FR2580908A1 - METHOD FOR MANUFACTURING SHOES WITH RODS COMPRISING A FINISHING COATING - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS A PROCESS FOR PREPARING SHOES WHOSE UPHOLS HAVE A POLYURETHANE FINISHING COATING AND WHOSE SOLES ARE THERMOS-WELDED, PROCESS ACCORDING TO WHICH IS APPLIED TO THE MATERIAL INTENDED TO FORM THE UPPER, BEFORE SHAPING THE UPPER A POLYURETHANE FINISHING COATING WITH TERMINAL HYDROXY GROUPS CONTAINING ETHERS AND OR ESTERS GROUPS AND WHOSE GLASS TRANSITION TEMPERATURE IS LESS THAN 200C, AND, AFTER SHAPING THE ROD AND ASSEMBLY OF THE ROD ON THE SHAPE, IT IS ASSEMBLED DIRECTLY THE SOLE BY THERMO-WELDING AT TEMPERATURES OF AT LEAST 50C.

Description

The subject of the invention is a process for the manufacture of

  shoes whose stems have a finish coating.

  For the assembly of shoe stems with soles

  the, it is generally necessary to card or to see the edges of the rods (to be mounted or already mounted on form) to which the sole

  outside is then glued. It has now been found that

  as a particular finishing coating on the material intended

  to form the rod, before shaping it, one can assemble di-

  the shoe rods to the sole by heat sealing without the need to card or

  stems and without having to use any other adhesive agent on the

said marginal areas.

  The subject of the present invention is therefore a process for

  a pair of shoes whose uppers have a polyurethane topcoat and the soles of which are heat-sealed, wherein the poly-hydroxy-containing topcoat is applied to the material for forming the rod before forming the same terminals containing ether groups and / or esters and whose glass transition temperature is below 200 C, and after shaping of the rod and mounting of the rod on the form, is directly connected to the rod to the

  sole by heat sealing at temperatures of at least 50 degrees C.

  The polyurethanes to be used according to the invention may be single-type polyurethanes or mixtures of

  polyurethanes. These polyurethanes can be obtained according to the

  known by reacting polyisocyanates with

  lyols and possibly with chain extending components.

  The polyurethanes with terminal hydroxyl groups are preferably polyaddition products (a) of polyisocyanates with (b) polyesterpolyols and / or long-chain polyether polyols and optionally (c) low molecular weight polyfunctional components.

reacting with isocyanates.

-2-

  The polyisocyanates (a) are preferably diisocyanates

  cyanate. The preferred diisocyanates are polymethylenediiso-

  cyanates comprising from 2 to 6 methylene groups, isophorone-

  diisocyanate, toluene diisocyanate, xylenediisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, aromatic diisocyanates, in particular

  diphenylmethane diisocyanate, being especially preferred.

  The polyols (b) are preferably polymeric diols

  nes, in particular polyester diols and polyether diols having terminal hydroxyl groups, having an average molecular weight of

  between 300 and 4000, preferably between 1000 and 3500. The polyester-

  Preferred diols are the reaction products of dicarboxylic acids.

  aliphatic or aromatic compounds with C2-C6 alkanediols,

  preferably ethylene glycol, 1,3-propanediol, 1,4-butane-

  diol, neopentyl glycol, 1,6-hexanediol or diethylene

  glycol. The preferred diacids contain from 4 to 8 carbon atoms.

  and include maleic acid, succinic acid, sebacic acid,

  spike and phthalic, adipic acid being preferred. We can also

  diols with a lactone, for example, capro-

  lactone, to obtain a polycaprolactone with hydroxyl groups

  nal. The preferred polyetherdiols are polymeric glycols, for example polypropylene glycol or polytetrahydrofurans with terminal hydroxyl groups (reaction products of the indicated diols

  above with tetrahydrofuran). Polyesterdiols are

especially preferred.

  The components (c) advantageously contain from 2 to 9 carbon atoms and are preferably aliphatic diamines,

  for example propylenediamine and isophoronediamine, alkane-

  diols such as those mentioned above, diethylene glycol or triethylene glycol. Component (c) is more preferably a

  alkanediol comprising from 2 to 6 carbon atoms.

