CN109476810A

CN109476810A - vamp

Info

Publication number: CN109476810A
Application number: CN201780042427.XA
Authority: CN
Inventors: A.A.拉索; L.德博福尔特
Original assignee: Solvay Specialty Polymers Italy SpA
Current assignee: Solvay Specialty Polymers Italy SpA
Priority date: 2016-07-07
Filing date: 2017-07-04
Publication date: 2019-03-15
Also published as: EP3481882A1; WO2018007359A1; JP2019523043A; US20200221825A1; KR20190024951A

Abstract

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

Description

Vamp

Cross reference to related applications

This application claims the priority for the European application number 16178295.8 submitted on July 7th, 2016, for all mesh All the contents of the application are incorporated herein by quoting mode.

Technical field

The present invention relates to a kind of vamp for footwear product, the vamp includes at least one panel, which has At least one layer, at least one layer are made of the composition comprising fluorinated thermoplastic polyether polyols.

Background technique

Vamp for footwear product is generally formed and multiple outer panel parts are stitched together.Outside these Portion's faceplate part can be made of several material, such as natural and leather, plastics, mesh fabric and supatex fabric.

" supatex fabric " is defined as passing through chemical treatment, mechanical treatment, heat treatment or solvent processing knot by long fibre It is combined and manufactured cloth-like material.The term is used to refer to fabric, such as felt in Textile Manufacturing Industry, they neither braiding , nor knitting.Typically, these long fibres hydrogenate the heat of hydrogenation of urethanes (H-TPU) by being based particularly on Thermoplastic polymer composition.

H-TPU polymer has been disclosed for the upper portion of manufacture shoes in the art, such as in US 20100186874 (Rudoiph Dassler Sports Poma AG (PUMA AKTIENGESELLSCHAFT RUDOLF DASSLER SPORT)), US 2013/0169219 (Puma SE (PUMA SE)) and US 2014/0082961 it is (sharp Walk international corporation (REEBOK INTERNATIONAL LIMITED)) in.

The machinable elastomer polyurethane of heat comprising (complete) perfluoroalkyl polyether block is for example disclosed in US5332798 (Meng Tegong Take charge of (AUSIMONT S.P.A.)) in.

Summary of the invention

Applicants have realised that providing a kind of needs of novel polymer material, which can be used for manufacturing The vamp of footwear product (especially shoes and boots), which is characterized in that when with the thermoplastic polyurethane polymer of hydrogenation (TPU) Compared to when, have improved characteristic.More specifically, the applicant, which is absorbed in, provides a kind of polymer material, the polymer material With improved resistance to soiling, improved chemical resistance and wearability, low temperature flexibility, silk smooth felling, while keeping good mechanical special Property.

Therefore, in a first aspect, the vamp includes at least one face the present invention relates to a kind of vamp for footwear product Plate, the panel have at least one layer [layer E], at least one layer is by comprising at least one fluorinated polyurethane, [F-TPU polymerize Object] composition [composition (C)] be made, the F-TPU polymer include derived from following item repetitive unit:

[monomer (a)] at least one glycol selected from the group below, the group include polyether glycol, polyester-diol, polybutadiene-two Pure and mild polycarbonate-glycol；

[monomer (b)] at least one hydroxy-end capped (complete) perfluoroalkyl polyether polymer [PFPE polymer]；

[monomer (c)] at least one aromatic, aliphatic or alicyclic diisocyanate；And

[monomer (d)] at least one aliphatic, alicyclic or aromatic glycol with from 1 to 14 carbon atom.

Preferably, the panel includes layer E as single layer

Preferably, the panel includes layer E as outermost layer.

For the applicant it has been unexpectedly discovered that when layer E is outermost layer, it provides the touching as soft silk Sense, without adding plasticizer into the composition (C).

In addition, applicant have surprisingly found that, when layer E is outermost layer, when with the thermoplastic polyurethane by hydrogenating (H-TPU) when panel made of polymer is compared, which goes out improved resistance to soiling and increased property easy to clean.

