A method of producing a laminate

 

(57) Abstract:

The invention relates to a method for producing a laminate, which comprises two substrate are glued together using a polymer adhesive, and one of the substrates includes ethylene or propylene polymer. The method comprises applying to the first substrate polymer adhesive and forming the second substrate. Using polymer adhesive containing an organic solvent and ethylene or propylene polymer. The polymer is grafted thereto an unsaturated carboxylic acid or its anhydride, ester, amide, imide, salt of the metal. The total weight of the grafted ethylene and/or propylene polymer and an organic solvent is at least 80%, based on the total weight of the adhesive. Forming the second substrate is carried out by injection molding the ethylene or propylene polymer and optional additives covered by an adhesive to the first substrate. Also described laminate and shoes obtained in the described manner. The invention provides for obtaining laminates containing natural or synthetic materials that cannot be or are not to be melting. 3 S. and 8 C. p. F.-ly, 4 PL.

control is by means of a polymeric adhesive, and one of the substrates includes ethylene or propylene polymer.

It is well known that polyolefins do not have the level of adhesion with respect to polar materials such as metals, concrete and polar resins. There are various methods of improving the adhesion, based either on the modification of polyolefins, or the coating of adhesive between the polyolefin and the polar substrate.

In U.S. patent 4 599 385 discloses graft copolymers, in which the crystalline poly(propanebutane) the main chain of the grafted maleic acid or anhydride is maleic acid. Such a graft copolymer can be used as a primer layer between the polar and non-polar substrate polypropylene, or it can be mixed with polypropylene, and this mixture can be used directly. If the graft copolymer is used as the primer layer, it is usually applied to the polar substrate as a powder coating and attached to a polar substrate in the process of heating and melting during the formation of a continuous film. In another embodiment, the graft copolymer can be dissolved in a hot solvent and coated kstewangel or spray. Applying a layer of polypropylene nniem with a pre-molded film.

According to the U.S. patent 4 599 385 is preferred powder coating, followed by melting. However, for the application of powder coating requires special equipment, and the types of materials shall be limited to those that can be deposited powder coating. In another embodiment, when the graft copolymer is mixed with polypropylene and the mixture is applied directly, to achieve sufficient adhesion required a higher amount of the graft-copolymer. To obtain laminates of polypropylene and films based on polar polymers using as the adhesive a graft-copolymer of the recommended methods of coextrusion. When using these methods, the layers of melted polypropylene, graft-copolymer and a polar polymer and simultaneously ekstragiruyut with the formation of the multilayer sheet. Naturally, these methods are limited to the use of thermoplastic polymers that can be coextrudable.

In U.S. patent 4 198 327 disclosed composition having improved adhesion to solid polar materials. This composition contains (A) from 99 to 70 mass parts of a modified crystalline polyolefin containing vaccinations monomial is th-metals and (B) 1-30 mass parts of a hydrocarbon elastomer. Such a polyolefin composition may be combined with a polar material by heating them in such a way that at least the polyolefin composition is melted, and then connecting them together under pressure. When the polar material is not thermoplastic, the molten composition can be applied in the form of a coating or laminated with a polar material. However, this U.S. patent does not mention about how to achieve adhesion between the polar material and the unmodified polyolefin.

U.S. patent 5 302 418 discloses a method of coating a polypropylene or polyethylene surface of polypropylene or polyethylene with vaccines maleic acid, which contains from 0.5 to 10 mass%, preferably not less than 4 mass%, of maleic acid. In this process, the surface is covered with an additive containing a graft copolymer and a solvent, at a temperature coating, sufficient to graft-copolymer remained dissolved in the solvent, namely when 85-100oC. This additive contains from 2 to 15 mass%, preferably from 3 to 10 mass parts of dry residue. The solvent is an aromatic solvent, tuitele additives, up until this copolymer is not bonded with the surface. This process is primarily used for coating on polypropylene fibers.

In European patent application EP 0 407 666 A1 disclosed a method of surface treatment of vulcanized molded rubber products made from polyolefin. For the manufacture of molded products using EPDM rubber obtained by copolymerization of ethylene, alpha-olefin and diolefin, and mix it with a softening agent, a filler and a vulcanizing agent. The mixture is formed into articles of desired configuration on the extruder. Rubber based on EPDM rubber is used for manufacturing automotive molded products. Such products are usually painted. In order to improve ink adhesion to molded products, these products are treated with a solution of the modified polymer having a characteristic viscosity in the organic solvent is not less than 0.3. The polymer modifies the graft-copolymerization of ethylene-propylene copolymer with maleic acid or its anhydride. The propylene content is from 10 to 90 mole%, especially from 20 to 80 mole percent. The concentration of the modified polymer is from 10 to 100 CI molded vulcanized rubber product is then covered with a paint or other coating material resin by electrostatic coating, spray or kstewangel. U.S. patent 4 299 754 offers a solution similar to the modified graft polymer as an agent for surface treatment of finished products made from polyolefins, such as automobile bumpers. The content of propylene in a modified graft polymer is from 50 to 75 mole percent.

