeric composite material based on cleavable films, characterized in that it comprises at least one fibrillated polyolefin cleavable film as reinforcement and at least one unfibrillated polyolefin matrix film, wherein both the reinforcing fibrillated film and the non-fibrillated matrix films comprise optionally .

The process for preparing the polymer composite of the present invention consists in; that the film is laminated at a temperature above the melting point of the fibrillated matrix film and below the temperature at which it disrupts the starting material. structure of fibrillated cleavable foil, at a pressure of 1 to 100 kPa,

The composite material of the present invention employs fibrillated cleavable film of eemicryetallic polymers prior to breaking them into fibers. Thus, the unidirectional orientation of the reinforcing fibrils is pre-ensured. The fibrillated cleavable film is laminated alternately between the layers of the fibrillated film with a substantially lower degree of orientation; that form a matrix. The lamination temperature is selected above the melting point of the matrix layers at a temperature lower than the temperature at which the ee cancels out! structure of fibrillated layers. It is advantageous if the fibrillated film is in the prestressed state during lamination. Instead of unwanted sarstish, on the contrary, rakryetalizačnlau firming can occur. For example, in laaining fibrillated isotactic polypropylene films between low density polyethylene films, the lamination temperature may be in the range of 130-170 ° C, preferably around 160 ° C. At the same time, several layers may be laminated and the same or different fiber orientation relative to one another.

CS 272 090 Bleached film · Also, only some locations of the base unfibrillated film along the expected mechanical stress can be reinforced with the fibrillar film, for example at the edges, around the grips, meshes, and the like. The initial films are subjected to a perpendicular pressure between 1 and 100 kPa for a maximum of two hours during lamination. Oak reinforcing fibrillated films and non-fibrillated matrix composite layers may contain tufted or fibrous fillers. · After lamination, the material cools either slowly in air, * or in liquid.

The composite materials prepared according to the invention exhibit anisotropic properties of mechanical properties and their yield strength in a particular direction is approximately determined by the mixing rule according to the volume representation of the components. Due to the high strength and stiffness of the cleavable foil, however, even with a relatively small proportion of the reinforcing component, the yield strength of the starting matrix can be significantly increased. In addition, the composite has a substantially greater coherence in the direction transverse to the fibrils than the fibrillated layer material alone. The fibrillated film itself breaks under brittle interfibrillar fracture while the fibrillated laminate composite between the two matrix layers is even capable of stretching the cross-reinforcing fibrils. In this case, 9a exploits both the significant surface effect on the plasticity of the polymeric materials, the ability of the metric material to fill the inter-fibrillar spaces, and the longitudinal cracks of the fibrillated layer. At the same time, however, the fibrillated layer retains the achopnoate to block cracks growing toward the flbrils.

The following examples characterize the subject matter of the invention; without limiting it.

The composite sets shown in the following examples were prepared from four starting films: two fibrillated films (reinforcements) labeled VI, V2 and two unfibrillated films (matrices) labeled M1, M2. The fibrillated films ee showed a significant anisotropil of mechanical properties; they had a much higher strength and stiffness in the emerence orientation (along the fibrils) than in the transverse direction. On the other hand, the unfibrillated films showed only a slight (predominantly planar) orientation obtained in the production of blow molding technology.

These films were made in the form of a closed sleeve, which in Examples 1, 2 was not cut open for lamination of the composite but only folded longitudinally. Therefore, in these cases, the corresponding layer in the composite had approximately twice the thickness of the starting film. An overview of the default transparencies is given in Table 1.

Table 1

Characteristics of starting foils

Default film Specifications Thickness (/ um) In 1 high-density polyethylene Llten PE VB 33, fibrillated 25 V 2 isotactic polypropylene Mosten 58412 with 30% vol micronized limestone, * fibrillated 30 Μ 1 low density polyethylene from the GDR Ringversuch 83, foil D, unfibrillated 100 ALIGN! M 2 high-performance polyethylene from production GDR, unfibrillated 100 ALIGN!

Mutual combination of starting foils were prepared model composite foils marked

Κ 1 to K 5. Their composition and preparation are shown in Table 2.

CS 272 090 Bl

Table 2

Preparation conditions of composite foil composition

Folio Show! layers Laminating conditions Podlí reinforcement % Tgplota Pressure kPa □ both min Cooling K 1 2xMl / Vl / 2xMl 136 10.9 60 AND 6 K 2 2xMl / V2 / 2xMl 157 9.9 5 AND 7 K 3 M1 / V2 / M1 / V2 (60 °) M1 139 10.9 30 (B) 14 K 4 M2 / V2 / M2 / V2 (60 degrees) M2 139 10.9 30 (B) 14 K 5 M2 / V2 / M2 175 10.9 10 AND 13

Cooling conditions; A - air cooling 3 ° C / min.

B - cooling in water at 20 ° C

Table 3

Properties of starting and composite foils

Material y MPa fy % E Bye □ y ₂ k3 / m Reinforcement VI 200 * 60 ⁺ 2.5 1 800. V2 reinforcement 230 ⁺ 20 ⁺ 2.9 800 Matrice Ml 9 9.5 0.30 13 Matrix M1 ^a 9 9.5 0.30 13 M2 matrix 18 10 0.60 25 K _o mpozit Kl 20 May 60 0.30 170 Composite Kl ^a 15 Dec 13.5 0.30 80 Composite K2 23 21 0.33 65 Composite K3 13 14 0.40 30 K4 composite 24 12 0.75 35

- yield stress; tensile stress at fracture - yield stress ⁺ ) deformation at break

E - modulus of elasticity in tension □ y - specific deformation energy to material failure

Test conditions; Temperature 25 + -1 ° C, test speed 1 cm / min., Working length of test specimens 20 mm, width 10 mm, ^a ) test specimens with one side notch of 0.5 mm depth. The direction of evaluation of the mechanical properties was given by the fibril reinforcing arm (foil K1, * K2), possibly along the oey smaller of the angles enclosed by the fibril reinforcing layers (,3, K4).