Specific embodiment

For the purpose of this specification and following claims:

Term " (complete) perfluoroalkyl polyether " is intended to refer to " complete or partial fluorinated polyethers "；

Statement " (complete) fluorine polyoxy alkylidene chain " is intended to refer to partially or fully fluorinated, linear chain or branched chain polyoxy alkylidene chain；

The use of round parentheses before and after the symbol of the part of mark compounds, chemical formula or formula or number has only Only make the more preferable difference purpose of those symbols or number and the remainder of the text, and therefore the round parentheses can also quilt It omits；

Term " vamp (upper) " (also referred to as " upper portion (vamp) ") is intended to refer to footwear product (such as shoes, boots) Covering toe, tiptoe, foot two sides and heel rear portion and the part being attached on the outer bottom of the footwear product；

Term " panel " is intended to refer to form one or more parts of vamp.Vamp can be used only a panel or will be more It is joined together to manufacture in a panel.When two or more panels are joined together to form vamp, these panels can To be selected from protheca (toe box), toe-cap (toe cap), the shoes waist (quarter), vamp, flap, heel of such as shoes (counter) band (back strap) and after shoes.

Preferably, the F-TPU polymer is block copolymer, that is, includes the polymerization of block (being also known as " section ") Object, each block include derived from least one monomer (a) as defined above, at least one monomer (b), at least one monomer (c) and the repetitive unit of at least one monomer (d).

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

Preferably, the F-TPU polymer has the fusing point (T from about 120 DEG C to about 240 DEG C_m)。

Preferably, at least one monomer (a) have from 500 to 4,000Da, more preferably from 1,000 to 4,000 number Average molecular weight.

Preferably, at least one monomer (a) selects in the following group, which includes following item, more preferably by its group At: polyethylene glycol, polypropylene glycol, poly- (tetramethylene) glycol (PTMG), poly- (1,4-butanediol) adipate ester, poly- (ethylene glycol- 1,4-butanediol) adipate ester, poly- (1,6- hexylene glycol-neopentyl) adipate, poly- caprolactone-glycol (PCL) and poly- Carbonic ester-glycol.

Poly- (tetramethylene) glycol, the pure and mild polycarbonate-glycol of poly- caprolactone-two are particularly preferred.

Preferably, at least one monomer (b) is hydroxy-end capped (complete) perfluoroalkyl polyether polymer [PFPE polymer], That is, comprising having (complete) fluorine polyoxy alkylidene chain [chain (R there are two chain end_pf)] (wherein one or two chain end is at least One-OH group end capping) polymer.

Preferably, the chain (R_pf) at least one chain end with the group end capping with following formula:

-CH₂(OCH₂CH₂)_t-OH(I)

Wherein

T is 0 or from 1 to 5.

It is highly preferred that chain (the R_pf) two chain ends with the group end capping as defined above with formula (I).

Preferably, the chain (R_pf) it is the chain with following formula:

-O-D-(CFX^#)_z1-O(R_f)(CFX^*)_z2-D^*-O-

Wherein

Z1 and z2 are same or different to each other, and are equal to or greater than 1；X^#And X^*It is same or different to each other, is-F or-CF3, on condition that When z1 and/or z2 is greater than 1, X^#And X^*It is-F；

D and D^*It is same or different to each other, is the alkylidene chain comprising from 1 to 6 and even more preferably from 1 to 3 carbon atom, The alkyl chain is optionally replaced by least one perfluoroalkyl for including from 1 to 3 carbon atom；

(R_f) it include repetitive unit R^○, be preferably made from it, the repetitive unit is independently selected from the following group, and the group is by following Item composition:

(i)-CFXO-, wherein X is F or CF₃；

(ii)-CFXCFXO-, wherein X is identical or different at each occurrence, is F or CF₃, with the proviso that at least one X is-F；

(iii)-CF₂CF₂CW₂O-, wherein each W is same or different to each other, it is F, Cl, H；

(iv)-CF₂CF₂CF₂CF₂O-；

(v)-(CF₂)_j- CFZ-O-, wherein j is from 0 to 3 integer and Z is with general formula-O-R_(f-a)The group of-T, wherein R_(f-a)It is the fluorine polyoxy alkylidene chain comprising from 0 to 10 repetitive unit, the repetitive unit is selected from the following terms :-CFXO- ,- CF₂CFXO-、-CF₂CF₂CF₂O-、-CF₂CF₂CF₂CF₂O-, wherein each X is independently F or CF₃And T is C₁-C₃Perfluor alkane Base.