In U.S. patent 4 058 647 revealed that complex polyester, polyamide or hydrolyzed ethylene vinyl acetate copolymer may be laminated with a polymeric composition comprising both modified and non-modified polyolefin and a rubber component. The modified polyolefin modified by an unsaturated acid or anhydride. Laminate receive in the form of a sheet material by extrusion from a melt of the above-mentioned materials, or a lamination method of forming blown. U.S. patent 4 588 648 discloses that the layers of polypropylene and nylon can be laminated via an adhesive layer comprising a mixture of grafting of polypropylene and a graft-copolymer of maleic anhydride and olefin polymer. Such a laminate is produced by means of coextrusion.

However, all known methods are not suitable for the production of laminates which contain natural or synthetic is Etiketka skin.

One of the purposes of the present invention is the provision of a new method of producing a laminate, which comprises two substrates connected to each other by means of a polymeric adhesive, and one of the substrates contains ethylene or propylene polymer.

For example, in the footwear industry there is a great need in the way, suitable for the production of laminates (multilayer materials) that contain the first substrate: which cannot or should not melt during production of the laminate, such as rubber, leather, synthetic fiber or synthetic resin, such synthetic leather or nylon, and which contains ethylene or propylene polymer as the second substrate.

Accordingly, the second objective of the present invention is a new method of obtaining the above-mentioned laminate, which does not include the use of the process of coextrusion.

One aspect of the present invention is a method of producing a laminate containing a first substrate (I) and second substrate (II), which includes ethylene or propylene polymer and which adhesive is connected to the first substrate via a polymer adhesive, otlichaetsia, containing an organic solvent and ethylene or propylene polymer having grafted thereto an unsaturated carboxylic acid or its anhydride, ester, amide, imide, salt of the metal.

B) injection molding the ethylene or propylene polymer and optional additives coated primer substrate (I).

Another aspect of the present invention is a laminate, which is obtained in accordance with the above method.

A preferred aspect of the present invention is the shoes received in accordance with the above method.

The resulting laminates are characterized by excellent adhesion between the second substrate, which contains ethylene or propylene polymer, and the first substrate, which may be polar. The method of the present invention is very effective. The particular advantage of the method of the present invention is that the adhesive is applied is not in the form of a powder layer, and as a melt or hot solution on the substrate. Such methods are proposed in the known solutions, but they are uncomfortable.

At stage (A) of the method of the present invention the polymeric adhesive is applied to the first substrate (I). Ethylene or propylene p. the GTC or its anhydride, ester, amide, imide, salt of the metal, hereinafter designated as "vaccinated connection". Grafted compound is preferably an aliphatic unsaturated dicarboxylic acid or its anhydride, ester, amide, imide or metal salt of such acid. The carboxylic acid preferably contains up to 6, more preferably up to 5, carbon atoms. Alkali metal salts are the preferred salts. Examples of unsaturated carboxylic acids are maleic acid, fumaric acid, taconova acid, acrylic acid, methacrylic acid, crotonic acid and Tarakanova acid. Examples of derivatives of unsaturated carboxylic acids are maleic anhydride, citraconic anhydride, itacademy anhydride, methyl acrylate, methyl methacrylate, acrylate, methacrylate, butyl acrylate, butylmethacrylate, glycidylmethacrylate, glycidylmethacrylate, monoethylether, diethylmaleate, monomethylfumarate, dimethylfumarate, monomethylfumarate, diethylmalonate, acrylamide, methacrylamide, monoallelic, timelined, N, N-diethyltoluamide, N-monobutylether, N, N-dibutylamine, monopolarly, difumarate, N-monoethylfumarate, N, N - diethylformamide, N-monomethylfumarate, N, N-dibutyl the lat potassium. Maleic anhydride is the preferred imparted connection. One or more, preferably one, teach compound grafted to the ethylene or propylene polymer.

The content of grafted compound in the ethylene or propylene polymer preferably ranges from 0.05, more preferably between 0.5 and most preferably from 0.8, preferably up to 15, more preferably up to 10, and most preferably up to 2 mass% per the total weight of the grafted ethylene or propylene polymer.

