Artificial leather based on vinyl chloride grafted copolymers

Abstract

The present invention relates to an artificial leather comprising a vinyl chloride graft copolymer and an ethylene-vinyl acetate copolymer with a vinyl acetate content of at least 38% by weight.

Description

[0001] The present invention relates to an artificial leather comprising a vinyl chloride graft copolymer and an ethylene-vinyl acetate copolymer with a vinyl acetate content of at least 38% by weight.

[0002] Artificial leather is a leather imitation, usually a composite of a textile base (e.g., a woven fabric) and a plastic top layer (e.g., PVC-P). The woven fabrics are made of natural fibers, synthetic fibers, or blends, often coated with soft PVC (PVC-P). This coating can be applied as a solid or foamed layer, depending on the application. The surface is frequently embossed with a grain pattern to resemble leather in texture.

[0003] Examples of applications for synthetic leather include jackets, belts, shoes (especially sports shoes), bags, balls (e.g., soccer balls), convertible tops and gearshift boots, flexible automotive trim, seat covers, and other furniture coverings such as sofas and armchairs. To achieve a certain softness in the coating, necessary for a pleasant feel and to give the material the appropriate fullness, as well as comfort, the coating is applied with a foam backing and a compact top layer. A foam structure is created, for example, in PVC-P using chemical blowing agents or expandable hollow spheres (e.g., Expancell).

[0004] There are several reasons for using synthetic leather instead of genuine leather. Synthetic leathers based on PVC-P are quite inexpensive and very robust, while polyurethane synthetic leathers, unlike leather, are machine washable and dry without hardening. Therefore, the latter are frequently used for athletic shoes. Because synthetic leather is produced as a continuous material on textile backings, cutting it is much easier than with leather. The quality is always consistent, and the manufacturing process is considerably shorter, as the complex tanning process is eliminated. Furthermore, synthetic leathers are not dependent on the market availability of specific animal hides.

[0005] However, commercially available synthetic leather currently reaches its limits under certain conditions. For example, PVC-P contains monomer or polymer plasticizers that can migrate to the surface or into a contact medium over time, leading to a sticky, dirt-prone surface and subsequently to embrittlement. Contact with oils or fats can accelerate this process and cause cracking. Such cracking is also observed in PU synthetic leather after relatively short periods of use (e.g., in furniture leather). This is often triggered by contact with human skin and a lack of resistance to grease and perspiration.

[0006] In JP S56 20045 A a resin composition for artificial leather with improved grip is provided, produced by dissolving an ethylene / vinyl acetate / vinyl chloride graft copolymer and an inorganic thixotropic agent in a solvent.

[0007] The object of the present invention was therefore to provide an artificial leather which overcomes the disadvantages of the prior art.

[0008] Surprisingly, it was found that the combination of vinyl chloride graft copolymers (e.g., as described in EP 0 647 663 A1) with an acetate-rich ethyl vinyl acetate copolymer (e.g., Levamelt® from Arlanxeo) can be processed into a soft synthetic leather without the use of additional plasticizers.

[0009] The synthetic leather according to the invention exhibits very good oil and grease resistance. Furthermore, it possesses excellent aging and weather resistance as well as high cold flexibility. It is vapor-permeable (e.g., to water vapor), thermoformable, recyclable, vegan, and shows virtually no fogging. Moreover, its hardness (Shore A / D) and flexibility can be adjusted within a wide range.

[0010] The invention relates to an artificial leather which contains the following components (I) and (II): (I) a vinyl chloride graft copolymer, such as described in EP 0 647 663 A1; and (II) an ethylene vinyl acetate copolymer with a vinyl acetate content of at least 38 wt.%.

[0011] The vinyl chloride graft copolymers disclosed in EP 0 647 663 A1 and their manufacture are expressly referred to herein.