It is highly preferred that chain (R_f) it is selected from following formula (R_f- a) to (R_f- c):

(R_f-a)-(CF₂O)_n(CF₂CF₂O)_m(CF₂CF₂CF₂O)_p(CF₂CF₂CF₂CF₂O)_q-

Wherein m, n, p, q are 0 or chain Rf are made to meet the integer that the mode that the above number-average molecular weight requires selects, with the proviso that If it is not 0 that p and q, which is simultaneously 0, n,；When m is not 0, m/n ratio is preferably between 0.1 and 20；When (m+n) is not 0 When, (p+q)/(m+n) is preferably between 0 and 0.2；

(R_f-b)-(CF₂CF(CF₃)O)_a(CF₂CF₂O)_b(CF₂O)_c(CF(CF₃)O)_d-

Wherein a, b, c, d are 0 or so that chain Rf meets the integer that the mode that the above number-average molecular weight requires selects；Its premise It is that at least one of a, c and d are not 0；When b is not 0, a/b is preferably between 0.1 and 10；When (a+b) is different from 0 When, (c+d)/(a+b) is preferably between 0.01 and 0.5, more preferably between 0.01 and 0.2；

(R_f-c)-(CF₂CF(CF₃)O)_e(CF₂O)_f(CF(CF₃)O)_g-

Wherein e, f, g are 0 or so that chain R_fMeet the integer that the mode that the above number-average molecular weight requires selects；When e is not 0 When, (f+g)/e is preferably between 0.01 and 0.5, more preferably between 0.01 and 0.2.

PFPE polymer is particularly preferably in the present invention, wherein chain (R_f) meet formula (R as defined above_f- a), wherein P and q is 0.

In a preferred embodiment, the PFPE polymer meets following formula (PFPE-I):

HO-(CH₂CH₂O)_t-CH₂-(R_pf)-CH₂(OCH₂CH₂)_u-OH(PFPE-I)

Wherein

T and u is 0 or from 1 to 5 each independently；And

R_pfIt is as defined above.

Preferably, there is the PFPE polymer from 400 to 10,000Da, the number more preferably from 1,000 to 5,000 to divide equally Son amount.

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

In a preferred embodiment, the amount of monomer (b) is so that the F-TPU polymer includes the fluorine from 4 to 30wt.%.

Preferably, at least one monomer (c) has 500Da or lower, the quantity point preferably from 10 to 500Da Son amount.

Preferably, at least one monomer (c) selects in the following group, which includes the following terms, preferably by following Items composition: 4,4 '-methylene-diphenylene-di-isocyanate (MDI), 1, hexamethylene-diisocyanate (HDI), 2,4- first Benzene-diisocyanate, 2,6- toluene diisocyanate, dimethylbenzene-diisocyanate, naphthalene-diisocyanate, to phenylene-two Isocyanates, hexa-methylene-diisocyanate, isophorone-diisocyanate, 4,4 '-dicyclohexyl-methanes-diisocyanate Ester and cyclohexyl-Isosorbide-5-Nitrae-diisocyanate.

MDI and HDI is particularly preferred.

Preferably, at least one monomer (d) selects in the following group, which includes the following terms, preferably by following Items composition: ethylene glycol, 1,4-butanediol (BDO), 1,6- hexylene glycol (HDO), N, N- diethanol amine and N, N- diisopropanol benzene Amine.

BDO and HDO is particularly preferred.

In a preferred embodiment, the sum of the block derived from monomer (c) and (d) is based on the total of the F-TPU polymer Weight is from 10 to 60wt.%.

Those skilled in the art will readily appreciate that comprising the block derived from monomer (a) and the repetitive unit of (b) be rubber Gluey block, and include the block of the repetitive unit derived from monomer (c) He (d) be hard block.