Grafted ethylene or propylene polymer and the ethylene or propylene polymer used for vaccination, preferably has a density of up to 0,902 g/cm3more preferably from 0,850 to 0,902 g/cm3most preferably from 0,860 to 0,890 g/cm3especially from 0,865 to 0,880 g/cm3. However, it should be understood that the grafting density of the polymer is slightly different. In the case of ethylene polymers have shown that the density of the polymer is an important parameter from the point of view of giving the primer a sufficient mechanical strength and flexibility and to achieve sufficient solubility grafted atie" refers to the ethylene polymer, propylene polymer, a mixture of different ethylene polymers, a mixture of different propylene polymers or a mixture of at least one ethylene polymer and at least one propylene polymer. Preferred ethylene polymers and propylene polymers discussed below.

Ethylene or propylene polymer preferably have a crystallinity of from 5 to 35%, more preferably from 10 to 20%.

Ethylene or propylene polymer may be ethylene or a propylene homopolymer or a copolymer of propylene with at least one C4-C20alpha-olefin and/or C4-C18-diolefines. Preferably the ethylene polymer is a copolymer of ethylene and at least one3-C20-alpha-olefin and/or C4-C18- diolefine. Most preferably the ethylene polymer is a copolymer of ethylene and C3-C20-alpha-olefin, having a density of up to 0,902 g/cm3. Used in this text, the term "copolymer" refers to polymers obtained by polymerization of at least two different monomers.

Thus, the General term copolymer comprises a copolymer that is typically used for oboznachennomu. The copolymer may be statistical or block copolymer.

Preferred alpha-olefins containing from 4 to 10 carbon atoms, of which the most preferred are 1-butene, 1-hexene, 4-methyl-1-penten and 1-octene. The preferred diolefin is isoprene, butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9 - decadiene, Dicyclopentadiene, methylene-norbornene and 5-ethylidene-2 - norbornene. The copolymers may contain other comonomers, such as C2-C20acetylanthracene monomer.

Primer most preferably contains statistical or block copolymer of ethylene and C4-C10-alpha-olefin, most preferably a copolymer of ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene. The content of propylene is preferably more than 50%, more preferably from 60 to 90%, most preferably from 70 to 80%, calculated on the total weight of the polymer.

Grafting can be used known ethylene polymers which preferably have a density in the above range of values. One of the types used for the ethylene polymer is a linear copolymer of ethylene and alpha-olefin having not less than four is the bookmark links of co monomer along the polymer chain and the index of homogeneity is not less than 75. Such polymers are described by Elston in U.S. patent 3 645 992. Other acceptable for use ethylene polymers and methods for their preparation are described in U.S. patent 5 324 800. They have a mass-average molecular weight of from 500 to 1 400 000, preferably from 1000 to 500,000, and a molecular weight distribution Mw/Mnfrom 1.5 to 4.0. They are linear copolymers of ethylene and C3-C20alpha-olefins. Other suitable polymers are described in U.S. patent 4 079 429. They are statistical copolymers of ethylene and alpha-olefins containing from 3 to 10 carbon atoms, which have a melt index from 0.1 to 50 g/10 minutes, preferably 1-30 g/10 minutes, density 0,870 to 0.900 g/cm3preferably from 0,875 to 0,895 g/cm3, crystallinity, specific rentgenograficheski, from 5 to 40%, preferably from 7 to 30%, a melting point of from 40oC to 100oC, preferably from 60oC to 90oC, and the ethylene content of 85-95 mole percent. The ethylene polymers include those polymers sold under the trademark TAFMER (Trade mark of the company "Mitsui Petrochemical") AND EXACT (Trade mark of the company "Exxon Chemical), especially those that have the density to 0,902 g/cm3.

The most preferred SOPs which are grafted above the inoculated connection, basically is a linear ethylene polymers, which are characterized by the following indicators:

i) from 0.01 to 3 long chain branches per 1000 carbon atoms in the polymer chain

ii) the ratio of the index melt flow, I10/I25,63;

iii) a molecular weight distribution, Mw/Mnby the equation (Mw/Mn) (I10/I2)-4,63,

and (iv) a critical shear stress at the beginning of the destruction of the mass of melt more than 4 of 106Dyne/cm2or the critical shear rate at the beginning of the destruction of the surface of the melt, at least 50% larger than the critical shear rate at the beginning of the destruction of the melt surface linear ethylene polymer having about the same melt index Mw/Mn.

Substantially linear ethylene polymers and methods for their preparation are described in more detail in U.S. patent 5 272 236 and 5 278 272.