Example 1

The fibrillated high density polyethylene film L1TEN PE VB 33 (reinforcement VI) was laminated between layers of low density polyethylene film prepared as laboratory film 0 in the IRingvarsuch 83 ring experiment in NOR (matrix M1). This film was used in the form of a closed sleeve (see FIG. 1) which melted into a single layer of double thickness during lamination. Laminaca composite material (composite K1) for «Ν.

CS 272 090 Bl _Α Bihala with fixed ends of fibrillated foil at 136 ° C, pressure 10/9 kPa for

Claims (3)

The layer K1 consisted of three layers with a thickness of 200 .mu.m (middle layer), i.e. the volume according to the reinforcement was Jan 6%. The mechanical properties of the K1 composite were evaluated in a direction along the orientation of the reinforcing layer VI. The results are summarized in Table 3. It can be seen from Table 3 that the relatively low reinforcement layer increased the toughness of the starting film M1 more than 13 times and the energy required to crack at least 6 times. The stress-strain curves of the starting components VI, M1 and the resulting composite K1 are plotted in FIG. The direction of evaluation of the mechanical properties is shown in Fig. 1. Example 2 Isotactic polypropylene MOSTEN 58412 fibrillated foil containing 30 vol *% micronized limestone (V2 reinforcement) was laminated between layers of low density polyethylene (matrix M1) as in Example 1. The lamination was carried out at 157 ° C, 9.9 kPa pressure for 5 hours. minutes. Cooling was carried out in air at a rate of 3 ° C / min. The resulting com- posite material K2 consisted of three spindles having a thickness of 200 µm (outer layers) and 30 µm (middle layer). The volume ratio of reinforcement was 7%. The results of the tensile mechanical measurements along the direction of orientation of the fibrillated layer V2 are shown in Table 3 and Figure 3. The composite material K2 exhibits approximately five times the toughness 3y determined as deformation work up to the serviceability limit per unit cross-section. In this case, the toughness of the K2 composite determines the failure of the reinforced reinforcement. Example 3 Verifying the layers of the fibrillated MOSTEN 58412 isotactic polypropylene film containing 30 vol% micronised limestone (V2 reinforcement) were alternately laminated between three layers of low density polyethylene film (matrix M1). In this case, the directions of orientation of the reinforcing layers of material V2 formed an angle of 60 DEG to each other. Laminaca was run at 139 ° C; The resultant composite material K3 consisted of five coils: three layers of low density polyethylene (matrix M1) of 100 µm thickness and two coils fibrillated polypropylene (reinforcement V2) with a thickness of 25 µm. The volume fraction of fiber reinforcement was thus 14%. The tensile mechanical characteristics were determined at an angle of 30 ° to the direction of orientation of the two reinforcing films V2. The resulting are shown in Table 3 and Figure 3, which shows a significant reinforcing effect of the fibrillated film V2. Importantly, the increase in yield strength (almost 1.5 times) and toughness (nearly 2.5 times) are also achieved outside the direction of the reinforcing fibrils. Example 4 A five-layer composite film K4 was prepared in the same manner as in Example 3, but a high density polyethylene film produced by NOR (matrix M2) was used to ground the low density polyethylene matrix. Tensile mechanical measurements were also performed as in Example 1. The results are shown in Table 3 and Figure 3. In this example, the effect of fibrillated foil on the strength properties of the composite was less pronounced than in Example 3 due to the use of a matrix with higher between yield and stiffness. Example 5 The fibrillated MOSTEN 58412 isotactic polypropylene film containing 30% by volume of milled limestone (V2 reinforcement) was laminated between the layers of high-density foil CS 272 090 B1 of polyethylene produced by the GDR (matrix M2). The lamination was carried out at 175 ° C, 10.9 kPa pressure for 10 minutes. The cooling rate was 3 ° C / min. During lamination, uneven shrinkage of the individual layers occurred, the material ee irregularly curled and contained bubbles. The lamination temperature in this case was too high to obtain a satisfactory composite film. Descriptions to borazkami Fig. 1 Preparation method of composite material K1 according to example 1 · Empty arrows show the effect of lamination pressure, thin solid arrows indicate the direction of tensile stress (and when evaluating the mechanical properties. MO indicates the film production direction (orientation). Giant. 2 Stress curves - deformation of the starting sheets M1 and VI and the resulting composite K1 according to example 1. For test conditions see Table 3 «test bodies with one side notch 0.5 mm. the arrows indicate the yield strength or tear failure (material failure limit). The area under the curve up to this limit, expressed as strain energy, is a measure of toughness. Giant. 3 Stress curves - deformation of starting films M1, M2, ^ø V2 and resulting composite films K2, K3 and K4 according to examples 2, 3 and 4. Meaning of arrows see Fig. 2, test conditions see Table 3. BACKGROUND OF THE INVENTION CLAIMS 1. Polymeric film composite material comprising at least one fibrillated cleavable polyolefin film as reinforcement and at least one non-fibrillated matrix polyolefin film, wherein both the reinforcing fibrillated film and the non-fibrillated matrix film optionally comprise particulate or fibrous filler. . 2. A process for preparing a polymer composite according to item 1; characterized in that the films are laminated at a temperature above the melting point of the unfibrillated matrix film and below a temperature at which the initial structure of the fibrillated cleavable film is abolished at a pressure in the range of 1 to 100 kPa. 3 drawings CS 272 090 Bl Giant. 1