In a preferred embodiment, at least 80% include derived from the monomer (b) repetitive unit block [block B] at least one their end be connected to by the inclusion of the block [block C] of the repetitive unit derived from monomer (c) and include On the block [block A] of repetitive unit derived from monomer (a).

In other words, at least the 80% of B block is contained in Types Below: in the sequence of-[A-C-B-C]-.

Advantageously, which can be according in US 5332798 (Meng Te company), particularly in example 15 It is prepared by the program of disclosure.

According to preferred embodiment, which is made of the composition (C) of not plasticizer-containing.

Preferably, the composition (C) includes F-TPU polymer as defined above as the main component.

It is highly preferred that the amount of the F-TPU polymer be with based on the composition (C) total weight at least 60wt.%, More preferably at least 80wt.%, even more desirably at least 85wt.%.

Other than the F-TPU polymer, the composition (C) can optionally include other additive, such as Antioxidant, heat stabilizer, dyestuff and filler.

Embodiment, wherein the composition (C) be substantially by the F-TPU polymer and up to 1wt.% amount with On made of any combination of additive for listing, which also includes by the present invention.

According to first embodiment, the vamp includes the multiple panels being stitched together, and each panel includes as above fixed The layer E of justice.

According to alternate embodiment, the vamp includes a single sided board, which extends to the whole surface of vamp It and include layer E as defined above.Vamp comprising a single sided board is also referred to as " design of integral type vamp ".

Layer E can be manufactured according to following methods known in the art, such as by such as in US 2010/ listed above Meltblown disclosed in 0186874

As example, layer E can be manufactured by method comprising the following steps:

(i) mold is provided；

(ii) filling of Xiang Suoshu mold includes at least one elastomer fluorinated polyurethane [F-TPU polymer] as defined above Composition；

(iii) mold is sealed；

(iv) it is heat-treated the mold of the sealing；And

(v) product is taken out from the mold.

Preferably, step (iv) includes two steps, and wherein first step includes heating and continuous from 10 at the first temperature Second to 10 minutes time, and second step includes the heating and continuous time from 30 seconds to 24 hour, institute under second step Second temperature is stated lower than first temperature.

It is highly preferred that first temperature is from 120 DEG C to 300 DEG C.

It is highly preferred that the second temperature is from 50 DEG C to 200 DEG C.

Alternatively, step (iv) only include one from 50 DEG C to 300 DEG C at a temperature of it is heating and continuous from 10 seconds to 24 The step of time of hour.

Preferably, after step (iv) and before step (v), allow to cool down the mold.

According to preferred embodiment, at least one described panel includes layer E group as sole layer.

According to another preferred embodiment, at least one described panel includes layer E as defined above and at least one A texture layer [layer T] being made of texture yarn.

For example, vamp according to the present invention includes that at least one includes the face of layer E as defined above according to embodiment Plate, the layer E has outer surface and inner surface, wherein at least part of the inner surface and the texture being made of texture yarn Layer [layer T] is connected.

According to another embodiment, vamp according to the present invention includes at least one panel, which includes as above fixed The layer E and two layer T being made of texture yarn, middle layer E of justice are inserted between two layer T.

When vamp includes layer E and when one or more layer T, the vamp by by layer E and one or more layer T welding one It rises and obtains.

Welding can be carried out for example using high-frequency welding method or ultrasonic fusing method.

In a further embodiment, the present invention relates to a kind of footwear products comprising vamp as defined above.

If by the disclosure content of quoting any patent, patent application and publication that mode is incorporated herein with The application's illustrates mutually to conflict to may cause the unclear degree of term, then this explanation should be preferential.

The present invention will be hereinafter illustrated in more details by means of the example being contained in following experimental part；These Example is merely illustrative and is in no way to be construed as limiting of the scope of the present invention.

