JP2019523043A - Upper - Google Patents

Abstract

The present invention relates to an upper for footwear articles, the upper comprising at least one panel having at least one layer made from a composition comprising a fluorinated thermoplastic polyurethane polymer. [Selection figure] None

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority from European Patent Application Publication No. 16178295.8 filed July 7, 2016, the entire contents of which are incorporated by reference for all purposes. Which is hereby incorporated by reference.

  The present invention relates to an upper for footwear articles, the upper comprising at least one panel having at least one layer made from a composition comprising a fluorinated thermoplastic polyurethane polymer.

  Uppers for footwear articles are generally formed by stitching together multiple outer panel sections. These outer panel sections can be made from several materials, such as natural and leather, plastic, mesh, and non-woven.

  “Nonwoven fabric” is defined as a fabric-like material made from long fibers joined together by chemical, physical, thermal or solvent treatment. The term is used in the textile manufacturing industry to describe fabrics such as felt that are not woven or knitted. Typically, long fibers consist of hydrogenated thermoplastic polymers (H-TPU), especially based on hydrogenated urethanes.

  H-TPU polymers are, for example, U.S. Patent Application Publication No. 20110168874 (PUMA AKTIENGESELSCHAFT RUDOLF DASSLER SPORT), U.S. Patent Application Publication No. 2013/0169219 (PUMA SE) and U.S. Patent Application Publication No. 2014/0082961. In the specification (REEBOK INTERNATIONAL LIMITED), it is disclosed in the art for the manufacture of the upper part of a shoe.

  Heat-treatable elastomeric polyurethanes containing (per) fluoropolyether blocks are disclosed, for example, in US Pat. No. 5,332,798 (AUSIMON SPA).

  Applicants may be useful in the manufacture of footwear articles, particularly shoes and boot uppers, characterized by having improved properties when compared to hydrogenated thermoplastic polyurethane polymers (TPU). The need to provide new polyurethane materials was recognized. More particularly, Applicants have found polymers that have good mechanical properties while having improved stain resistance, improved chemical and wear resistance, low temperature flexibility, silky feel Focused on providing materials.

Accordingly, in a first aspect, the present invention provides at least one fluorinated polyurethane [F-TPU polymer], wherein the F-TPU polymer is
[Monomer (a)] At least one diol selected from the group comprising poly-ether type diols, poly-ester type diols, polybutadiene diols, and polycarbonate diols;
[Monomer (b)] At least one hydroxy-terminated (per) fluoropolyether polymer [PFPE polymer];
[Monomer (c)] at least one aromatic, aliphatic, or alicyclic diisocyanate; and [Monomer (d)] at least one aliphatic, alicyclic, or having 1 to 14 carbon atoms Aromatic diols;
For footwear articles comprising at least one panel having at least one layer [layer E] made from a composition [composition (C)] comprising an F-TPU polymer comprising repeating units derived from Regarding the upper.

  Preferably, the panel comprises layer E as a single layer.

  Preferably, the panel includes layer E as the outermost layer.

  Applicant has surprisingly found that when layer E is the outermost layer, it gives a soft silky feel without adding a plasticizer to the composition (C).

  Furthermore, Applicants have surprisingly improved that when layer E is a re-outer layer, the panel is improved when compared to a panel made from hydrogenated thermoplastic polyurethane (H-TPU) polymer. It has been found that it exhibits stain resistance and increased ease of cleaning.

In this specification and the following claims,
The term “(per) fluoropolyether” is intended to indicate “fully or partially fluorinated polyether”;
The expression “(per) fluoropolyoxyalkylene chain” is intended to indicate a partially or fully fluorinated linear or branched polyoxyalkylene chain;
-The use of parentheses around a symbol or number identifying a compound, chemical formula, or part of a formula only serves to help distinguish those symbols or numbers from the rest of the text, and therefore The brackets can be omitted;
The term “upper” (also referred to as “bump”) covers a toe, an upper part of the foot, a side of the foot and the back of the heel; , Shoes, boots, etc.)
The term “panel” is intended to indicate the part forming the upper; The upper can be manufactured using only one panel or joining two or more panels together. If more than two panels are joined together to form an upper, the panel is selected from, for example, a foot toe box, toe cap, waist leather, bump, tongue, counter and back strap Can be done.