Substantially linear ethylene polymers contain from 0.01, preferably from 0.05 to 3, preferably up to 1 long chain branches per 1000 carbon atoms in the polymer chain. Long chain branching is defined here as segments of a chain length of at least presvetlenie may have the same length, as the polymer chain. For copolymers of ethylene/alpha-olefin long-chain branching has at least one carbon atom more than the short-chain branching, which is a consequence of the introduction of the alpha-olefin(s) into the polymer chain. The empirical effect due to the presence of long chain branching in the substantially linear ethylene/alpha-olefin copolymers, manifested in improved rheological properties.

There are known methods used to detect the presence of long chain branches in ethylene polymers, including ethylene/1-oktanovyh copolymers. Two such methods are helpanimals chromatography in combination with detector laser light scattering at low angles (GPC-LALLS) and helpanimals chromatography coupled with a differential viscometer (GPC-DV). Using these methods to determine long-chain branching and the underlying theory is well represented in the literature. CM. Zimm, G. H. , Stockmayer, W. H. , J. Chem. Phys. , 17, 1301 (1949); Rudin, A. , Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. (103 - 112).

Unlike the term "substantially linear" term "linear" means the. that is, the polymer is substituted by an average of less than 0.01 long chain branches/1000 carbon atoms.

Under the "melt index" or "I2it is the melt index measured in accordance with the method of ASTM D-1238, Condition 190oC/2,16 kg "I10" measured in accordance with the method of ASTM D-1238, Condition 190oC/10 kg to the melt Index I2substantially linear ethylene polymer is usually from 0.01 g/10 min to 1000 g/10 minutes, preferably from 0.01 g/10 minutes to 100 g/10 minutes. The ratio of the index melt flow, i.e., I10/I2is at least 5,63, preferably at least 6, more preferably 7, and practically does not depend on the index polydispersity, unlike traditional polyethylenes, which are characterized by the dependence of the index melt flow from polydispersity. This dependence is presented in Figure 2 of U.S. patent 5 272 236.

The rate of polydispersity substantially linear ethylene polymers (i.e., molecular weight distribution or the ratio of mass-average molecular weight to srednekamennogo molecular mass (Mw/Mn), determined by the method of gel chromatography, preenche 3,5, more preferably from 1.5 to 2.5.

In addition, substantially linear ethylene polymers, especially in the substantially linear ethylene polymers, have an index of a critical shear stress at the beginning of the destruction of the melt mass, a gas extrusion rheometric more than 4 of 106Dyne/cm, or nature gas extrusion rheology such that the critical shear rate at the beginning of the destruction of the melt surface for substantially linear ethylene polymer is at least 50% larger than the critical shear rate at the beginning of the destruction of the melt surface for a linear ethylene polymer, where the substantially linear ethylene polymer and the linear ethylene polymer contain the same comonomer or comonomers, the linear ethylene polymer has I2, Mw/Mnand density within 10% of the corresponding value characteristic of the substantially linear ethylene polymer, and where the corresponding critical shear rate substantially linear ethylene polymer and the linear ethylene polymer are measured at the same melt temperature using a gas extrusion reome the value of the melt, and other rheological properties are carried out using a gas extrusion rheometer (GER). The gas extrusion rheometer is described by M. Shida, R. N. Shroff, L. V. Cancio Polymer Engineering Science, Vol. 17, N 11, p. 770 (1977); "Rheometers for Molten Plastics" by John the dealy, published by Van Nostrand Reinhold Co. (1982), pp. 97-99.

Substantially linear ethylene polymer has a single melting peak, determined by the method of differential scanning calorimetry, DSC, in the range between -30oC and 150oC. a Single melting peak may have, depending on the sensitivity of the measuring equipment, "shoulder" or "hump" on the lower branches of melting, which is less than 12%, usually less than 9% and more typically less than 6%, of the total heat of melting of the polymer.

Methods of grafting the above-mentioned grafted compounds to the above unvaccinated ethylene or propylene polymer are well known and described, for example, in U.S. patents 4 739 017 and 4 762 890.

Polymer adhesive used in the implementation of the method of the present invention contains (A) one or more of the above-described grafted ethylene or propylene polymer and (B) an organic solvent, wherein the total number of grafted ethylene polymer clay is a polymer adhesive contains from 2%, more preferably from 3%, preferably up to 30%, more preferably up to 20% and most preferably up to 10% of the grafted ethylene polymer and/or the propylene polymer (A), based on the total weight of (a) and (B).