  The polyurethanes to be used according to the present invention comprise terminal hydroxy groups and the weight ratio of the components (a), (b) and (c) must therefore be chosen from

  so that for each equivalent of polyisocyanate, one uses

  read more than one equivalent of the total component (b) reactive with isocyanate and, if any, component (c). For each equivalent of polyol (b), it is advantageous to use from 0.8 to 0.9995, preferably from 0.85 to 0.9991 equivalent of polyisocyanate.

  (at). If component (c) is also present, then we can use

  more polyisocyanate, preferably so that the

  component (c) produces an elongation of the chain with the polyiso-

  additional cyanate. For each equivalent of component (b), preferably equivalents of component (c) and (y + x) equivalent of component (a) where y represents a number between 0.8 and

  0.9995, more preferably between 0.85 and 0.9991, and x is greater than

  0. According to a particularly preferred variant, the polyurethanes are at least partly such that x signifies a number of 0 to 1, more particularly 0.2 to 1, especially of

  0.2 to 0.8, the remaining polyurethanes being such that x is pre-

  greater than 1, and more particularly less than 2,

  usually less than 1.8, especially up to 1.77. A team

  valent represents the amount corresponding to the divided molar weight

  by the functionality of the compound. When using

  of the same functionality, the preferred components are all difunctional, the ratio of equivalents obviously corresponds to

molar ratio.

  The polyurethanes can be obtained according to the known methods by reacting the components (a), (b) and (c) with each other under the usual conditions, mainly to

  temperatures between 40 C and the boiling point

  preferably between 50 and 75 ° C., advantageously in a sol-

  inert organic matter which is volatile under the conditions of application

  cation (that is, at temperatures between 50 and C). Suitable solvents include dialkyl ketones (preferably methyl ethyl ketone), cyclohexanone and aliphatic esters of carboxylic acids (preferably ethyl acetate or ethoxyethyl acetate), optionally in admixture with solvents. aromatic, preferably toluene or xylene. The reaction is preferably carried out in the presence of a suitable catalyst, advantageously a tin compound such as

  tin di (2-ethylhexanoate) or dibutyltin dilaurate.

  The polyurethanes to be used according to the invention may, if desired, be mixed with copolymers of vinyl chloride, in particular copolymers of vinyl chloride and vinyl acetate, in which from 10 to 50% by weight of the copolymer consists of vinyl acetate monomer, which may further contain a copolymerized unsaturated dicarboxylic acid,

  preferably maleic acid, the proportion of the dicarboxylic acid

  In the copolymer, up to 10% by weight of the copolymer is unsaturated. These copolymers are preferably soluble in organic solvents (for example as defined above) and have an average molecular weight of between 500 and 20000,

  more particularly between 1000 and 8000. The proportion of the copoly-

  The amount of vinyl chloride in the polyurethane is preferably 20% by weight maximum, more preferably 0.5% to 20% by weight.

  weight, more especially from 2 to 20% by weight.

  The proportion of hydroxyl-terminated polyurethane defined above wherein x means a number of 0 to 1, based on the total of the polymers of the finishing coating of

  the invention is preferably at least 10% by weight, preferably

  at least 17% by weight, in particular up to 74% by weight. The proportion of polyurethanes with terminal hydroxy groups

  in which x> 1 with respect to all the polymers of the coating

  finishing part of the invention is preferably at least 22%

  by weight, in particular up to 80%.

  Polyurethanes possibly associated with copoly-

  vinyl chloride are advantageously formulated as

  of liquid compositions in the solvents mentioned above.

  For example, they may contain only the solvent used for their synthesis or may also be diluted with the same

  inert solvents or with other inert solvents which are

  under the conditions of application, preferably with

  ethyl acetate, cyclohexanone, xylene, toluene or di-

  methylformamide. For concentrated compositions, the concentration

  is preferably in the range of 15 to 40% by weight, more particularly

  25 to 40% by weight, calculated as solid residue in the composition. The viscosity of these concentrated compositions may vary within wide limits, for example between 5000 and 50000 mPas at 20 C. For their application on substrates, these compositions

  may, if necessary, be further diluted with solvents

  properties, preferably the solvents indicated above, for

  to achieve the correct viscosity for the chosen method of application

  sie. These compositions are generally clear and are usually

  solutions or colloidal solutions.

  The polyurethane compositions mentioned above may optionally contain conventional additives such as antioxidants, UV absorbers, fungicides, opacifying agents and / or suitable dyes. Dyes can

  be inorganic or organic pigments, especially

  metalliferous plexes, for example as described by Becker and Braun in "Kunststoffhandbuch", volume 7 ("Polyurethane"), Karl Hanser

  Verlag, MUnchen / Wien, 1983, page 108.