[0012] The present invention relates to an artificial leather comprising the following components (I) and (II): (I) a vinyl chloride graft copolymer containing: A) 35 to 60 wt%, based on the total weight of the vinyl chloride graft copolymer, of a grafted, cross-linked copolymer, producible by copolymerization of: 80 to 99.95 wt% vinyl chloride, 0.05 to 3.0 wt% polyethylene unsaturated comonomers and 0 to 19.95 wt% other copolymerizable ethylene unsaturated comonomers, or 35 to 60 wt%, based on the total weight of the vinyl chloride graft copolymer, of a grafted (co)polymer, producible by (co)polymerization of 80 to 100 wt% vinyl chloride and 0 to 20 wt% other copolymerizable ethylene unsaturated comonomers, at a polymerization temperature of 30 to 85°C, and B) 40 to 65 wt.%, based on the total weight of the vinyl chloride graft copolymer, a cross-linked graft base containing a cross-linked acrylic acid ester copolymer with 0.01 to 5 wt.-% polyethylene unsaturated comonomer units and optionally further comonomer units copolymerizable with acrylic acid esters; and (II) an ethylene-vinyl acetate copolymer with a vinyl acetate content of 38 to 92 wt.%. Component (I):

[0013] Preferably the vinyl chloride graft copolymer (component (I)) contains 40 to 55 wt.% of the grafted, cross-linked copolymer A) or the grafted, uncross-linked (co)polymer A) and 45 to 60 wt.% of the cross-linked graft base B).

[0014] Suitable polyethylene unsaturated comonomers for crosslinking the grafted vinyl chloride copolymer A) are those which do not have conjugated double bonds, for example divinyl esters of dicarboxylic acids such as divinyl adipate; diallyl esters of polycarboxylic acids such as diallyl phthalate, diallyl fumarate; divinyl ethers of polyhydric alcohols such as ethylene glycol divinyl ether; divinyl aromatics such as divinylbenzene; allyl and methallyl esters of ethylene unsaturated monocarboxylic acids such as allyl methacrylate; Di- and triacrylates of polyhydric alcohols such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate (DEGDA), diethylene glycol dimethacrylate (DEGDMA), trimethylene glycol diacrylate, butylene glycol diacrylate, pentamethylene glycol diacrylate, glyceryl triacrylate, trimethylolpropane triacrylate (TMPTA), trimethyolpropane trimethacrylate (TMPTMA); tetraacrylates of polyhydric alcohols such as pentaerythritol tetraacrylate and triallyl cyanurate.

[0015] Preferred materials include diallyl phthalate, divinyl adipate, triallyl cyanurate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, and trimethylpropane triacrylate, or mixtures thereof. Preferably, the amount of copolymerized crosslinker is 0.1 to 1.5 wt.%, based on the total weight of the grafted copolymer A).

[0016] In addition to vinyl chloride and, if applicable, polyethylene-unsaturated comonomers, the grafted copolymer A) may contain one or more further copolymerized, ethylene-unsaturated comonomers. Examples include vinyl esters of saturated carboxylic acids with 2 to 12 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl laurate, or versatic acid vinyl ester; (meth)acrylic acid esters of alcohols with 1 to 8 carbon atoms, such as methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, 2-ethylhexyl acrylate; glycidyl methacrylate; ethylene-unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid; mono- and diesters of ethylene-unsaturated dicarboxylic acids, such as diisopropyl fumarate; vinyl aromatics, such as styrene; and olefins, such as ethylene.

[0017] The graft base used in the present invention contains a cross-linked acrylic ester copolymer with 0.01 to 5 wt.% polyethylene unsaturated comonomer units and optionally further copolymerizable comonomer units or mixtures of such copolymers.

[0018] Suitable acrylic acid ester copolymers are those made from one or more acrylic acid esters of alcohols with 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate.

[0019] The term "polyethylene unsaturated comonomer units" preferably refers to structural units obtained by reacting the corresponding polyethylene unsaturated comonomers. The term "comonomer units copolymerizable with acrylic esters" preferably refers to structural units obtained by reacting the corresponding comonomers copolymerizable with acrylic esters.

[0020] Suitable polyethylene unsaturated comonomer units can be based on or produced from the comonomers already mentioned above. Preferably, the cross-linked acrylate graft base contains 0.05 to 0.5 wt%, based on the total weight of the graft base, copolymerized diallyl phthalate, divinyl adipate, triallyl cyanurate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethyol propane triacrylate, or mixtures thereof.