Examples of organic solvents that are used in polymer adhesive, are aromatic hydrocarbons, such as benzene, toluene or xylene; aliphatic hydrocarbons such as hexane, heptane, octane or decane; cyclic hydrocarbons, such as cyclohexane or methylcyclohexane; solvents, forming a bond at an average hydrogen atom, such as methyl ethyl ketone, tetrahydrofuran or tertiary butanol; or chlorinated hydrocarbons such as trichlorethylene, perchlorethylene, dichloroethylene, dichloroethane or chlorobenzene. Preferred are aromatic hydrocarbons, particularly alkyl substituted aromatic hydrocarbons. The polymer adhesive may contain a mixture of organic solvents.

The total weight of the grafted ethylene and/or propylene polymer (s) (a) and organic solvent (s) (B) is at least 80%, more preferably at least 90%, even more preferably at least 95%, based on the total weight of polimernogo and/or propylene polymer (s) (a) and organic solvent (s) (B).

Polymer adhesive used in the implementation of the method of the present invention may contain one or more other components, such as additional adhesive, which increases the stickiness of the resin, stabilizer, for example, the known UV stabilizers or depletability, and/or one or more unvaccinated ethylene and/or propylene polymers, such as those described above.

Increase the adhesiveness of the resin is usually aliphatic resin, policarpova resin, gidrirovanny resin or mixed aliphatic aromatic resin. Examples of increasing the adhesion of the resins include those resins sold under the trade name ESCOREZ (Exxon Chemical Co. ), PICCOTAC, PICCOVAR, PICCOLYTE (Hercules, Ink. ), WINGTACK (Goodyear) and ZONAREZ (Arizona). If the polymer adhesive used in the implementation of the method of the present invention includes an additional adhesive, its amount is preferably up to 15%, more preferably from 0.5 to 10%, most preferably from 1 to 5% , based on the total weight of the polymer adhesive. The adhesive may be, for example, one - or two-component adhesive. Examples of suitable adhesives include epoxies, urethanes, latex, acrylates, mortar elastomania or prepolymer, preferably di - or triisocyanate connection or prepolymer, such as Tris(4-isocyanatophenyl)thiophosphate, colorvision, methylene di-p-phenylisocyanate or urethane prepolymers. Examples of industrially available polyisocyanate compounds or prepolymers include VKFE (produced by Fratelli Zucchini's. r. l), DESMODUR RF'-E (trade name Miles lnc. ), PAPI polymeric MDI (trademark of The Dow Chemical Co. And UPACO 3570 (produced by Worthen Industries, UPACO Division).

The inclusion in the polymer of the adhesive increases the adhesiveness of the resin or additional adhesive is advantageous if, for example, the first substrate (I) contains a synthetic resin, such as PVC (synthetic leather), or synthetic fibres such as polyamide or polyester. If the second substrate (I) contains a natural resin or natural fibers such as cotton or jute fiber, the above-described grafted ethylene or propylene polymer preferably is the only adhesive that is included in the polymer adhesive. The polymer adhesive is prepared by mixing the grafted ethylene or propylene polymer or mixtures thereof, and optional additives with organic solvent (s), preferably at temperamental ethylene or propylene polymer. It may be helpful stirring the mixture, for example, within 30-90 minutes.

At least the above-described preferred grafted copolymers of ethylene and at least one3-C20-alpha-olefin and/or C4-C18-diolefine, which have a density of up to 0,902 g/cm3possess sufficient solubility in an organic solvent to be dissolved, even if the temperature of the polymer of the adhesive is lowered to room temperature or slightly elevated temperature. This provides a significant advantage because it eliminates the need for special precautions to keep the primer hot and put it on a hot substrate.

At stage (A) of the method of the present invention the polymeric adhesive can be applied to the first substrate (I) in any convenient way, for example by kstewangel, by immersion or spraying. Polymer adhesive preferably has a temperature of less than 80oC, more preferably from 10oC to 80oC, most preferably from 15oC to 60oC, after applying it on the first substrate (I). When the concentration of the grafted ethylene or propylene polymer in the polymer adhesive is kerny the adhesive on the substrate (I) at a higher temperature.