  The polyurethanes mentioned previously used for

  the coatings of the invention are essentially polyurethanes

  single component (or mixtures of these polyurethanes).

  The substrate constituting the stem of the shoe can be

  generally any substrate usually

  finished with polyurethanes and used in the manufacture of

  footwear, mainly synthetic materials (in particular polyurethane and polyvinyl chloride) and

  leather (especially crust and sanded leather). Before the

  finishing garment according to the invention is applied, these

  Trats are preferably coated with other layers, in particular

  of a base layer (or adhesive layer) and a top layer

  Higher (preferably a lacquer); an intermediate layer can

  be applied to the basecoat before application of the

  top, especially when the substrate is synthetic.

  When the substrate is leather, it can be more or less nourished and / or waterproofed; for this purpose, the base layer can

  contain, in addition to the polymers, waxes and / or

  riture; these waxes and / or food oils preferably represent up to 30% by weight of the synthetic polymer in the composition of the base layer. A higher proportion of these

  food agents can affect the strength of adhesion of the

with the rod.

  The various layers mentioned above are preferably all based on polyurethane. For the base layer,

  polyurethane single component systems are preferably used.

  thane in which the polyurethanes contain hy-

  and terminated from polyester polyols (as indicated above), short-chain diols (essentially as indicated

  above) and aromatic or aliphatic diisocyanates (mainly

  mainly as described previously), in a molar ratio such

  as indicated previously. These polyurethanes are preferably used

  in the form of their solutions in organic solvents

  inert, for example as indicated above. For the inner layer

  medium, two-component systems are preferably used

  which, after application to the substrates, are polymerized into poly-

  corresponding urethanes, one of the components being a polyurethane with terminal isocyanate groups derived from aromatic diisocyanates

  and / or aliphatic and polyether polyols and / or polyester-

  polyols, for example as described above, and the other

  wherein it is an aliphatic or aromatic polyamine which, when reacted with the terminal polyisocyanate-terminated polyurethane, produces a polyurea-urethane layer. In general, the polyamines may be any conventional low molecular weight amine, preferably a polymethylenediamine comprising from 2 to 6 carbon atoms, diethylenetriamine,

  triethylenetetramine, dipropylenetriamine, meta-phenylene

  Diamine, isophoronediamine, 4,4'-dicyclohexylmethanediamine,

  4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodide

  cyclohexylmethane or diaminotoluene. These compositions of the intermediate layer are preferably applied in the absence of any solvent on the substrate on which the reaction is carried out. For the upper layer, one-component polyurea urethane systems preferably containing terminal hydroxyl groups derived from polyesterpolyols (for example as indicated above), polyisocyanates (for example as indicated above) and polyamines ( for example as shown

  previously), polyesterpolyols, polyisocyanates and polyiso-

  lyamines being preferably aliphatic; these polyurea systems

  Single-component urethanes are preferably applied as their solutions in organic solvents, as previously described. If desired, the intermediate layer and the top layer may contain conventional additives, for example

as indicated above.

  The different layers can be applied according to

  any usual method, for example by means of a rou-

  water, a rubber cylinder, a curtain machine, an air knife, a pressure screen, an airless gun or a compressed air gun, each layer obtained being suitably dried, preferably at temperatures between 40 and

   C, more particularly between 40 and 90 C.

  Polyurethanes with terminal hydroxy groups intended for

  finishing coating according to the invention can be applied se-

  any known method, for example according to the methods

  previously mentioned or according to the transfer method,

  at temperatures between 50 and 230 C, more particularly

  between 80 and 110 C, suitably by means of a printed textile or non-textile support which is temperature stable

  application and transfer. For this purpose, the composition of the poly-

  The urethane of the invention may be applied to the support and, preferably before drying, transferred to the previously coated substrate of the other layers as previously indicated. All the different layers can also be applied to the support in reverse order, each of the layers being dried except for the last one, and the set of layers is then

  transferred to the substrate on which no layer has been applied.

  cated. The transfer temperature is preferably lower or

  equal to 110 ° C when at least one of the layers contains a solvent.