[0021] Examples of other copolymerizable, ethylene-unsaturated comonomers include vinyl esters of saturated carboxylic acids with 2 to 12 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl laurate, or versatic acid vinyl ester; methacrylic acid esters of alcohols with 1 to 8 carbon atoms, such as methyl methacrylate and n-butyl methacrylate; ethylene-unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid; mono- and diesters of ethylene-unsaturated dicarboxylic acids, such as diisopropyl fumarate; vinyl aromatics, such as styrene; olefins, such as ethylene; and sulfonates, such as vinylsulfonate and 2-acrylamido-2-methylpropanesulfonate.

[0022] Crosslinked acrylic ester copolymers of n-butyl acrylate and / or 2-ethylhexyl acrylate are preferred. Crosslinked acrylic ester-ethylene vinyl ester copolymers with an acrylic ester content of 35 to 70 wt.%, an ethylene content of 10 to 30 wt.%, and a vinyl ester content of 20 to 50 wt.%, based on the total weight of copolymer B), are also preferred as graft bases (B), particularly crosslinked copolymers containing n-butyl acrylate, ethylene, and vinyl acetate units. Optionally, mixtures of the aforementioned acrylic ester copolymers may also be included.

[0023] Particularly preferably, according to the present invention, vinyl chloride graft copolymers are used as component (I), comprising: A) 40 to 55 wt%, based on the total weight of the graft copolymer, of a grafted, cross-linked copolymer of 98.5 to 99.9 wt% vinyl chloride and 0.1 to 1.5 wt% of one or more polyethylene unsaturated comonomers from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethylpropane triacrylate, or 40 to 55 wt%, based on the total weight of the vinyl chloride graft copolymer, of a grafted VC polymer, producible by graft polymerization of vinyl chloride at a polymerization temperature of 30 to 85°C, and B) 45 to 60 wt%, based on the total weight of the graft copolymer, of a cross-linked graft base consisting of a cross-linked copolymer of n-Butyl acrylate and / or 2-Ethylhexyl acrylate, or from a cross-linked acrylic acid ester-ethylene vinyl acetate copolymer with an acrylate content of 35 to 70 wt.-% or mixtures of the aforementioned copolymers, wherein the copolymers are crosslinked with 0.05 to 0.5 wt% of one or more copolymerized, polyethylene unsaturated comonomers from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, and trimethyolpropane triacrylate.

[0024] The preparation of the vinyl chloride graft copolymers to be used as component (I) is described in detail in EP 0 647 663 A1. Component (II):

[0025] Component (II) is an ethylene-vinyl acetate copolymer with a vinyl acetate content of at least 38 wt.%. The ethylene-vinyl acetate copolymers used as component (II) preferably have a vinyl acetate content of 38 to 92 wt.%, particularly preferably 43 to 75 wt.%; and especially preferably 48 to 72 wt.%. The vinyl acetate content specified in this application always refers to the total amount of ethylene units and vinyl acetate units in the ethylene-vinyl acetate copolymer, which is 100 wt.%.

[0026] Suitable manufacturing processes for the ethylene-vinyl acetate copolymers used as component (II) are mentioned, for example, in EP 0 341 499 A2, EP 0 510 478 A1, DE 37 31 054 A1 and DE 38 25 450 A1.

[0027] Suitable ethylene-vinyl acetate copolymers as component (II) are commercially available, for example, under the trade name Levamelt®< from ARLANXEO. These are preferably ethylene-vinyl acetate copolymers such as Levamelt®< 400, Levamelt®< 450, Levamelt®< 452, Levamelt®< 456, Levamelt®< 500, Levamelt®< 600, Levamelt®< 686, Levamelt®< 700, Levamelt®< 800 or Levamelt®< 900.

[0028] The artificial leather according to the invention contains component (I) and component (II) preferably in a weight ratio of component (I) to component (II) of 98:2 to 70:30; particularly preferably of 95:5 to 75:25.

