Method for producing a thermoplastic film

Abstract

In a method for producing a thermoplastic film having a three-dimensionally textured, embossed surface, the film is subjected prior to a subsequent shaping kind of processing step to electron-beam crosslinking, which differently crosslinks the individual surface-area regions of the film, so that the regions that undergo greater degrees of drawing out during deforming have different degrees of crosslinking than their neighboring regions.

Claims

1. A process for crafting a thermoplastic film having a three-dimensionally structured surface, the process comprising the steps of: providing a film having a surface with an embossed surface structure formed in an embossing method of a preceding shaping step; subjecting the film to electron beam crosslinking for crosslinking individual regions of the film surface differently from each other and substantially in a manner such that regions of the film surface subjected to higher degrees of drawing in a subsequent shape-imparting processing step have degrees of crosslinking differing from neighboring regions of the film surface; performing the electron beam crosslinking by applying doses of radiation on two sides of the film such that the degrees of crosslinking on the two sides of the film are different due to the radiation; and subsequently subjecting the film to the shape-imparting processing step.

2. The process according to claim 1, wherein the regions subjected to higher degrees of drawing in the subsequent shape-imparting processing step have higher degrees of crosslinking than the neighboring regions.

3. The process according to claim 1, which further comprises effecting the electron beam crosslinking of the film by irradiation of at least one film surface with an electron beam source several times at least in regions.

4. The process according to claim 1, which further comprises: carrying out the electron beam crosslinking of a film surface line by line in succession; and adjusting a beam width of the electron beam with an aid of an aperture.

5. The process according to claim 3, which further comprises disposing a mask which changes an intensity of electron radiation at least in partial regions of a beam cross section between an electron beam source and an irradiated film surface.

6. The process according to claim 1, which further comprises performing a shape-imparting thermoforming step as the shape-imparting processing step.

7. The process according to claim 1, which further comprises providing the thermoplastic film as a multilayer polymer film composite.

8. The process according to claim 1, which further comprises providing the thermoplastic film with a thickness of 0.4 to 4 mm.

9. The process according to claim 1, which further comprises providing the regions subjected to higher degrees of drawing in the subsequent shape-imparting processing step with a gel content of at least 30%.

10. The process according to claim 1, which further comprises providing the regions subjected to higher degrees of drawing in the subsequent shape-imparting processing step with a gel content of 40 to 60%.

11. The process according to claim 1, which further comprises providing a difference in a gel content between regions of the film which have a high degree of crosslinking and regions of the film which have a low degree of crosslinking to be from 10 to 60%.

12. The process according to claim 1, which further comprises providing a difference in a gel content between regions of the film which have a high degree of crosslinking and regions of the film which have a low degree of crosslinking to be from 20 to 50%.

13. The process according to claim 1, wherein the shape-imparting processing step includes drawing the film into a mold.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The crosslinking of polymers takes place through formation of covalent bonds between the polymer chains. Usually, the crosslinking is effected by the classical vulcanization with elemental sulfur or silanes, by peroxide crosslinking, by crosslinking with electron beams or by a combination of the methods. In electron beam crosslinking, the free radicals initiating the crosslinking process form through the action of high-energy radiation on the polymer molecules. The accelerated electrons interact with the irradiated molecules. The kinetic energy of the electrons is transferred to atoms with the molecular assembly by elastic impacts. The atoms affected are thus converted into a more highly excited state. If the energy thus supplied is greater than the bond energy of the covalent bonds, the bond is cleaved and free radicals, macroradicals and ions form.

(2) The free radicals react in subsequent reactions with the molecules of the polymer chains or with themselves and lead both to the formation of covalent bonds between the individual chains and to the degradation of the macromolecules by chain cleavage. Chain cleavage and chain synthesis take place in parallel. The polymer type used and the processing conditions, such as radiation dose, type of radiation, temperature, etc. determine which reaction dominates. Establishing process parameters in electron beam crosslinking is therefore of primary importance. Since chain degradation also takes place, crosslinking of all polymer chains present with one another cannot be realized. Although complete crosslinking is not achieved by radiation crosslinking, main features of the irradiated polymers are nevertheless strongly influenced.