  Preferably, said F-TPU polymer is a block copolymer, i.e. a polymer comprising blocks (also referred to as "segments"), each block comprising at least one monomer (a ), Repeating units derived from at least one monomer (b), at least one monomer (c) and at least one monomer (d).

  Preferably, the F-TPU polymer has a number average molecular weight of 30,000 to about 70,000 Da.

Preferably, the F-TPU polymer has a melting point ( _Tm ) of about 120 <0> C to about 240 <0> C.

  Preferably, the at least one monomer (a) has a number average molecular weight of 500 to 4,000 Da, more preferably 1,000 to 4,000 Da.

  Preferably, said at least one monomer (a) is poly (ethylene) glycol, poly (propylene) glycol, poly (tetramethylene) glycol (PTMG), poly (1,4-butanediol) adipate, poly (ethane) Diol-1,4-butanedio) adipate, poly (1,6-hexanediol-neopentyl) glycol adipate, poly-caprolactone diol (PCL), and polycarbonate diol, more preferably selected from the group consisting of them. Poly (tetramethylene) glycol, polycaprolactone diol and polycarbonate diol are particularly preferred.

Preferably, said at least one monomer (b) is a hydroxy-terminated (per) fluoropolyether polymer [PFPE polymer], i.e. having two chain ends, one or both chain ends being at least one -OH. A polymer comprising a (per) fluoropolyoxyalkylene chain [chain (R _pf )] terminated with a group.

Preferably, at least one chain end of said chain (R _pf ) has the formula:
_{-CH 2 (OCH 2 CH 2)} t -OH (I)
(Where
t is 0, or 1 to 5)
It is terminated with

More preferably, both chain ends of said chain (R _pf ) are terminated with a group of formula (I) as defined above.

Preferably, said chain _{(R pf)} has the formula ^{_{-O-D- (CFX #) z1}} -O (R f) (CFX *) z2 -D * -O-
(Where
z1 and z2 are equal to or different from each other and are 1 or more;
X ^# and X ^* are equal to or different from each other and are -F or -CF3, provided that when z1 and / or z2 is greater than 1, X ^# and X ^* are -F;
D and D ^* are equal to or different from each other and are alkylene chains containing 1 to 6, even more preferably 1 to 3 carbon atoms, wherein the alkyl chain contains at least 1 to 3 carbon atoms Optionally substituted with one perfluoroalkyl group;
(R _f ) comprises, preferably consists of a repeating unit R °, said repeating unit comprising:
(I) -CFXO- (wherein, X is F or CF _3);
(Ii) -CFXCFXO- (wherein X is equal to or different from each occurrence and is F or CF ₃ , provided that at least one of X is -F),
(Iii) —CF ₂ CF ₂ CW ₂ O—, wherein each of W is equal to or different from each other and is F, Cl, H;
_{(Iv) -CF 2 CF 2 CF} 2 CF 2 O-;
_{(V) - (CF 2)} j -CFZ-O- ( wherein, j is an integer of 0 to 3, Z is the formula _{-O-R (f-a)} -T group, in the formula , R ₍ fa ₎ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are: -CFXO-, -CF ₂ CFXO-, -CF ₂ CF ₂ CF ₂ O—, —CF ₂ CF ₂ CF ₂ CF ₂ O— (each of X is independently F or CF ₃ ), and T is a C ₁ -C ₃ perfluoroalkyl group is there)
Selected independently from the group consisting of)
The chain.