[0029] The artificial leather of the present invention may optionally further comprise additives.

[0030] Additives may include, for example, fillers (e.g., chalk, talc), stabilizers (e.g., Ca / Zn or Ba / Zn soaps, organic stabilizers), costabilizers (e.g., epoxidized soybean oil), antistatic agents, flame retardants (e.g., aluminum hydroxide), lubricants (e.g., internal and external lubricants), pigments (e.g., organic and inorganic pigments, TiO2, carbon black), blowing agents, antibacterial agents, and mixtures thereof.

[0031] The amount of additives is preferably 0.1 to 80 wt.%, based on the weight of the vinyl chloride graft copolymer, and particularly preferably 2 to 20%.

[0032] The artificial leather according to the invention may optionally contain further plasticizers (e.g., monomeric or polymeric plasticizers). Preferably, however, the artificial leather according to the invention does not contain any further plasticizers.

[0033] The artificial leather of the present invention can be produced, for example, as follows: To produce the artificial leather according to the invention, the components (I) and (II) and, if applicable, the additional additives can be mixed and homogenized, for example, in a mixer (e.g., Henschel).

[0034] The resulting mixture can then be plasticized, for example, on a mixing mill or in an extruder.

[0035] The mixture can then be calendered or extruded into a film, for example using a calender.

[0036] The resulting foil can optionally be further embossed on one or both surfaces.

[0037] According to a preferred embodiment, the artificial leather according to the invention is produced as a film with a thickness of 100 µm to 2000 µm.

[0038] In contrast to conventional synthetic leather, the synthetic leather of the present invention does not require a textile arrangement (e.g., no textile backing). Its homogeneous structure facilitates recyclability. Furthermore, the synthetic leather according to the invention is thermoformable without a textile arrangement.

[0039] However, the artificial leather according to the invention may optionally comprise a textile arrangement.

[0040] This textile arrangement can, in principle, be designed in a variety of ways and preferably adapted to the desired area of ​​application.

[0041] For example, the textile arrangement can include a textile layer selected from the group consisting of a woven fabric, a knitted fabric, a crocheted fabric, a nonwoven fabric, or even a 3D spacer fabric. The textile materials described above can be used not only individually but also as a suitable mixture.

[0042] Furthermore, the textile arrangement, or a textile layer contained therein, may be designed to be based on natural fibers or on artificial or synthetic fibers. The specific selection of fibers for the textile layer can, in turn, be made in a manner readily understandable to a person skilled in the art, based on the specific application intended.

[0043] The advantage of a textile arrangement can be, for example, that this layer gives the entire artificial leather a higher mechanical stability.

[0044] Another advantage of a textile arrangement (especially as a carrier layer in a layered structure of the artificial leather) can be that by providing a textile layer, a textile feel of the artificial leather can be achieved, which can significantly improve the acceptance of the artificial leather.

[0045] The artificial leather according to the invention can be printed using all common methods. A coating for surface protection is also possible. Examples

[0046] Table 1 shows various synthetic leather compositions. The synthetic leathers in comparative examples 1 and 2 contain an S-PVC in combination with a DOTP plasticizer. The synthetic leathers according to the invention (examples 1 to 4) contain a vinyl chloride graft copolymer in combination with an ethylene-vinyl acetate copolymer (EVA).

