阅读说明：本技术 包含半晶质vdf聚合物和氟化热塑性弹性体嵌段共聚物的组合物 (Compositions comprising semicrystalline VDF polymers and fluorinated thermoplastic elastomeric block copolymers ) 是由 D.麦基尔罗伊 K.S.高塔姆 S.斯里尼瓦桑 于 2018-03-13 设计创作，主要内容包括：本发明涉及一种基于热塑性偏二氟乙烯(VDF)聚合物和热塑性氟化弹性体的氟聚合物组合物,其具有有利的性能,包括改进的在柔性与刚度之间的折衷,并且适合于值得注意地在制造移动电子装置的零件和附件中使用；一种制造所述组合物的方法；以及一种由所述组合物制造所述零件的方法,以及使用所述零件的移动电子装置。(The present invention relates to a fluoropolymer composition based on a thermoplastic vinylidene fluoride (VDF) polymer and a thermoplastic fluorinated elastomer, which has advantageous properties, including an improved compromise between flexibility and stiffness, and is suitable for notably use in the manufacture of parts and accessories for mobile electronic devices; a method of making the composition; and a method of manufacturing the part from the composition, and a mobile electronic device using the part.)

1. A fluoropolymer composition [ composition (C) ], said composition comprising:

-at least one thermoplastic elastomer [ polymer (F-TPE) ], comprising:

(i) At least one elastomeric block (A) consisting of a sequence of repeating units comprising repeating units derived from at least one fluorinated monomer, said block (A) having a glass transition temperature of less than 25 ℃ as determined according to ASTM D3418, and

(ii) at least one thermoplastic block (B) consisting of a sequence of repeating units comprising repeating units derived from at least one fluorinated monomer,

Wherein the crystallinity of said block (B) and its weight fraction in the polymer (F-TPE) is such as to provide the polymer (F-TPE) with a heat of fusion (Δ H) of at most 20J/g, when determined according to ASTM D3418_f) The amount of said polymer (F-TPE) being at least 50% wt;

-at least one thermoplastic vinylidene fluoride (VDF) polymer [ polymer (F) ]]Comprising recurring units derived from VDF in an amount of at least 85% moles with respect to the total moles of recurring units of polymer (F) having a composition of at least 25J/g when determined according to ASTM D3418heat of fusion (. DELTA.H) of the polymer (F-TPE)_f) (ii) a And optionally

-at least one methyl methacrylate polymer [ polymer (M) ] in an amount of up to 25% wt,

the% wt refers to the sum of the weights of polymer (F), elastomer (F-TPE) and polymer (M).

2. Composition (C), wherein the polymer (F-TPE) comprises, preferably consists of:

-at least one elastomeric block (a) selected from the group consisting of:

(1) Vinylidene fluoride (VDF) -based elastomer block (A) consisting of a sequence of repeating units_VDF) Said sequence comprising recurring units derived from VDF and recurring units derived from at least one fluorinated monomer different from VDF, typically selected from the group consisting of:

(a)C₂-C₈Perfluoroolefins, such as Tetrafluoroethylene (TFE), Hexafluoropropylene (HFP);

(b) Hydrogen-containing C other than VDF₂-C₈Fluoroolefins, e.g. vinyl fluoride, trifluoroethylene (TrFE), Hexafluoroisobutylene (HFIB), of formula CH₂＝CH-R_f1Wherein R is_f1Is C₁-C₆a perfluoroalkyl group;

(c)C₂-C₈Chlorine-and/or bromine-containing fluoroolefins, such as Chlorotrifluoroethylene (CTFE);

(d) Having the formula CF₂＝CFOR_f1Perfluoroalkyl vinyl ethers (PAVE) of (A), wherein R_f1Is C₁-C₆Perfluoroalkyl radicals, e.g. CF₃(PMVE)、C₂F₅Or C₃F₇；

(e) having the formula CF₂＝CFOX₀Perfluoroalkyloxy vinyl ethers of (i) wherein X₀is C containing one or more than one ether oxygen atom₁-C₁₂Perfluoroalkoxyalkyl, notably including those having the formula CF₂＝CFOCF₂OR_f2in which R is_f2Is C₁-C₃perfluoro (oxy) alkyl, e.g. -CF₂CF₃、-CF₂CF₂-O-CF₃and-CF₃(ii) a And

(f) (per) fluorodioxoles having the formula:

Wherein R is_f3、R_f4、R_f5and R_f6Each of which is the same or different from each other, is independently a fluorine atom, C optionally containing one or more oxygen atoms₁-C₆Perfluoro (oxy) alkyl, e.g. -CF₃、-C₂F₅、-C₃F₇、-OCF₃or-OCF₂CF₂OCF₃(ii) a And

(2) Tetrafluoroethylene (TFE) -based elastomer blocks (A) consisting of a sequence of repeating units_TFE) Said sequence comprising recurring units derived from TFE and recurring units derived from at least one fluorinated monomer different from TFE, typically selected from the group consisting of those of classes (b), (c), (d), (e) as defined above;

-at least one thermoplastic block (B) consisting of a sequence of repeating units comprising repeating units derived from at least one fluorinated monomer.