More preferably, the chain (R _f ) is selected from the following formulas (R _f -a) to (R _f -c):
_{(R f -a) - (CF} 2 O) n (CF 2 CF 2 O) m (CF 2 CF 2 CF 2 O) p (CF 2 CF 2 CF 2 CF 2 O) q -
(Wherein m, n, p, q are integers selected such that 0 or the chain R _f satisfies the above number average molecular weight requirements, provided that when p and q are 0 at the same time, When n is not 0 and m is other than 0, the m / n ratio is preferably 0.1 to 20, and when (m + n) is other than 0, (p + q) / (m + n) is preferred. Is subject to 0 to 0.2);
_{(R f -b) - (CF} 2 CF (CF 3) O) a (CF 2 CF 2 O) b (CF 2 O) c (CF (CF 3) O) d -
Wherein a, b, c, d are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirement, provided that at least one of a, c and d is not 0 When b is other than 0, a / b is preferably 0.1 to 10, and when (a + b) is different from 0, (c + d) / (a + b) is preferably 0.01. To 0.5, more preferably 0.01 to 0.2));
_{(R f -c) - (CF} 2 CF (CF 3) O) e (CF 2 O) f (CF (CF 3) O) g -
(Wherein e, f and g are 0 or an integer selected so that the chain R _f satisfies the above-mentioned number average molecular weight requirement, and when e is other than 0, (f + g) / e is (Preferably 0.01 to 0.5, more preferably 0.01 to 0.2)
Selected from.

PFPE polymers according to the formula (R _f -a) in which the chain (R _f ) is as defined above, where p and q are 0 are particularly preferred according to the invention.

In a preferred embodiment, the PFPE polymer has the following formula (PFPE-I):
_{HO- (CH 2 CH 2 O)} t -CH 2 - (R pf) -CH 2 (OCH 2 CH 2) u -OH (PFPE-I)
(Where
t and u are each independently 0, or 1 to 5;
R _pf is as defined above)
Follow.

  Preferably, the PFPE polymer has a number average molecular weight of 400 to 10,000 Da, more preferably 1,000 to 5,000.

  In a preferred embodiment, the molar ratio between monomer (a) and monomer (b) is 2-20, more preferably 2-10.

  In a preferred embodiment, the amount of monomer (b) is such that the F-TPU polymer contains 4-30% by weight fluorine.

  Preferably, said at least one monomer (c) has a number molecular weight of 500 Da or less, preferably 10 to 500 Da.

  Preferably, the at least one monomer (c) is 4,4′-methylenediphenylene diisocyanate (MDI), 1,6-hexane diisocyanate (HDI), 2,4-toluene diisocyanate, 2,6- Including, preferably consisting of toluene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and cyclohexyl-1,4-diisocyanate Selected in group. MDI and HDI are particularly preferred.

  Preferably, said at least one monomer (d) is ethylene-glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), N, N-diethanolamine, and N, N-dii. Contains sopanol aniline, preferably selected from the group consisting of them. BDO and HDO are particularly preferred.

  In a preferred embodiment, the sum of blocks derived from monomers (c) and (d) is 10-60% by weight, based on the total weight of the F-TPU polymer.

  Those skilled in the art will understand that the blocks containing repeating units derived from monomers (a) and (b) are rubber-like blocks, while the blocks containing repeating units derived from monomers (c) and (d) are hard blocks. Easy to understand.

  In a preferred embodiment, at least 80% of the block [block B] containing a repeating unit derived from the monomer (b) is a block [block containing a repeating unit derived from the monomer (c) on at least one of the terminals [block B]. It is connected to a block [block A] containing a repeating unit derived from the monomer (a) via C]. In other words, at least 80% of the block B is contained in the following type of sequence:-[A-C-B-C]-.

  Advantageously, the F-TPU polymer can be prepared according to the procedure disclosed in US Pat. No. 5,332,798 (AUSIMON SPA), in particular Example 15.

  According to a preferred embodiment, the upper is made from a composition (C) containing no plasticizer.

  Preferably said composition (C) comprises an F-TPU polymer as defined above as the main component.

  More preferably, the F-TPU polymer is in an amount of at least 60 wt%, more preferably at least 80 wt%, even more preferably at least 85 wt%, based on the total weight of the composition (C).

  In addition to the F-TPU polymer, the composition (C) may optionally contain further additives such as antioxidants, heat stabilizers, dyes and fillers.