The first substrate (I) may include or be composed largely of a wide range of materials, especially of polar materials, for example metal, such as aluminum, iron, brass or plated (galvanized) iron; inorganic materials such as glass, cement, asbestos, or natural materials such as wood. However, the preferred materials are synthetic or natural rubbers, synthetic leather, such as PVC, natural leather like skin type nubuck, canvas, suede or grainy leather, the materials obtained from natural fibers such as cotton or other cellulose materials, flax or jute, or materials derived from synthetic resin, or synthetic fibers such as polyamides, practicelink nylon 6, nylon 10, nylon 11, nylon 12, nylon 66 or nylon 610, polyesters, such as polyethylenterephtalate or polybutylenterephthalate, polycarbonates, polyurethanes, the products of the saponification of the ethylene/vinyl acetate copolymer, epoxy resin, vinyl chloride resin, vinylidenechloride resin, polymethyl methacrylate, or a mixture thereof. The first substrate (I) may consist of one or more layers, and each layer may consist of the o is from 1 to 100 g/m2surface of the first substrate, preferably from 10 to 90 g/m2, more preferably from 30 to 80 g/cm2.

Typically a polymeric adhesive cover, at least partially one of the surfaces. After coating all or part of the amount of solvent included in the composition of the polymer adhesive, it is possible to evaporate, though, as a rule, the drying coated with a polymer adhesive substrate (I) is not required.

Before applying the above polymer adhesive on the first substrate (I) on the first substrate (I) can be applied more of the above-described adhesive or increase the stickiness of the resin as such or dissolved in the solvent. However, preferably, if the first substrate (I) is applied to only the above-described polymer adhesive to the second substrate (II) is coated on the first substrate by a method of injection molding. This means that the above-described polymer adhesive preferably is the only adhesive that is applied to the first substrate (I) for bonding two substrates together.

At the stage B of the method of the present invention the ethylene or propylene polymer and optional additives is applied to Pokrovsky (II) is formed on coated with a polymer adhesive first substrate (I). The term "ethylene or propylene polymer" refers to ethylene polymer, propylene polymer, a mixture of different ethylene polymers, a mixture of different propylene polymers or a mixture of at least one ethylene polymer and at least one propylene polymer. To illustrate their examples are polypropylene, branched low-density polyethylene from 0,915 to 0,940 g/cm3, high density polyethylene, density 0,940 to 0,960 g/cm3linear low density polyethylene (LLDPE) or polyethylene, very low density (VLDPE) having a density between 0.900 for up to 0,915 g/cm3or mixtures thereof. These polymers are well known materials.

The density of grafting the ethylene or propylene polymer is preferably up to 0,902 g/cm3but it can be higher. The density of the ethylene or propylene polymer in the second substrate (II) is usually from 0,850 to 0,960 g/cm3more preferably from 0,850 to 0,902 g/cm3most preferably from 0,860 to 0,890 g/cm3. Preferred ethylene and propylene polymers are those described above as starting materials for producing grafted ethylene, etc the customers USA 3645992; 5324800; 4 079 429 and 5 272 236 supra. The most preferred ethylene polymers are substantially linear ethylene polymers, which are described in more detail above.

Ethylene or propylene polymer can be mixed with one or more optional additives, such as depletability, stabilizers against atmospheric aging, antistatic agents, nucleation agents, fillers, pigments, dyes, flame retardants, foaming agents, protivoraketami and/or oils such as paraffin oil or naphthenic oil. In addition to one or more of ethylene or propylene polymers of the second substrate may contain one or more other polymers, such as styrene block copolymers, PVC, chlorinated polyethylene, EVA, chloroprene, ethylene-propylene rubbers, EPDM rubbers, natural rubbers, thermoplastic polyurethanes or silane grafted polyolefin. However, the number of ethylene or propylene polymer (s) is preferably not less than 40%, more preferably at least 50%, even more preferably at least 70%, calculated on the total weight of the second substrate. Most preferably, when the second substrate in a significant stne stage (B) is as follows.

Coated with a polymer adhesive substrate (I) is placed in the mold machine for injection molding so that the coated polymer adhesive surface directed to the entry points. Ethylene or propylene polymer and optional additives is heated to a temperature sufficient to plasticization of the polymer (s), preferably to a temperature of from 80oC to 350oC, more preferably from 100oC to 250oC, most preferably from 120oC to 180oC. the Temperature of the mold is typically 0oC to 80oC, more preferably from 5oC to 40oC. Ethylene or propylene polymer and optional additives otverzhdajutsja, and coated with a polymer adhesive surface of the substrate (I) is formed in the second substrate (II). This stage usually takes from 5 to 300 seconds, preferably from 15 to 120 seconds. Suitable for use with machines for injection molding are well known. The second substrate (II) preferably has a thickness of from 1 mm to 30 cm, more preferably from 4 mm to 5 see the Second substrate (II) may be monolithic or foam, depending on the type of additives, mixed with ethylene or propylene polymer before the start of the process injects the further operations, such as cutting it into pieces of the desired size, staining, sanding or polishing.