[0047] The individual ingredients were first homogenized in a Collette mixer for 10 minutes at room temperature. The mixture was then plasticized in a mixing roller mill for 5 minutes at 165°C. Subsequent processing into a 400 µm thick film was carried out on a 4-roll experimental calender at 180°C and a speed of 2 m / min. Table 1 Ingredient* (trade name) Comparative example 1 Comparative example 2 Example 1 Example 2 Example 3 Example 4 S 4170 Standard 100 100 K 707 E Standard 92,0 85,0 90 80 Baerostab NT580A 2,5 2,5 2,5 2,5 2,5 2,5 Barerostab ASM711 3 3 3 3 3 3 Eastman 168 67 83 Paradoid K120N 1 1 1 1 1 1 Loxiol G70 0,3 0,3 0,3 0,3 0,3 0,3 Kronos 2220 1 1 1 1 1 1 Printex V 0,05 0,05 0,05 0,05 0,05 0,05 Levamelt 600 8 15 10 20 K221 Standard 10 10 Alfrimal 446 15 15 * S 4170 Standard: S-PVC K-value 70; K 707 E Standard: Vinyl chloride graft copolymer; Baerostab NT580A: Ca / Zn stabilizer; Baerostab ASM711: Booster; Eastman 168: DOTP plasticizer; Paraloid K120N: Processing aid; Loxiol G70: Lubricant; Kronos 2220: TiO2 pigment; Printex V: Carbon black; Levamelt 600: EVA; K221 Standard: Antiblocking / structuring agent; Alfrimal 446: Flame retardant.

[0048] The artificial leather samples were examined for various properties. The results are shown in Table 2. Table 2 Shore hardness A DIN 53505 Comparative example 1 Comparative example 2 Example 1 Example 2 Example 3 Example 4 before storage 80,0 70,8 85,2 73,9 83,7 72,3 After storage for 8 days in paraffin oil at 70 °C 88,0 84,0 85,6 74,4 82,6 73,1 after storage for 8 days in IRM 90,8 89,8 72,0 58,0 69,9 56,0 after storage for 32 days in IRM 903 96,8 96,4 67,0 53,0 65,0 48,6 After storage for 32 days in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C 95,5 83,0 78,6 67,2 77,2 65,7 Cold fracture temperature in °C (based on ISO 8570) before storage -45,0 -41,0 -45,0 -43,0 -35,0 -32,0 After storage for 8 days in IRM at 90 °C 20,0 20,0 -49,0 -50,0 -31,0 -30,0 After storage for 32 days in paraffin oil at 70 °C 20,0 20,0 -48,0 -48,0 -20,0 -29,0 After storage for 32 days in mixed oil at 40 °C 20,0 20,0 -54,0 -52,0 -35,0 -39,0 Fogging according to DIN 75201 method B in mg 2,41 2,75 0,00 0,05 0,05 0,00 Oven stability at 200°C in the Mathis - Oven No discoloration after 70 min 70 min 70 min 70 min 70 min 70 min Water vapor permeability in g / m² < day DIN 53122 4,24 5,58 8,23 8,15 6,90 7,30 Tensile properties DIN EN ISO 527 1-3 before storage (tear strength in MPa) 18,3 16,0 17,4 15,6 12,8 11,3 before storage (elongation at break in %) 349,0 378,1 246,7 268,6 221,2 271,4 After storage for 8 days in mixed oil at 40 °C (tear strength in MPa) 23,2 20,3 13,2 10,1 9,7 7,26 After storage for 8 days in mixed oil at 40 °C (elongation at break in %) 4,2 52,8 236,4 248,8 224,6 264,2 After storage for 8 days in IRM 903 oil at 90°C (tear strength in MPa) 29,3 27,9 8,25 6,08 6,51 4,31 After storage for 8 days in IRM 903 oil at 90°C (elongation at break in %) 3,8 3,7 187,0 200,3 181,7 212,3 After storage for 32 days in IRM 903 oil at 90°C (tear strength in MPa) 36,8 36,2 7,94 6,29 6,22 4,51 After storage for 32 days in IRM 903 oil at 90°C (elongation at break in %) 2,4 2,9 173,0 194,2 173,4 209,6 After storage for 32 days in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C (tear strength in MPa) 25,7 23,3 11,3 8,51 7,83 5,43 After storage for 32 days in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C (elongation at break in %) 4,4 4,5 226,8 237,2 205,1 239,3 After storage, 14 days at 120 °C in a heating oven (tear strength in MPa) 28,5 21,7 16,6 13,1 12,1 9,9 After storage for 14 days at 120 °C in a heating oven (elongation at break in %) 327,75 378,4 242,9 259,6 229,3 284,8 After storage for 14 days at 140 °C in a heating oven (tear strength in MPa) 34,2 35,7 18,4 17,4 16,3 14,8 After storage for 14 days at 140 °C in a heating oven (elongation at break in %) 32,7 19,8 77,5 91,2 50,1 58,7 Determination of behavior towards liquid chemicals in accordance with DIN EN ISO 175 (mass change in %) in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C after 2 days -14,30 -19,70 3,16 3,78 2,69 3,69 in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C after 4 days -15,60 -19,40 4,79 5,78 4,10 5,68 in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C after 8 days -15,20 -19,20 7,04 8,51 6,03 8,39 in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C after 16 days -15,00 -19,30 9,75 11,68 8,49 11,53 in mixed oil (jojoba oil, babassu oil, squalene 1:1:1) at 40 °C after 32 days -15,60 -19,80 12,28 14,50 11,02 14,28 in paraffin oil at 70 °C after 2 days -11,10 -17,5 0,99 1,08 0,92 1,19 in paraffin oil at 70 °C after 4 days -14,20 -21,30 1,31 1,45 1,21 1,52 in paraffin oil at 70 °C after 8 days -17,40 -24,80 1,62 1,83 1,52 1,87 in paraffin oil at 70 °C after 16 days -20,00 -27,20 1,82 2,09 1,70 2,07 in paraffin oil at 70 °C after 32 days -22,20 -28,20 1,85 2,13 1,74 2,10 in IRM 903 at 90 °C after 2 days -14,90 -20,10 25,75 28,07 23,44 26,64 in IRM 903 at 90 °C after 4 days -17,80 -22,70 26,70 29,23 24,69 27,99 in IRM 903 at 90 °C after 8 days -20,50 -25,00 27,58 30,23 25,59 29,04 in IRM 903 at 90 °C after 16 days -22,70 -27,00 29,06 31,75 26,84 30,22 in IRM 903 at 90 °C after 32 days -24,20 -28,50 30,79 33,72 28,49 31,77