  Embodiments in which the composition (C) is made essentially from the F-TPU polymer combined with any of the additives listed above in an amount up to 1% by weight are also encompassed by the present invention. .

  According to a first embodiment, the upper comprises a plurality of panels stitched together, each panel comprising a layer E as defined above.

  According to an alternative embodiment, the upper comprises a single panel, which extends over the entire surface of the upper and comprises a layer E as defined above. An upper comprising a single panel is also known as a “unit upper design”.

  Layer E can be produced by methods known in the art, for example, by a meltblown process as disclosed in US Patent Application Publication No. 2010/0186874 cited above.

As an example, layer E is
(I) preparing a mold;
(Ii) filling the mold with a composition comprising at least one elastomeric fluorinated polyurethane [F-TPU polymer] as defined above;
(Iii) sealing the mold;
(Iv) may be manufactured by a process comprising heat treating the sealed mold; and (v) withdrawing the article from the mold.

  Preferably, step (iv) comprises two steps, the first step comprises heating at a first temperature for 10 seconds to 10 minutes, and the second step is at a second temperature, said step Heating at a second temperature lower than the first temperature for 30 seconds to 24 hours.

  More preferably, the first temperature is 120 ° C to 300 ° C.

  More preferably, the second temperature is 50 ° C to 200 ° C.

  Alternatively, step (iv) includes only one step of heating at a temperature of 50 ° C. to 300 ° C. for 10 seconds to 24 hours.

  Preferably, the mold is allowed to cool after step (iv) and before step (v).

  According to a preferred embodiment, said at least one panel comprises layer E as the only layer.

  According to another preferred embodiment, said at least one panel comprises layer E as defined above and at least one texture layer [layer T] consisting of texture yarns.

  For example, according to an embodiment, an upper according to the invention comprises at least one panel comprising a layer E as defined above, said layer E having an outer surface and an inner surface, wherein At least a part of the inner surface is connected to a texture layer [layer T] made of texture yarn.

  According to another embodiment, the upper according to the invention comprises at least one panel comprising two layers T consisting of a layer E and a textured yarn as defined above, where layer E is Located between the two layers T.

  If the upper includes layer E and layer T, the upper is obtained by welding layers E and T together.

  The welding can be performed using, for example, a high frequency welding process or an ultrasonic welding process.

  In a further embodiment, the invention relates to an article of footwear comprising an upper as defined above.

  In the event that the disclosure of any patent, patent application, and publication incorporated herein by reference contradicts the description of this application to the extent that it may obscure the terms, this description shall control. .

  The invention is illustrated in more detail below by means of the examples contained in the following experimental section, which are merely illustrative and should not be construed as limiting the scope of the invention in any way. Absent.

Experimental Part Raw Material-Monomer (a):
(A1) CAPA ^™ 2201 (manufactured by Perstorp) polycaprolactone diol (PLC) having a molecular weight (Mw) of about 2,000 and a hydroxyl group value of about 56 mg KOH / g;
(A2) Polytetramethylene glycol (PTMEG) having a Mw of about 2,000
(A3) ETERNACOLL (registered trademark) UH200 (manufactured by UBE) polycarbonate diol (PCD) having a Mw of about 2,000
(A4) BESTER ^™ (manufactured by DOW) polyester diol having a Mw of about 2,000-monomer (b) (formula:
_{H (OCH 2 CH 2) p} OCH 2 CF 2 O (CF 2 CF 2 O) m (CF 2 O) n -CF 2 CH 2 O (CH 2 CH 2 O) p H
Have)
(B1) p = 4.7 and Mw of about 2,000
(B2) p = 1.6 and Mw of about 1,700
Have)
Monomer (c):
(C1) Diphenylene-4,4′-diisocyanate (MDI)
(C2) 1,6-hexane-diisocyanate (HDI)
Monomer (d):
(D1) 1,4-butanediol (BDO)
(D2) 1,6-hexanediol (HDO)
-Catalyst:
Bismuth neodecanoate

Preparation of F-TPU polymer specimen-Method A
F-TPU polymer specimens 1-4 in the form of sheets are examples of US Pat. No. 5,332,798 (against Ausimont SpA) cited above, starting from the monomers described above. Prepared according to the same procedure detailed in 15. The F-TPU polymer thus obtained contained 20% by weight of repeating units derived from monomer (b).