The laminate obtained in accordance with the method of the present invention is used for a variety of purposes, including as scales for bathrooms, the basis of carpets, textile base parts interior decoration of car and most preferably for the production of footwear type shoes. Shoes of this type the second substrate (II), which contains ethylene or propylene polymer that forms the sole of the Shoe, while the first substrate (I) forms the upper part of the shoes.

The following examples are only illustrative and in no way limit the scope of claims of the present invention. Except where otherwise indicated, all parts and percentages are massive.

Example 1

To produce the polymer adhesive was used substantially linear ethylene polymer having a density of 0,870 g/cm3and a melt index of 5.0 g/10 minutes, which is industrially available product of Dupont Dow Elastomers L. L. C. , produced under the trademark ENGAGE EG 8200 ethylene-1-octanoyl copolymer. For substantially linear ethylene polymer grafted 0,95 mass is substantially linear ethylene polymer was boiled for 1 hour under reflux. The polymer adhesive is cooled to room temperature, and then apply the strips of skin the size 17.5 cm x 2.5 cm x 0,12 cm, pre-treated according to the standard DIN 53273. Treatment according to standard DIN 53273 includes Asturiana skin with an average fat content (8-10 weight percent) in order to remove the granular layer, the polishing abrasive paper P40 and removal of all waste with a soft brush. Using a brush caused 50 g of polymer adhesive per square meter of leather strips. Coated with a polymer adhesive skin left to dry for 30 minutes at 23oC. and Then coated with a polymer adhesive and dried leather strips placed in the mold size 170 mm x 170 mm x 4 mm injection molded machine ENGELTM80. On strips of leather made respectively of a composition consisting of 30 parts of polyolefin elastomer (supplied by DuPont Dow Elastomers L. L. C. ), 14 parts of polyolefin elastomer Affinity PF1140 (supplied by the company The Dow Chemical Company), both are etilenoksidom copolymers, 23 parts of a filler based on calcium carbonate, 30 parts of oil Shellflex 371 supplied by the company Shell, and 3 parts of high density polyethylene IP90 from the company The Dow Chemical Company. The temperature in the four cylinders was 160oC, Stavila of 8,000 kPa, step screw nut 68 mm, the cooling time of 40 seconds and the speed of injection 80-80-80-80-80-80-80-40-30 mm/sec. Adhesion between the skin and the substrate, obtained from the ethylene/1 - actinophage copolymer was determined by the method of DIN 53273 L (3D). The power of exfoliation was 6H/mm

Comparative Example AND

Repeating Example 1, except that the polymeric adhesive was applied to strips of leather before the ethylene/1-octenoyl copolymer was applied to strips of skin injection molding. The power of exfoliation between the skin and the substrate, obtained from the ethylene/1-actinophage copolymer amounted to only 0.9 N/mm

Comparative Example B

The polymeric adhesive of Example 1 was applied to a strip of leather and dried as in Example 1. From the same composition that was used in Example 1 for injection molding, prepared plate size 8 cm x 2.5 cm x 0.2 see this polymer plate caused 50 g of the primer of Example 1 is based on a square meter of surface area. Coated with a polymer adhesive polymer plate was left to dry for 30 minutes at 23oC. and Then coated with a polymer adhesive polymer plate was heated to 80oC and extruded at coated with a polymer adhesive leather strip at a pressure of 400 kPa.

Power from.

Comparative Example

5 parts of a substantially linear ethylene polymer having a density of 0,902 g/cm3and a melt index 1.0 g/10 minutes, supplied by the company The Dow Chemical Company under the trademark AFFINITY PL 1880TMand 95 parts of toluene was heated as described in Example 1. Substantially linear ethylene polymer has not been grafted maleic anhydride. Formed a turbid dispersion. When defending in 19oC of this dispersion was precipitated polymer.

Comparative Example D

5 parts propylene copolymer, having a density of 0,902 g/cm3and delivered by the company Union Carbide under the trademark CEFOR DS4D25L, and 95 parts of toluene was heated as described in Example 1. Propylene polymer was not grafted maleic anhydride. A homogeneous solution was not observed, only the gel structure. Dispersion and gel obtained in accordance with Comparative Examples C and D, was not suitable as polymeric adhesives in the method of the present invention.

Examples 2-7

A solution with a concentration of 7.5% of the same grafted maleic anhydride substantially linear ethylene polymer as in Example 1, was prepared by heating with reverse holodiliny composition 20% tert-butanol, 9.5% of toluene and 63% of cyclohexane. In Examples 2, 4 and 6 as primers used resulting solution. In Examples 3, 5 and 7 after cooling the solution to room temperature, added 5% isocyanate compounds VKFE supplied by the company Fratelli Zucchini's. r. 1.