  The finished materials can then be cut,

  rods and rods are mounted on form, the rods thus mounted are then assembled directly to the sole (outer) by heat sealing. By direct assembly of the rod with the sole means the securing of the rod with the sole without dropping or carding the edges of the stem, and without

  use of any other adhesive agent on these edges. Even a gonad

  Edging is not necessary or even recommended. The creases of the edges of the shaped rod may, however, be cut off if desired. If desired, a thicker layer of polyurethane can be applied to the edges of the rod.

  the terminal hydroxy group invention, which is

  as a finishing coating on the remainder of the rod. The amount of hydroxy-terminated polyurethane to be used for the topcoat, optionally in admixture with copolymers of vinyl chloride, is preferably in the range of 3 to 20 g / m 2, and in the case of an edge rod coated with an additional layer of 3 to 50 g / m 2, preferably 5 to 25 g / m 2 (calculated as solid products of the coating). The weight per m2 of the

  the totality of the polymers used for all the layers is

  from 100 to 600 g of solid matter, more particularly

initially from 150 to 450 g.

  The assembly, that is to say the joining of the sole with the rod, can be carried out by any heat-sealing method, preferably by direct molding or by injection

  for the assembly of synthetic soles or by heating the se-

  already formed at the desired temperature, for example by reaction

  IR shock, and by joining the stem and the sole, for example

with an AGO machine. -

  For the heat sealing of the rod (more exactly the edges of the rod) with the sole, the coating is heated in order to reactivate the polyurethane layer of the invention. If the layer

  polyurethane is partially or totally free of

  However, the coating is preferably heated to a temperature

  at least 100 C for reactivation. The temperature is advantageous

  less than the melting point of the polyurethane, preferably

  in the field of crystallite melting of polyurethane or above; the assembly temperature for the assembly process in the absence of solvent is more particularly of the order of 105 to 230 C, especially of the order of 140 to 220 C. This process is particularly suitable for applying soles synthetic materials by direct molding or by injection molding. The molding temperature of the soles of polyurethane foam is preferably

  140 to 210 ° C, and for polyvinyl chloride soles

  vinyl preferably 150 to 220 C. The heat stored by the melt or spongy enough to reactivate the coating of

  polyurethane and makes it possible to obtain a resilient sole / rod assembly

  both folding and breaking. If the polyurethane coating or at least one of the polyurethane layers contains a solvent, for example

  example as described above for the compositions, the temperature

  of reactivation can be lowered accordingly, ie

  say at values of at least 50 C; in this case, the temperature is advantageously of the order of 50 to 110 C, preferably 60 to 100 C, more particularly 60 to 90 C. For the application of preformed soles which could be damaged or deformed

  at the assembly temperatures in the absence of solvent, it is

  able to operate with an additional polyurethane layer containing a solvent, preferably by applying to the edges of the rod a layer of a polyurethane composition of the invention containing a solvent as defined above and / or by applying a layer of such a polyurethane composition on the soleplate, preferably 20 to 50 g solids per m 2 and

  assembling the soleplate and stem before the solvent has come together

  thoroughly evaporated, at temperatures between 50 and 110 C,

- 10 -

  preferably between 60 and 90 ° C; for this purpose, it is advantageous to heat the soleplate to the desired reactivation temperature and to assemble it immediately with the rod; the heat stored by the sole is sufficient to reactivate the polyurethane and provides a solid assembly whose resistance to bending and breaking

is excellent.

  After cooling, the shoe in its raw state is

  ready and can, if necessary, be completed according to the

  for example, if necessary, be equipped with heels, then be finished according to conventional methods (sole finishing,

  glassware, milling, polishing, cleaning, etc.).

  The polyurethane topcoats of the invention

  meet the high demands that polyurethane finishes

  thane are subject to, and are particularly resistant to

  lysis and stains, impervious to water and permeable to steam, and are characterized by a great deal of flexibility and elasticity; they are also suitable for making shoes

temperature resistant.

  An impression of the material of the stem coated or not

  is not affected by the finish coating of the invention.

  The following examples illustrate the present invention without in any way limiting its scope. In these examples, the term

  "polyol" is used to refer to specific polymeric diols (polyes-

  terdiols). The polylactones used are commercial products

  under the names "TONE 0221" (molecular weight 1000) and "TONE 0260" (molecular weight 3000) by Union Carbide, USA.