Preparation of F-TPU polymer specimen-Method B
Sheet form F-TPU polymer specimens 5-7, and 8 (the latter as a comparison) were prepared as follows:
The hydrogenated prepolymer was synthesized by reacting monomer (c) and monomer (a) in an equivalent ratio of 2 to 1 at a temperature of 90 ° C .;
The fluorinated prepolymer was synthesized by reacting monomer (c) and monomer (b) in an equivalent ratio of 2 to 1 at a temperature of 90 ° C .;
The hydrogenated prepolymer and the fluorinated prepolymer were then mixed together and stirred at 90 ° C. for 30 minutes;
-Monomer (c) was further added depending on the selected stoichiometric ratio;
The reaction was continued for 3 minutes at 90 ° C. until chain extension was complete;
The polymer thus obtained was cast at 100 ° C. for 24 hours.

  The composition of the F-TPU polymer obtained according to Method A and Method B described above, and the composition of the comparative hydrogenated polyurethane polymer (H-TPU) are reported in Table 1 below.

For further comparison, a commercially available hydrogenated TPU (H-TPU9 ^* ) was used. The monomer ratio of H-TPU 9 ^* has not been published.

  The mechanical properties of the sheets made from F-TPU and H-TPU polymers were evaluated and the results are reported in Table 2.

  The above results indicate that the F-TPU polymer according to the present invention has mechanical properties comparable to those of the H-TPU polymer typically used in the manufacture of uppers for footwear articles, and therefore F- The TPU polymer is shown to impart good mechanical properties to the finished upper.

  The sheet was used in the examples described below.

Example 1-Contact Angle This test is expected to predict both stain resistance and chemical resistance.

  The static contact angle (SCA) of water and n-hexadecane droplets (about 5 μL) as solvent was measured with a DSA30 instrument (Kruess GmbH, Germany). The standard deviation as well as the SCA value was calculated within 10 contact angles.

  Surface free energy (SFE) is calculated according to the Owens, Wendt, Rabel and Kaelble method (WORK method), which is a standard method for calculating the surface free energy of a solid from the contact angle with several liquids. It is.

  The results are summarized in Table 3 below.

The above results show that while the surface energy is reduced to the range of 15-16 mN / m compared to 31 mN / m for the hydrogenated thermoplastic polyurethane used as the reference compound, water (H ₂ O) and hexadecane ( It shows that the contact angle measured in both of C ₁₆ ) increased. These data are consistent with the increase in stain and chemical resistance afforded by F-TPU compared to H-TPU polymer.

Example 2-Blue Denim Test This test is expected to predict both stain and abrasion resistance.

The test was performed using a Taber Industries 5750 Linear Abraser (linear wear tester), which was set to operate under the following conditions:
-Cycle speed: 30 cycles / min-Stroke length: 2.54 cm (1 inch)
-Number of cycles: 200
-Full load: 1 kg.

  The test was performed once for dry denim and once for wet denim against F-TPU1, F-TPU2, F-TPU3, F-TPU5, and F-TPU7.

  Before testing with wet denim, the denim was soaked in water for 10 seconds, then removed, and the water was squeezed by hand so that it did not drip from the denim but was wet to the touch.

  The test was performed as follows: A denim sample measuring approximately 30 mm × 30 mm was secured to a fixture so that the sample did not move during the test. The F-TPU and H-TPU samples were then placed on the denim samples and similarly fixed to the fixture.

Checkpoints were set as follows:
After rubbing and after cleaning with isopropyl alcohol (IPA).

  Results for tests in the dry state: No contamination was observed for F-TPU1, F-TPU2, F-TPU3, F-TPU5, and F-TPU7.

  Results for wet testing: A very bright halo was observed for F-TPU1, F-TPU2, F-TPU3, F-TPU5, and F-TPU7.