(3) The crosslinking points newly formed during crosslinking induced by electron beams hinder the folding process of the polymer chains. This results in a reduction in the crystallinity, in particular the mechanical strength and brittleness decreasing with decreasing crystallinity whereas toughness and insulation properties increase. In most cases, however, a decrease in the strength which is to be expected owing to the decrease in crystallinity does not in fact occur. The reason for this is that the lower crystallinity is overcompensated by the increased structural strength of the crosslinked amorphous regions. The cohesive forces between the crosslinked polymer chain segments are several times greater than in the uncrosslinked state, where only van der Waals interaction forces act between the chains. The sliding and displacement of the polymer chains are made substantially more difficult as a result of the crosslinking. These changes manifest themselves, for example, in an increase in the mechanical strength and the heat distortion resistance.

(4) Because the regions which are subjected to higher degrees of drawing in the subsequent shape-imparting processing step have degrees of crosslinking differing from their neighboring regions, in particular and advantageously higher degrees of crosslinking, an extremely uniform surface structure is retained even after the subsequent deformation step, for example after the application of the film to a three-dimensional component.

(5) This is because the strongly formed film regions, i.e. for example those on projecting geometries having small radii, extend to a greater degree than the neighboring regions and therefore transmit the deformation stresses to the neighboring region. Viewed over the total area, the surface tension of the film after the deformation then becomes uniform. As a result, the surface structure is also substantially retained, but in any case so that a change is not noticeable to the naked eye. In the conventional processes in the prior art, the regions having higher degrees of drawing had to adsorb the total elongation alone, i.e. for example were elongated by 60%, while the directly adjacent regions were not elongated. The differences in the structure were therefore often noticeably large. In the process according to the invention, the elongation of the regions having higher degrees of drawing is greatly reduced by the crosslinking, with the result that transmission of the forming stresses also takes place to the adjacent regions so that both regions are elongated by approximately equal amounts of, for example 25-30%. Structural differences in the transition between the regions are thus substantially reduced.

(6) A distribution of the newly formed crosslinking points which is inhomogeneous over the film surface, i.e. the crosslinking density distribution or network arc densityfor example expressed by the gel content as a known measure for the crosslinkingcan be particularly advantageously achieved if the film is exposed from both sides to electron radiation, it being possible for the degrees of crosslinking to be different on the two film sides or film surfaces.

(7) As a result, the total crosslinking of individual regions can be influenced both via the irradiated area and via the radiation intensity and thereby influenceable effect of the crosslinking in the thickness direction of the film.

(8) In the case of irradiation on one side, the region of maximum dose adsorption can be varied and hence defined in the case of the crosslinking density distribution by the choice of the acceleration voltage for the electrons, depending on the film thickness.

(9) In the case of irradiation on two sides, the crosslinking density distribution can moreover be influenced by the relation of the applied doses with variation of the respective acceleration voltage. Depending on the respective compositions of the films to be irradiated, these have to be adapted again for each chemical system.

(10) In an advantageous further development, the electron beam crosslinking of the film is effected by irradiation of at least one film surface with an electron beam source several times at least in regions. The desired difference in the crosslinking can be produced simply through the simple local control of the radiation source of the electron beam. Since the films to be processed are usually present as web material, the width of the film webs being determined by the preceding production, it is of course possible in the context of the invention to carry out different irradiation variants which are adapted to the further processing of the film web. If, for example, it is certain that the middle region of a film web is always that which occurs in the region of the instrument cover of a dashboard during the subsequent shaping and hence masked bear the greatest degrees of drawing, it is just this middle region of the film which is crosslinked once or several times according to the invention.

(11) An advantageous further development relates in carrying out the electron beam crosslinking of the film surface line by line in succession, the beam width of the electron beam being adjustable by use of an aperture. With the aid of such scanning, a degree of crosslinking differing over the film width can be established in a simple manner.

(12) This also applies to another advantageous further development which relates to arranging a mask, which changes the intensity of the electron radiation at least in partial regions of the beam cross section, between the electron beam source and the irradiated film surface.

(13) A thermoplastic film of crosslinked polymeric material having a three-dimensionally structured, embossed surface which is formed of a thermoplastic elastomer, in particular a thermoplastic olefin (TPO) or a polyolefin mixture, is particularly suitable for use in the process according to the invention.

(14) The particular advantage of using this polymer type in the case of the film according to the invention is that the originally present intermolecular crosslinking of a thermoplastic olefin (hydrogen bridges, crystalline structures) is predominantly thermoreversible and substantially of a physical nature, which is fundamental with regard to the suitability for deformation. The additional electron beam crosslinking of certain regions of the polyolefin provides the particular and surprising property of the film in which on the one hand elongation behavior required for the forming and on the other hand sufficient resistance to excessive elongations of the surface for reliable material handling of the process are present during the forming step usually taking place at elevated temperature.