- 11 -

Example 1

  In a container equipped with a paddle stirrer, introduce

  1000 g of methyl ethyl ketone are added. 1000 g of polyesterdiol (a polycondensation product of ethylene glycol and adipic acid having a molecular weight of 2000) are added to this solvent. We

  heat the mixture to 600C. At this temperature, and when

  solution, 13.52 g of 1,4-butanediol are added and

  support all. When the solution is completely clear, 113.10 g of toluene diisocyanate 80/20 are added. We set the temperature of

  reaction at 65-70 ° C. After one hour, 0.1 g of di-

  (2-ethylhexanoate) tin as a catalyst. While the viscosity of the solution increases, 690 g of acetate are added

  ethyl. After 5 hours, the reaction mixture is cooled.

  The viscosity of the solution is 20000 mPas at 20 C. x = 0.3.

Example 2

  In a container that can be heated and equipped with a

  350 g of methyl ethyl ketone are added and 266.283 g of a hydroxyl-terminated polyester diol (condensation product of ethylene glycol and adipic acid having an average molecular weight of 2000) are added to this solvent. The mixture is heated to C until a solution is obtained, then added and

  dissolves 3,600 g of 1,4-butanediol. When the solution is total-

  30.117 g of toluene diisocyanate 80/20 are added. The reaction temperature is adjusted to 65-70 ° C. After one hour, 0.1 g of dibutyltin dilaurate is added as a catalyst. As the viscosity of the solution increases, 350 g of ethyl acetate are added. After 5 hours, the reaction mixture is cooled. The

  solution has a viscosity of 30000 mPas at 20 C. x = 0.3.

Example 3

  The procedure is analogous to that described in the

  ple 2 using a polyesterdiol which is the product of condensation

  1,4-butanediol and adipic acid and has a moderate weight of

  average lecular of 2000, as well as 1,4-butanediol, 4,4'-

  diphenylmethane diisocyanate (MDI) and solvents as follows:

- 12 -

  polyol 244.492 g 1I4-butanediol 6.610 g MDI 48.898 g methyl ethyl ketone 350,000 g toluene 350,000 g

x = 0.6.

Example 4

  The procedure is analogous to that described in the

  ple 2 using a polyesterdiol which is the product of condensation

  1,4-butanediol and adipic acid and has a moderate weight of

  the average lecular of 2000 (polyol 1) and a polycaprolactonediol having

  an average molecular weight of 1000 (polyol 2) as well as 1,4-

  butanediol, 4,4'-diphenylmethane diisocyanate and solvents as follows: polyol 148.558 g polyol 56.804 g 1,4-butanediol 16.381 g MDI 78, 257 g toluene 350,000 g dimethylformamide 350,000 g

Example 5

  The procedure is analogous to that described in the

  ple 2 using a polyesterdiol which is the product of condensation

  1,4-butanediol and adipic acid (molecular weight

  average = 2000), as well as 1,4-butanediol, 4,4'-diphenyl-

  methane-diisocyanate and solvents-as follows:

- 13 -

  polyol 210.377 g 1,4-butanediol 16.779 g MDI 72.844 g toluene 350,000 g dimethylformamide 350,000 g

x = 1.77.

Example 6

* The procedure is analogous to that described in the

  ple 2 using a polyesterdiol which is the product of condensation

  1,6-hexanediol and adipic acid (molecular weight =

  3000), as well as 1,4-butanediol, 4,4'-diphenylmethane di-

  isocyanate and solvents as follows: polyol 258.862 g 1,4-butanediol 5,184 g MDI 35,954 g dimethylformamide 200,000 g toluene 300,000 g methyl ethyl ketone 200,000 g

x = 0.67.

Example 7

  The procedure is analogous to that described in the

  ple 2 using a polyesterdiol which is the product of condensation

  1,6-hexanediol and 1,4-butanediol (in equim-

  ) with adipic acid (average molecular weight = 3000), as well as 1,4-butanediol, toluene diisocyanate (TDI) and solvents as follows:

- 14 -

  polyol 276.648 g 1,4-butanediol 2,493 g TDI 20,859 g dimethylformamide 200,000 g toluene 300,000 g methyl ethyl ketone 200,000 g

x = 0.3.