Example 3-Contamination test One drop of each of the above-mentioned contaminants was brought into contact with the surface of a test piece made from F-TPU1 and allowed to stand at ambient conditions for 24 hours. The specimen was then cleaned with water.

  Specimens made from H-TPU were used as a comparison and were processed as disclosed above.

The results are summarized in Table 4 below, where
++ = no contamination + = trace / halo- = contamination.

  The above results clearly showed an increase in both the stain and chemical resistance of the F-TPU specimen compared to the H-TPU specimen.

Example 4-Evaluation of tactile properties F-TPU and H-TPU's tactile properties (especially the feeling of softness) were measured by subjectively testing a sheet of material with the touch of five people.

  The soft feel is measured subjectively by hand and is graded on a scale of 1 to 5, with 1 being poor in soft feel (hard feel) and 5 being excellent and soft feel. Participants participated in this study individually and therefore they did not affect each other in their response. Participants were asked to present the four samples in a random order and touch and grade them.

  The results are summarized in Table 5 below.

  The above results show that the sheet obtained using F-TPU according to the present invention shows better tactile properties, especially improved softness, when compared to the sheet obtained from H-TPU polymer. Clearly indicated.

Claims (15)

For footwear articles comprising at least one panel having at least one layer [layer E] made from a composition [composition (C)] comprising at least one fluorinated polyurethane [F-TPU polymer] The F-TPU polymer is an upper
[Monomer (a)] At least one diol selected from the group comprising poly-ether type diols, poly-ester type diols, polybutadiene-diols, and polycarbonate-diols;
[Monomer (b)] At least one hydroxy-terminated (per) fluoropolyether polymer [PFPE polymer];
[Monomer (c)] at least one aromatic, aliphatic or alicyclic diisocyanate; and [Monomer (d)] at least one aliphatic, alicyclic having 1 to 14 carbon atoms, Or an aromatic diol;
Upper, containing repeating units derived from.   The at least one monomer (a) is poly (ethylene) glycol, poly (propylene) glycol, poly (tetramethylene) glycol (PTMG), poly (1,4-butanediol) adipate, poly (ethanediol-1 2,4-butanedio) adipate, selected from the group comprising poly (1,6-hexanediol-neopentyl) glycol adipate, poly-caprolactone-diol (PCL), and polycarbonate-diol. Upper. Said at least one monomer (b) has two chain ends, one or both chain ends terminated with at least one -OH group (per) fluoropolyoxyalkylene chain [chain (R The upper according to claim 1 or 2, which is a hydroxy-terminated PFPE polymer comprising _pf )]. At least one chain end of the chain (R _pf ) is represented by the formula (I):
_{-CH 2 (OCH 2 CH 2)} t -OH (I)
(Where
t is 0, or 1 to 5)
The upper according to claim 3, terminated with Both chain ends of the chain (R _pf ) have the formula (I):
_{-CH 2 (OCH 2 CH 2)} t -OH (I)
(Where
t is 0, or 1 to 5)
The upper according to claim 3, terminated with The chain (R _pf ) has the formula:
-OD- (CFX ^# ) _z1- O ( _Rf ) (CFX ^* ) _z2- D ^* -O-
(Where
z1 and z2 are equal to or different from each other and are 1 or more;
X ^# and X ^* are equal to or different from each other and are -F or -CF3, provided that when z1 and / or z2 is greater than 1, X ^# and X ^* are -F age;
D and D ^* are equal to or different from each other and are alkylene chains containing 1 to 6, even more preferably 1 to 3 carbon atoms, wherein the alkyl chain contains at least 1 to 3 carbon atoms Optionally substituted with one perfluoroalkyl group;
(R _f ) comprises, preferably consists of a repeating unit R °, said repeating unit comprising:
(I) -CFXO- (wherein, X is F or CF _3);