Experimental section

Material

Monomer (a):

(a1) there is the CAPA of about 2,000 molecular weight (Mw) and-OH value of about 56mg KOH/g^TM2201 is (public from Bai Situo Take charge of (Perstorp)) polycaprolactone-glycol (PLC)；

(a2) there is the polytetramethylene glycol (PTMEG) of about 2,000 Mw

(a3) have about 2,000 Mw'sUH200 (coming from UBE company) polycarbonate-glycol (PCD)

(a4) there is the BESTER of about 2,000 Mw^TM(coming from the Dow Chemical Company (DOW)) polyester-glycol

Monomer (b) with following formula:

H(OCH₂CH₂)_pOCH₂CF₂O(CF₂CF₂O)_m(CF₂O)_nCF₂CH₂O(CH₂CH₂O)_pH

(b1) p=4.7 and about 2,000 Mw

(b2) p=1.6 and about 1,700 Mw

Monomer (c):

(c1) diphenylene -4,4 '-diisocyanate (MDI)

(c2) 1, hexamethylene-diisocyanate (HDI)

Monomer (d):

(d1) 1,4-butanediol (BDO)

(d2) 1,6- hexylene glycol (HDO)

Catalyst:

Bismuth neodecanoate

The preparation of F-TPU polymer samples-method A

Since above-mentioned monomer according to being described in detail in the example 15 of US 5,332,798 (authorizing Meng Te company) listed above Identical program preparation is in the F-TPU polymer samples 1 to 4 of sheet form.

Therefore the F-TPU polymer obtained contains the repetitive unit derived from monomer (b) of 20wt.%.

The preparation of F-TPU polymer samples-method B

The F-TPU polymer samples 5 to 7 and 8 (the latter as compare) of following preparation in the form of a sheet:

Synthesize the prepolymer of the hydrogenation with the monomer (c) of equivalent proportion 2 to 1 and monomer (a) by reaction at a temperature of 90 DEG C；

The fluorinated prepolymer is synthesized with the monomer (c) of equivalent proportion 2 to 1 and monomer (b) by reaction at a temperature of 90 DEG C；

Then the prepolymer of the hydrogenation and the fluorinated prepolymer are mixed and stirring continues 30 points at 90 DEG C Clock；

Monomer (c) is further added according to selected stoichiometry；

Continue the reaction at 90 DEG C and continues 3 minutes until completing chain elongation；

It is cast the polymer therefore obtained at 100 DEG C and continues 24 hours.

The composition of the F-TPU polymer that method A and B as described above are obtained and right is reported in the following table 1 Than the composition of the polyether polyols (H-TPU) of hydrogenation.

Compare as further, uses the TPU (H-TPU9*) of commercially available hydrogenation.Monomer ratio for H-TPU9* is not It is publicly available.

Table 1

(*) comparison

The unavailable value of n/a=

It has evaluated the mechanical property of the piece made of F-TPU and H-TPU polymer and result is reported in table 2.

Table 2

(*) comparison

Result above, which shows F-TPU polymer according to the present invention, to be had and the allusion quotation in the production of the vamp of article of footwear The comparable mechanical property of the mechanical property of the H-TPU polymer used to type, and therefore F-TPU polymer is finished product vamp Good mechanical property is provided.

These pieces are used in the example being described below.

Example 1- contact angle

This test is considered having predictability for both resistance to soiling and chemical resistance.

(about 5 μ L) is dripped with the seat of DSA30 instrument (Kr ü ss GmbH, Germany) measurement water and hexadecane (as solvent) Static contact angle (SCA).SCA value and standard deviation are calculated among ten contact angles.

According to Owens, Wendt, Rabel and Kaelble method (WORK method) gauging surface free energy (SFE), the party If method is the standard method for the surface free energy by calculating solid with the contact angle of dry liquids.

As a result it is summarised in the following table 3.

Table 3

Sample	SCA H₂O	SCA C₁₆	SFE(mN/m)
				F-TPU 1	104	64.5	16.1
F-TPU 2	110.5	63.6	15.09
				F-TPU 3	106.7	62.9	15.90
F-TPU 4	86	61	23.6
				F-TPU 5	105	68	14.9
F-TPU 6	103	66	16
				F-TPU 7	98	70	16.9
H-TPU 8(*)	77	46	30.93
				H-TPU 9(*)	81	29	31.7

(*) comparison

SCA=static contact angle

H₂O=water

C₁₆=hexadecane

SFE=surface free energy

Result above is shown with water (H₂) and hexadecane (C O₁₆) both measurement contact angle increase, and be used as reference The 31mN/m of the thermoplastic polyurethane of the hydrogenation of compound is compared, and surface can be decreased until the range from 15 to 16mN/m.These Data and the increase by one for the resistance to soiling and chemical resistance given with H-TPU polymer phase ratio by these F-TPU polymer It causes.