(15) In another advantageous further development, the film formed of precrosslinked polymeric materials, in particular of a composition of polypropylene, polyethylene and copolymers and terpolymers thereof, which are particularly suitable for use as a film for a motor vehicle interior. This too gives a particularly uniform surface structure without striking excess elongations after the subsequent deformation step. The precrosslinking is effected by chemical method by addition of customary crosslinking agents.

(16) In another advantageous further development, the film is in the form of a multilayer polymer film composite. Such a formation promotes the influenceable effect of the crosslinking in the thickness direction of the film and hence the total crosslinking of individual film regions.

(17) The constituents of the polymer films are preferably polyolefins. The range of polyolefins which may be used is not subject to any fundamental limitation. Polyolefins, such as PP, PE, poly(1-butene), polyisobutylene, poly(4-methylpentene), PP copolymer or terpolymers with C.sub.2, C.sub.4-C.sub.12--olefins, PE copolymers or terpolymers with C.sub.3 to C.sub.12--olefins or mixtures thereof can preferably be used, it also being possible to use as co- or termonomers diene monomers which contain nonconjugated double bonds, such as, for example, 1,4-hexadiene, 5-methyl-1,5-hexadiene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, dicyclopentadiene, 1,4-octadiene, cyclohexadiene or cyclooctadiene; copolymers of propylene and/or ethylene with polar comonomers, such as acrylic acid and/or the C.sub.1-C.sub.12-esters thereof, methacrylic acid and/or the C.sub.1-C.sub.12-esters thereof, ionomers based on acrylic acid and/or with methacrylic acid and sulfuric acid, vinyl esters of saturated C.sub.1-C.sub.8-carboxylic acids, optionally with carbon monoxide as a termonomer; graft copolymers of propylene and/or ethylene having 8-45% of grafted-on units of unsaturated carboxylic acids, dicarboxylic acids, the esters and/or anhydrides thereof and mixtures of the polymers.

(18) In another advantageous further development, the film has a thickness of from 0.4 to 4 mm. As a result, the adjustability of the depth of crosslinking is further facilitated.

(19) With the aim of making the elongation highly uniform, the crosslinking of the film is advantageously adjusted so that, in the regions which are subjected to higher degrees of drawing in the subsequent shape-imparting processing step, the film has a gel content of at least 30%, preferably a gel content of from 40 to 60%. As a result, the grain tightness of the elongated regions of the film is sufficiently high to prevent a distortion of the surface structure/grain structure, the other regions of the film which have the lower gel content providing sufficient extensibility to achieve reliable deformation in the process for covering a three-dimensional component.

(20) In an advantageous development, the difference in the gel content between regions of the film which have a high degree of crosslinking and a low degree of crosslinking is from 10 to 60%, preferably from 20 to 50%. As a result, sufficient uniformity of the elongations of the material is achieved even in the case of strongly deformed components, such as, for example, in the case of covers for the transmission tunnel of a car.

(21) The determination of the gel content is usually effected via an extraction method in which first samples with a thickness of about 0.5 mm are cut into squares having an edge length of about 1.0 mm. The samples (about 100 mg) are then initially introduced into test tubes which are provided with plugs which are made of stainless steel wire and prevent the samples from floating. The test tubes are filled with 100 ml of xylene and closed with aluminum foil in order to prevent evaporation of the solvents. The xylene is then heated to the boil. The test specimens are left in the boiling xylene for about 24 h. Thereafter, the gel-xylene mixture is filtered over a drum screen having a mesh size of 200 mesh, the gel remaining in the drum screen. The drum screens are placed on metal plates and dried at 140 C. for 3 h in a through-circulation oven. After cooling to room temperature, the content is weighed out and related to the sample weight.

(22) The abovementioned production process can be particularly advantageously used for a dashboard for the interior cladding of motor vehicles with an outer surface in the form of a foam-backed film. Such dashboards often have highly formed regions which are directly and permanently visible to driver and passenger. This applies, for example, to the instrument cover, to the glove compartment and to ventilation nozzles and cut-outs. Here, making the elongations uniform, as is achieved in the film by the process according to the invention, is particularly important for esthetic reasons.