(Ii) -CFXCFXO- (wherein, X, equal or different at each occurrence, is F or CF _3, provided that at least one of X is conditional that the -F);
(Iii) —CF ₂ CF ₂ CW ₂ O—, wherein each of W is equal to or different from each other and is F, Cl, H;
_{(Iv) -CF 2 CF 2 CF} 2 CF 2 O-;
_{(V) - (CF 2)} j -CFZ-O- ( wherein, j is an integer of 0 to 3, Z is the formula _{-O-R (f-a)} -T group, in the formula R ₍ fa ₎ is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are the following: —CFXO—, —CF ₂ CFXO—, —CF ₂ CF ₂ CF ₂ O—, —CF ₂ CF ₂ CF ₂ CF ₂ O— (each of X is independently F or CF ₃ ), and T is a C ₁ -C ₃ perfluoroalkyl group. )
Selected independently from the group consisting of)
The upper according to any one of claims 3 to 5, wherein the upper is a chain. The chain (R _f ) is represented by the following formula (R _f -a) to formula (R _f -c):
_{(R f -a) - (CF} 2 O) n (CF 2 CF 2 O) m (CF 2 CF 2 CF 2 O) p (CF 2 CF 2 CF 2 CF 2 O) q -
(Wherein m, n, p, q are integers selected such that 0 or the chain R _f satisfies the above number average molecular weight requirements, provided that when p and q are 0 at the same time, n is not 0; if m is other than 0, the m / n ratio is preferably 0.1-20; if (m + n) is other than 0, (p + q) / (m + n) is preferred Is subject to 0 to 0.2);
_{(R f -b) - (CF} 2 CF (CF 3) O) a (CF 2 CF 2 O) b (CF 2 O) c (CF (CF 3) O) d -
Wherein a, b, c, d are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirement, provided that at least one of a, c and d is 0 None; when b is other than 0, a / b is preferably from 0.1 to 10; when (a + b) is different from 0, (c + d) / (a + b) is preferably 0.00. 01-0.5, more preferably 0.01-0.2).
_{(R f -c) - (CF} 2 CF (CF 3) O) e (CF 2 O) f (CF (CF 3) O) g -
(Wherein e, f, g are 0 or an integer selected such that the chain R _f satisfies the above number average molecular weight requirements; when e is other than 0, (f + g) / e is preferred. Is 0.01 to 0.5, more preferably 0.01 to 0.2)
The upper according to claim 6 selected from. The PFPE polymer has the following formula (PFPE-I):
_{HO- (CH 2 CH 2 O)} t -CH 2 - (R pf) -CH 2 (OCH 2 CH 2) u -OH (PFPE-I)
(Where
t and u are each independently 0, or 1 to 5;
R _pf is as defined in claim 6)
The upper according to any one of claims 1 to 7, according to claim 1.   The at least one monomer (c) is 4,4-methylene-diphenylene-di-isocyanate (MDI), 1,6-hexane-diisocyanate (HDI), 2,4-toluene-diisocyanate, 2,6-toluene. -Selected from the group comprising diisocyanate, xylylene-diisocyanate, naphthalene-diisocyanate, paraphenylene-diisocyanate, hexamethylene-diisocyanate, isophorone-diisocyanate, 4,4-dicyclohexyl-methane-diisocyanate, and cyclohexyl-1,4-diisocyanate The upper according to any one of claims 1 to 8.   The at least one monomer (d) is ethylene-glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), N, N-diethanolamine, and N, N-diisopananolaniline. The upper according to any one of claims 1 to 9, which is selected from the group comprising:   At least 80% of the block [block B] containing the repeating unit derived from the monomer (b) passes through the block [block C] containing the repeating unit derived from the monomer (c) on at least one of the terminals thereof. The upper according to any one of claims 1 to 10, which is connected to a block [block A] containing a repeating unit derived from the monomer (a).   The upper part as described in any one of Claims 1-11 in which the said composition (C) does not contain a plasticizer.   The former according to any one of the preceding claims, wherein the composition (C) comprises the F-TPU polymer in an amount of at least 60% by weight, based on the total weight of the composition (C). leather.   The upper according to any one of claims 1 to 13, wherein the panel includes a layer E as an outermost layer.   An article of footwear comprising the upper according to any one of claims 1 to 14.