The test of example 2- blue denim

This test is considered having predictability for both resistance to soiling and wearability.

It is tested using Taber Industries 5750LinearAbraser instrument, which is set as following Under the conditions of run:

Circulation rate: 30 circulation/min

Stroke length: 2.54cm (1 inch)

Recurring number: 200

Total load: 1kg.

It is once used with dry denim and once on F-TPU 1, F-TPU 2, F-TPU 3, F-TPU 5 and F-TPU 7 Wet denim is tested.

It is before carrying out the test with wet denim, denim is submerged in water for 10 seconds, it is then moved out simultaneously And it is wet that water is squeezed out to the water so that denim does not drip with hand but is touched.

Carry out these tests as follows: by the denim sample of about 30mm x 30mm measurement be fixed on fixed device so as to Prevent the displacement of the sample during the test.Then the sample of each F-TPU and H-TPU is placed on the denim sample And it is equally fixed on the fixation device.

Checkpointing is as follows:

After friction and

After with isopropanol (IPA) cleaning.

The result of the dry test: it for F-TPU 1, F-TPU 2, F-TPU 3, F-TPU5 and F-TPU7, is not observed Stain.

The result of the wet test: it for F-TPU 1, F-TPU 2, F-TPU 3, F-TPU 5 and F-TPU7, observes very Slight haloing.

The test of example 3- stain

The drop of every kind of coloring agent listed above is positioned to contact and make with the surface of the sample made of F-TPU 1 Continue 24 hours under ambient conditions.Then the sample is cleaned with water.

The sample made of H-TPU, which is used, makes comparisons and such as processing disclosed above.

As a result it is summarised in the following table 4, wherein

Not ++=do not have stain

+=trace/dizzy

=stain

Table 4

(*) comparison

Result above clearly show the resistance to soiling and chemical resistance two of the F-TPU sample compared with the H-TPU sample The increase of person.

The assessment of example 4- tactile characteristics

The tactile characteristics of F-TPU and H-TPU are measured by subjectively testing the piece of these materials by 5 individual feels (especially soft feel).

Soft feel is subjectively to touch measurement by hand and graded with from 1 to 5 scale, wherein 1 is poor Soft feel (hard feel) and 5 be excellent soft feel.Participant individually participated in this research, so they It reacts aspect and does not influence each other.Four kinds of samples are presented to participant with random sequence and them is required to experience and to them Grading.

As a result it is summarised in the following table 5.

Table 5

(*) comparison

Result above is clearly shown, when compared with the piece obtained by H-TPU polymer, with F- according to the present invention The piece that TPU is obtained shows better tactile characteristics, particularly improved soft feel.

Claims

1. a kind of vamp for footwear product includes at least one panel, which has at least one layer [layer E], this is extremely A few layer is made, the F- of the composition [composition (C)] comprising at least one fluorinated polyurethane [F-TPU polymer] TPU polymer includes the repetitive unit derived from following item:

[monomer (c)] at least one aromatic, aliphatic or alicyclic diisocyanate；And

2. vamp according to claim 1, wherein at least one monomer (a) selects in the following group, which includes poly- Ethylene glycol, polypropylene glycol, poly- (tetramethylene) glycol (PTMG), poly- (1,4-butanediol) adipate ester, poly- (ethylene glycol-Isosorbide-5-Nitrae- Butanediol) adipate ester, poly- (1,6- hexylene glycol-neopentyl) adipate, poly- caprolactone-glycol (PCL) and poly- carbonic acid Ester-glycol.

3. vamp according to claim 1 or 2, wherein at least one monomer (b) is that there are two chain ends comprising tool (complete) fluorine polyoxy alkylidene chain [chain (R_pf)] hydroxy-end capped PFPE polymer, wherein one or two chain end is at least One-OH group end capping.