Example 8

  The procedure is analogous to that described in the

  pie 2 using a polyesterdiol which is the product of condensation

  1,4-butanediol and adipic acid (molecular weight =

  1000), as well as 1,4-butanediol, 4,4'-diphenylmethane di-

  isocyanate and solvents as follows: polyol 169.915 g 1,4-butanediol 23, 233 g MDI 106.852 g dimethylformamide 350,000 g toluene 350,000 g

x = 1.51.

Example 9

  A polyurethane composition is prepared by mixing the compositions of Examples 3 and 8, adding a UV stabilizer and an antioxidant, and diluting with cyclohexanone as follows:

8 0908

- 15 -

  Composition of Example 3 380.228 g Composition of Example 8 570.342 g

  UV stabilizer: 2- (2'-hydroxy-5'-methyl)

  phenyl) -benzotriazole 0.950 g anti-oxidant: 2,4-dimethyl-6-tert. butylphenol (technical grade) 0.950 g cyclohexanone 47.530 g

Example 10

  A polyurethane composition is prepared by mixing the compositions of Examples 4 and 7, adding a UV stabilizer and an antioxidant and diluting with cyclohexanone as follows: Composition of Example 4760.456 g Composition of Example 7 190.114 g

  UV stabilizer: 2- (2'-hydroxy-3 ', 5'-di-

  tert.-amylphenyl) -benzotriazole 0.950 g

  antioxidant: tetra- [B- (3 ', 5'-di-tert.-butyl)

  4'-hydroxy-phenyl) -propionyl methyl] -methane 0.950 g cyclohexanone 47.530 g

Example 11

  The procedure is analogous to that described in the

  ple 10 using the composition of Example 6 instead of

composition of Example 7.

Example 12

  A polyurethane composition is prepared by mixing the compositions of Examples 2 and 4, adding a UV stabilizer and an antioxidant and diluting with cyclohexanone as follows:

- 16 -

  composition of Example 2 700,000 g composition of Example 4 250,000 g UV stabilizer (as in Example 10) 0.950 g anti-oxidant (as in Example 10) 0.950 g cyclohexanone 47.530 g Examples 13 to 16

  The procedure is analogous to that described in the examples

  ples 9 to 12, adding a copolymer of polyvinyl chloride as follows: compositions of Examples 9 to 12 100,000 g PVC copolymer: 84% by weight of vinyl chloride, 15% by weight of vinyl acetate and 1% by weight of maleic acid, (molecular weight = 2000) 2,000 g

  and stirring until the copolymer is dissolved.

  As previously described, a PVC copolymer (84% by weight of vinyl chloride, 15% by weight of vinyl acetate and 1% by weight of maleic acid) having a molecular weight is used.

1000 or 3000.

Examples 17 to 20

  The procedure is analogous to that described in the examples

  ples 9 to 12, adding a polyvinyl copolymer as follows: compositions of Examples 9 to 12 100,000 g PVC copolymer: 60% by weight of vinyl chloride and 40% by weight of vinyl acetate (molecular weight = 4000) 5,000 g

  and stirring until the copolymer is dissolved.

- 17 -

  Similarly, a chloride copolymer is used

  of vinyl (60% by weight of vinyl chloride and 40% by weight of

  vinyl acetate) having a molecular weight of 2500 or 5500.

  In the following application examples, the parts are indicated by weight and the application quantities of the layers are

  data in g of solid substance per m2 of substrate.

  Application Example A On an undyed cowhide crust of 1.5 mm thickness, two basecoats having the following composition are applied: polyurethane parts with terminal hydroxyl groups obtained at

  from 3 molar parts of 4,4'-diphenylmethane

  diisocyanate, 1 molar portion of polycaprolactonediol having a molecular weight of 3,000 and 2 molar parts of 1,4-butanediol, parts of toluene and parts of dimethylformamide, pigmented with 10 g / kg of titanium dioxide in an application amount of 50 g of solid material per m2 for each layer

  and a top layer of polyurethane (lacquer) having the composition

following statement:

  parts of polyurea-urethane obtained from 2 parts mo-

  4,4'-dicyclohexyl-methane-diisocyanate, 1 part

  molar mass of a polycaprolactonediol with a moderate weight

  lecular of 3000 and 0.95 molar part of isophorone-

diamine and

  solvent parts (toluene / monomethyl ether of ethylene-

glycol / isopropanol)

  in an application amount of 100 g of solid material per m2.