[0049] As can be seen from Table 2, the artificial leathers according to the invention exhibit comparable flexibility (Shore hardness A) to the artificial leathers of the comparative examples. In contrast to the comparative examples, the artificial leathers according to the invention do not harden when stored in oil. Furthermore, unlike the comparative examples, the artificial leathers according to the invention do not lose their cold flexibility when stored in oil.

[0050] In contrast to the comparison examples, the artificial leathers according to the invention show practically no fogging.

[0051] The high water vapor permeability of the artificial leather according to the invention is advantageous, for example, for clothing and shoes.

[0052] The investigations to determine the behavior against liquid chemicals clearly show that in the comparison examples, the plasticizer is dissolved by the oils.

[0053] This behavior is also confirmed in tensile tests. Oil contact reduces the plasticizer content and increases the tensile strength. The elongation at break drops significantly in some cases due to the accompanying embrittlement.

Claims

1. Artificial leather comprising the following components (I) and (II): (I) a vinyl chloride graft copolymer comprising: A) 35 to 60% by weight, based on the total weight of the vinyl chloride graft copolymer, of a grafted, crosslinked copolymer obtainable by copolymerisation of: 80 to 99.95% by weight of vinyl chloride, 0.05 to 3.0% by weight of ethylenically polyunsaturated comonomers, and 0 to 19.95% by weight of further copolymerisable ethylenically unsaturated comonomers, or 35 to 60 % by weight, based on the total weight of the vinyl chloride graft copolymer, of a grafted (co)polymer obtainable by (co)polymerisation of 80 to 100 % by weight vinyl chloride and 0 to 20 % by weight of other copolymerisable, ethylenically unsaturated comonomers, at a polymerisation temperature of 30 to 85 °C, and B) 40 to 65 % by weight, based on the total weight of the vinyl chloride graft copolymer, of a crosslinked graft base comprising a crosslinked acrylic acid ester copolymer containing 0.01 to 5 % by weight of ethylenically polyunsaturated comonomer units and optionally further comonomer units copolymerisable with acrylic acid esters; and (II) an ethylene-vinyl acetate copolymer with a vinyl acetate content of 38 to 92 % by weight.