As described in Example 1, and then struck a polymer adhesive, using chistiana, test strips of woven synthetic material based on Nylon, PET and synthetic leather U-PVC. Before applying the polymeric adhesive strips scraped the bark from the abrasive paper R40, purified 1,1,2,2-tetrachlorethane and methyl ethyl ketone, respectively. The coated strips were then used in the process of injection molded and tested as described in Example 1 (see tab. 1).

Examples 8 AND 9

5% solution of the same grafted maleic anhydride polymer as in Example 1, was prepared by heating under reflux for one hour grafted maleic anhydride polymer in a mixture of solvents with the formation of the final composition of 18% methyl ethyl ketone, 10% toluene, and 67% of cyclohexane. In Example 8, the resulting solution was used as such as a polymer adhesive.

In Example 9, after cooling the solution to room is described in Example 1, on the strips of skin samples with a high fat content (15-16%) with a brush struck a polymer adhesive. The coated strips were then used in the process of injection molding and testing peeling and creep, as described in Example 1 (see tab. 2).

The resistance to aging of the adhesive bond is important for skin high fat content, where the adhesive properties may be reduced due to the impact of fat on the adhesive bond. Test results of creep method DIN 53273 after aging were as follows (see tab. 3).

Examples 10 and 11

a 2.5% solution of the same grafted maleic anhydride polymer as in Example 1, was prepared by boiling for one hour grafted maleic anhydride polymer in toluene. In Example 10 solution was used as such as a polymer adhesive. In Example 11, after cooling the solution to room temperature, added 5% isocyanate compounds VKFE supplied industry firm Fratelli Zucchini's. r. 1.

As described in Example 1, this polymer adhesive is then struck with a brush on the strips of skin samples high fat content. Covered with strips used in the process of injection molding and have experienced and the second substrate, comprising ethylene or propylene polymer and associated with the first substrate using a polymer adhesive, in which the coating on the first substrate polymer adhesive and forming a second substrate, characterized in that use polymer adhesive containing an organic solvent and ethylene or propylene polymer having grafted thereto an unsaturated carboxylic acid or its anhydride, ester, amide, imide, salt of the metal, and the total mass of the grafted ethylene and/or propylene polymer and an organic solvent is at least 80%, based on the total weight of the adhesive, and forming the second substrate is carried out by injection molding the ethylene or propylene polymer and optional additives covered by the first adhesive substrate.

2. The method according to p. 1, wherein the polymer adhesive includes a copolymer of ethylene and at least one3-C20-alpha-olefin and/or C4-C18-diolefine, having a density of up to 0,902 g/cm3.

3. The method according to p. 1 or 2, characterized in that the polymeric adhesive is applied to the first substrate at a temperature less than 80oC.

4. Sposa, of ester, amide, imide and metal salt is from 0.05 to 15%, based on the total weight of the grafted ethylene or propylene polymer.

5. The method according to any of paragraphs. 1-4, characterized in that the second substrate contains ethylene or propylene homopolymer, propylene copolymer, at least one4-C20-alpha-olefin and/or C4-C18-diolefins, or a copolymer of ethylene, at least one WITH3-C20-alpha-olefin and/or C4-C18-diolefins, or a combination of both.

6. The method according to PP. 1-5, characterized in that the second substrate contains ethylene polymer density to 0,902 g/cm3.

7. The method according to p. 2 or 5, characterized in that the polymer adhesive or the second substrate is a copolymer of ethylene, at least one WITH3-C20-alpha-olefin and/or C4-C18-diolefine is a substantially linear ethylene polymer having: (i) from 0.01 to 3 long chain branches per 1000 carbon atoms in the polymer chain; (ii) the ratio of the index melt flow I10/I25,63; (iii) molecular mass distribution, Mw/Mndefined by the equation: Mw/Mn(I10/I2 or the critical shear rate at the beginning of the destruction of the surface of the melt, at least 50% larger than the critical shear rate at the beginning of the destruction of the melt surface linear ethylene polymer having the same melt index and Mw/Mn.

8. The method according to any of paragraphs. 1-7, characterized in that the polymeric adhesive further comprises isocyanate compound or prepolymer.

9. The method according to any of paragraphs. 1-8, characterized in that the first substrate contains synthetic and/or natural resin, rubber, leather and/or fiber.

10. The laminate obtained according to the method according to any of paragraphs. 1-9.

11. The shoes received in accordance with the method according to any of paragraphs. 1-9.

 

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