4. vamp according to claim 3, wherein the chain (R_pf) at least one chain end with the base with formula (I) Group's sealing end:

-CH₂(OCH₂CH₂)_t-OH(I)

Wherein

T is 0 or from 1 to 5.

5. vamp according to claim 3, wherein the chain (R_pf) two chain ends with the group of formula (I) seal End:

-CH₂(OCH₂CH₂)_t-OH(I)

Wherein

T is 0 or from 1 to 5.

6. vamp according to any one of claim 3 to 5, wherein the chain (R_pf) it is the chain with following formula

-O-D-(CFX^#)z₁-O(R_f)(CFX^*)z₂-D*-O-

Wherein

Z1 and z2 are same or different to each other, and are equal to or greater than 1；X^#It is same or different to each other with X*, is-F or-CF3, on condition that When z1 and/or z2 is greater than 1, X^#It is-F with X*；

D and D* are same or different to each other, and are the alkylidene chains comprising from 1 to 6 and even more preferably from 1 to 3 carbon atom, The alkyl chain is optionally replaced by least one perfluoroalkyl for including from 1 to 3 carbon atom；

(R_f) include R ° of repetitive unit, be preferably made from it, the repetitive unit is independently selected from the following group, and the group is by following Item composition:

(i)-CFXO-, wherein X is F or CF₃；

(iv)-CF₂CF₂CF₂CF₂O-；

7. vamp according to claim 6, wherein the chain (R_f) it is selected from following formula (R_f- a) to (R_f- c):

(R_f-a)-(CF₂O)_n(CF₂CF₂O)_m(CF₂CF₂CF₂O)_p(CF₂CF₂CF₂CF₂O)_q-

(R_f-b)-(CF₂CF(CF₃)O)_a(CF₂CF₂O)_b(CF₂O)_c(CF(CF₃)O)_d-

(R_f-c)-(CF₂CF(CF₃)O)_e(CF₂O)_f(CF(CF₃)O)_g-

Wherein e, f, g are 0 or so that chain Rf meets the integer that the mode that the above number-average molecular weight requires selects；When e is not 0 When, (f+g)/e is preferably between 0.01 and 0.5, more preferably between 0.01 and 0.2.

8. vamp according to any one of the preceding claims, wherein the PFPE polymer meets following formula (PFPE-I):

HO-(CH₂CH₂O)_t-CH₂-(R_pf)-CH₂(OCH₂CH₂)_u-OH(PFPE-I)

Wherein

T and u is 0 or from 1 to 5 each independently；And

R_pfIt is as defined in claim 6.

9. vamp according to any one of the preceding claims, wherein at least one monomer (c) is selected in the following group It selects, which includes 4,4- methylene-diphenylene-di-isocyanate (MDI), 1, hexamethylene-diisocyanate (HDI), 2,4- first Benzene-diisocyanate, 2,6- toluene diisocyanate, dimethylbenzene-diisocyanate, naphthalene-diisocyanate, to phenylene-two Isocyanates, hexa-methylene-diisocyanate, isophorone-diisocyanate, 4,4- dicyclohexyl-methane-diisocyanate With cyclohexyl-Isosorbide-5-Nitrae-diisocyanate.

10. vamp according to any one of the preceding claims, wherein at least one monomer (d) is selected in the following group It selects, which includes ethylene glycol, 1,4-butanediol (BDO), 1,6- hexylene glycol (HDO), N, N- diethanol amine and N, N- diisopropanol Aniline.

11. vamp according to any one of the preceding claims, wherein at least 80% comprising be derived from the monomer (b) at least one their end of the block [B block] of repetitive unit is by the inclusion of the repetition for being derived from the monomer (c) The block [block C] of unit is connected on the block [block A] comprising the repetitive unit derived from the monomer (a).

12. vamp according to any one of the preceding claims, wherein the composition (C) not plasticizer-containing.

13. vamp according to any one of the preceding claims, wherein the composition (C) includes to be based on the combination The F-TPU polymer of the total weight of object (C) at least amount of 60wt.%.

14. vamp according to any one of the preceding claims, wherein the panel includes layer E as outermost layer.

15. a kind of footwear product, comprising according to claim 1 to vamp described in any one of 14.