  The compositions are rolled on the crust side and dried after each layer at 40 to 80 in a drying tunnel. On the substrate thus treated, the

- 18 -

  by means of a compressed air gun the composition of Example 1 diluted with ethyl acetate at a viscosity of 10-12 seconds in the beaker of 4 mm Ford, in an application amount of

  g of solid material per m2, then the substrate is dried at 40

  than 80 ° C in the drying tunnel. A shoe stem made of the treated leather is assembled directly, without dropping or inflation of its edges, with an integral sole of polyurethane foam, according to the injection molding process. The temperature of the sole / rod contact surface of the rod reaches 190C. The shoe thus formed

  is cooled, then finished and cleaned according to usual

  and then is ready for use.

  The upper of the shoe can also be assembled with a synthetic material made of polyvinyl chloride at a temperature

injection molding of 190 * C.

  In the example above, an airless vaporizer is used instead of a compressed air gun, the composition being

  diluted to a viscosity of 12 to 40 seconds.

Application example B

  On a 1.5 mm thick polyurethane sheet

  forced upside down with a cotton knit, successively applied

the following layers:

  firstly 50 g / m 2 of a basecoat having the following composition:

  parts of polyurethane with terminal hydroxyl groups obtained

  2.5 molar parts of 4,4'-diphenylmethane

  diisocyanate, 1.5 molar portion of 1,4-butanediol and 1 molar portion of a polycaprolactonediol having a molecular weight of 3000, and parts of solvent (toluene / dimethylformamide),

- 19 -

  then 300 g / m 2 of an intermediate layer having the following composition:

  83.3 parts of polyurethane diisocyanate obtained from 2 parts

  molar toluenediisocyanate and a part of

  molar polypropylene glycol having a molecular weight

  from 2000 and 16.7 parts of 3,3'-dimethyl-4,4'dicyclohexylmethanediamine, pigmented in white with 8 g of titanium dioxide per kilo of composition,

  and finally 30 g / m 2 of an upper layer having the following composition

boasts:

  30 parts of polyurea urethane obtained from 2 parts mo-

  isophorone diisocyanate, 1 molar part of polycaprolactonediol having a molecular weight of 3000 and 0.95 molar parts of isophorone diamine, parts of toluene, and 35 parts of isopropanol, pigmented in white with 10 g of titanium dioxide per kilo of composition. The different layers are applied by means of a roll, the layers being dried between each application at 40 ° -140 ° C. On the substrate thus treated, is applied by means of a rubber cylinder the composition of Example 1 to 10 g / m 2 and dried at 80 ° C. From this substrate, a shoe rod is manufactured which is assembled directly (without dropping or inflating the edges of the stem) with an integral foam sole.

  polyurethane with a gross density of 500 kg / m3, depending on the

  transferred injection molding. The temperature of the edge of the stem

  mounted on form increases up to 160 C during assembly.

  After the usual finishing and cleaning work, the shoe

  sure obtained is ready for use.

8 0908

- 20 -

  Application Example C On a crust 1 mm thick, covered with two base layers (adhesive layers) as used in Application Example A (total application amount = 150 g / m 2) and of an upper layer (lacquer) as used in Application Example A (90 g / m 2), a finishing coating is applied by the transfer method. For this purpose, the composition of Example 1 is applied to 20 g / m 2 on a grained paper support and the surface of the support bearing the coating.

  is applied to the leather (with the layers indicated

  ously). The coating is transferred to a temperature included

  between 80 and 110 ° C and the paper support is removed. With the

  Trat thus treated, is prepared a shoe rod on which is formed at 200 ° C a polyvinyl chloride sizing as described in Application Example A. After cooling,

  finish the shoe according to the usual methods.

  According to a variant, it is applied to the paper support

  all the polyurethane layers mentioned earlier in the

  reverse the composition of Example 1, 2 ', the lacquer layer, 3 and 4' the basecoats) by drying after application of the first, second and third layers, but not after

  fourth. The transfer is then carried out on the leather at a time

  between 80 and 110OC. The leather thus treated is

  then worked as described above.

  Application Example D A rod with a treated crust is formed as described in application example C. On the edge of the rod mounted on

  form, a layer of the composition of the

  1 to 20 g / m2. On a preformed polyurethane sole,

  a layer of the composition of Example 1 at 20 g / m 2 without complete drying of the layer, and then heating the soleplate to 70.degree.

  reactivation IR shock and assembles with the stem. After cooling

  deformation and finishing according to the usual methods, we obtain

a shoe ready to wear.