2. Artificial leather according to claim 1, wherein the ethylenically polyunsaturated comonomers have no conjugated double bonds, for example divinyl esters of dicarboxylic acids such as divinyl adipate; diallyl esters of polycarboxylic acids such as diallyl phthalate, diallyl fumarate; divinyl ethers of polyhydric alcohols such as ethylene glycol divinyl ether; divinyl aromatics such as divinylbenzene; allyl and methallyl esters of ethylenically unsaturated monocarboxylic acids such as allyl methacrylate; di- and triacrylates of polyhydric alcohols such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate (DEGDA), diethylene glycol dimethacrylate (DEGDMA), trimethylene glycol diacrylate, butylene glycol diacrylate, pentamethylene glycol diacrylate, glyceryl triacrylate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA); Tetraacrylates of polyhydric alcohols such as pentaerythritol tetraacrylate; Triallyl cyanurate.

3. Artificial leather according to claim 1, wherein the ethylenically polyunsaturated comonomers are selected from diallyl phthalate, divinyl adipate, triallyl cyanurate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate and trimethylolpropane triacrylate or mixtures thereof.

4. Artificial leather according to one of the preceding claims, wherein the further copolymerisable ethylenically unsaturated comonomers are selected from: vinyl esters of saturated carboxylic acids having 2 to 12 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl laurate or vinyl ester of versatic acid; (meth)acrylic acid esters of alcohols with 1 to 8 carbon atoms, such as methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, 2-ethylhexyl acrylate; glycidyl methacrylate, ethylenically unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid; mono- and diesters of ethylenically unsaturated dicarboxylic acids such as diisopropyl fumarate; vinyl aromatics such as styrene; and olefins such as ethylene.

5. Artificial leather according to one of the preceding claims, wherein the crosslinked acrylic acid ester copolymer was manufactured from one or more acrylic acid esters of alcohols having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate.

6. Artificial leather according to claim 1, containing as component (I): A) 40 to 55 % by weight, based on the total weight of the graft copolymer, of a grafted, crosslinked copolymer comprising 98.5 to 99.9 % by weight of vinyl chloride and 0.1 to 1.5 % by weight of one or more ethylenically polyunsaturated comonomers from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethylolpropane triacrylate, or 40 to 55 % by weight, based on the total weight of the vinyl chloride graft copolymer, of a grafted VC polymer obtainable by graft polymerisation of vinyl chloride at a polymerisation temperature of 30 to 85 °C, and B) 45 to 60 % by weight, based on the total weight of the graft copolymer, of a crosslinked graft base consisting of a crosslinked copolymer of n-butyl acrylate and / or 2-ethylhexyl acrylate, or of a crosslinked acrylic acid ester-ethylene-vinyl acetate copolymer with an acrylate content of 35 to 70 % by weight, or mixtures of the aforementioned copolymers, wherein the copolymers are crosslinked with 0.05 to 0.5 % by weight of one or more copolymerised, ethylenically polyunsaturated comonomers from the group consisting of diallyl phthalate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylene glycol diacrylate, trimethylolpropane triacrylate.

7. Artificial leather according to one of claims 1 to 6, wherein component (II) is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 43 to 75 % by weight.

8. Artificial leather according to one of claims 1 to 6, wherein component (II) is an ethylene-vinyl acetate copolymer with a vinyl acetate content of 48 to 72 % by weight.

9. Artificial leather according to one of claims 1 to 8, containing component (I) and component (II) in a weight ratio of 98:2 to 70:30.

10. Artificial leather according to one of claims 1 to 8, containing component (I) and component (II) in a weight ratio of 95:5 to 75:25.

11. Artificial leather according to one of claims 1 to 10 further comprising 0.1 to 80 % by weight additives based on the weight of the vinyl chloride graft copolymer.

12. Artificial leather according to claim 11, wherein the additives are selected from fillers, stabilisers, co-stabilisers, antistatic agents, flame retardants, lubricants, pigments, blowing agents, antibacterial agents and mixtures thereof.