- 21 -

Application example E

  On a calf skin sanded 1.8 mm thick on the

  applied a basecoat and a lacquer as described in

  Application example C is applied by means of a rim machine.

  20 g / m 2 of the composition of Example 1 diluted with ethyl acetate at a viscosity of 20 seconds in the Ford 4mm beaker, and the substrate was dried at 80-85C. from this treated leather, we prepare a shoe stem which is assembled, by reactivation at 85 C, with an AGO machine directly without dropping or inflating the edges of the stem and without any other adhesive agent

  at the edges, with a preformed poly-chloride

  vinyl on which 30 g / m 2 of the composition of Example 1 was applied with a solvent. The shoe thus obtained is finished

according to the usual methods.

Application example F

  The procedure is analogous to that described in the example

  application E, but by applying, before assembling the rod with the sole, 100 g / m2 of an additional layer of the composition

  of Example 1 on the edges of the mounted rod.

  The compositions of Examples 2, 3, 6, 7 and 9 to 20 can be used in place of the composition of Example 1 in the

application examples above.

Claims (14)

  1.- A process for the preparation of shoes whose rods comprise a polyurethane topcoat and whose soles are heat-sealed, the method of which is applied to the material intended to form the rod, before forming it, a finishing coating of polyurethane having terminal hydroxyl groups containing ether and / or ester groups and having a glass transition temperature of less than 200 ° C., and after shaping the rod and mounting the rod on the form, the rod is directly assembled to the sole by heat sealing at temperatures of minus 50 C.   2. A process according to claim 1, characterized in that the polyhydroxide terminated hydroxy groups is the polyaddition product of (a) at least one polyisocyanate with   (b) at least one polyester polyol and / or at least one polyether   polyol having an average molecular weight of from 300 to 4000, and optionally (c) at least one isocyanate-reactive low molecular weight polyfunctional component of from 0.8 to 0.9995 equivalent of the compound (a) being used; per component equivalent (b).   3. A process according to claim 2, characterized in that component equivalents (c) and (x + y) of component equivalents are used per component equivalent (b). (a), where x is a number from 0 to 1 and there is a number from 0.8 to 0.9995.   4. A process according to claim 3, characterized in that the polyurethane specified in claim 3 is used in admixture with a polyhydroxide-terminated hydroxy groups obtained by polyaddition of components (a), (b) and (c) as specified in claim 3 and ox means a number greater than 1 and y has the meaning given to claim 3.   5. A process according to any one of the claims   1 to 4, characterized in that the hydroxy terminated polyurethane is used in admixture with a copolymer of vinyl chloride and vinyl acetate and optionally an unsaturated dicarboxylic acid.   6. A process according to any one of the claims   1 to 5, characterized in that the polyhydroxy terminated polyurethane, optionally in admixture with a vinyl chloride copolymer, is used in the form of a solution in a volatile inert organic solvent under the conditions of application.   7.- A process according to any one of the claims   1 to 6, characterized in that the material of the rod is a material selected from polyvinyl chloride, polyurethane and leather.   8. A process according to claim 7, characterized in that the material, before the application of the coating   finish is coated with other layers.   9. A process according to claim 8, characterized in that the material is coated with a base layer and   of an upper layer, and possibly of an inner layer   mediate between the base layer and the upper layer,   each of these layers being based on polyurethane.   10. A process according to any one of the claims   1 to 9, characterized in that an additional layer of polyurethane with terminal hydroxyl groups is applied.   as defined in any one of claims 1 to 6,   on the edges of the rod to be assembled.   11. A process according to any one of the   dications 1 to 10, characterized in that for the assembly of preformed soles, is applied to the soles a polyurethane composition with terminal hydroxyl groups such   as defined in any one of claims 1 to 6.   12. A process according to any one of the   1 to 11, characterized in that the heat-sealing is carried out at a temperature of between 50 and 110 ° C.   when at least one polyurethane layer contains a solvent.   13. A process according to any one of the claims   1 to 11, characterized in that the heat-sealing is carried out at temperatures of at least 100 C when substantially   no solvent is present in the different layers.   14. A process according to any one of the claims   1 to 10, 12 and 13, characterized in that the rod is assembled with a synthetic sole by direct molding or by injection, at temperatures corresponding to the   reactivation of the finishing coat of the stem.