3. The composition (C) of claim 2, wherein the elastomeric block (A) is a block (A) consisting of a sequence of repeating units_VDF) The sequence comprises, preferably consists of: relative to block (A)_VDF) The total moles of repeating units of the sequence of (a),

-from 45% to 80% by moles of recurring units derived from vinylidene fluoride (VDF),

-from 5% to 50% by moles of recurring units derived from at least one fluorinated monomer different from VDF,

-optionally up to 1.0% by moles OF recurring units derived from at least one bis-Olefin (OF) having the formula:

R_AR_B＝CR_C-T-CR_D＝R_ER_F

Wherein R is_A、R_B、R_C、R_D、R_EAnd R_FAre the same or different from each other and are selected from the group consisting of H, F, Cl, C₁-C₅alkyl and C₁-C₅(per) fluoroalkyl and T is a linear or branched C optionally containing one or more than one ether oxygen atom₁-C₁₈Alkylene or cycloalkylene, or is (per) fluoropolyoxyalkylene; and

-optionally up to 30% by moles of recurring units derived from at least one hydrogenated monomer.

4. The composition (C) of any one of the preceding claims, wherein the block (B) is selected from the group consisting of:

-block (B)_VDF) Consisting of a sequence of recurring units derived from vinylidene fluoride and optionally one or more than one additional fluorinated monomer different from VDF, such as HFP, TFE or CTFE, and optionally a hydrogenated monomer, such as a (meth) acrylic monomer, as detailed above, wherein the amount of recurring units derived from VDF is based on the block (B)_VDF) 85 to 100 mol% of the total moles of recurring units of (a);

-block (B)_TFE) Consisting of a sequence of recurring units derived from tetrafluoroethylene and optionally an additional perfluorinated monomer different from TFE, wherein the amount of recurring units derived from TFE is 75 to 100% moles, based on the total moles of recurring units of block (B);

-block (B)_E/(C)TFE) Consisting of a sequence of recurring units derived from ethylene and recurring units derived from CTFE and/or TFE, possibly in combination with additional monomers.

5. Composition (C) according to any one of the preceding claims, wherein the weight ratio between block (A) and block (B) in polymer (F-TPE) is from 95:5 to 65:35, preferably from 90:10 to 70: 30.

6. The composition (C) of any one of the preceding claims, wherein the crystallinity of block (B) and its weight fraction in the polymer (F-TPE) is such as to provide the polymer (F-TPE) with a heat of fusion of at most 20J/g, preferably of at most 18J/g, more preferably of at most 15J/g, when determined according to ASTM D3418; on the other hand, the polymer (F-TPE) combines thermoplastic and elastomeric characteristics so as to have a certain crystallinity, providing a heat of fusion of at least 2.5J/g, preferably at least 3.0J/g.

7. The composition (C) of any one of the preceding claims, wherein the polymer (F) is a polymer comprising:

(a') at least 85% by moles of recurring units derived from vinylidene fluoride (VDF);

(b') optionally from 0.1% to 15%, preferably from 0.1% to 12%, more preferably from 0.1% to 10% by moles of recurring units derived from a fluorinated monomer different from VDF; and

(c') optionally from 0.1 to 5% by moles, preferably from 0.1 to 3% by moles, more preferably from 0.1 to 1% by moles of recurring units derived from one or more hydrogenated comonomers,

All the above% by moles refer to the total moles of recurring units of the polymer (F).

8. The composition (C) of claim 7, wherein the polymer (F) is a polymer consisting essentially of:

(a') at least 85% by moles of recurring units derived from vinylidene fluoride (VDF);

(b') optionally from 0.1% to 15%, preferably from 0.1% to 12%, more preferably from 0.1% to 10% by moles of a fluorinated monomer different from VDF; said fluorinated monomers are preferably selected in the group consisting of: vinyl Fluoride (VF)₁) Chlorotrifluoroethylene (CTFE), Hexafluoropropylene (HFP), Tetrafluoroethylene (TFE), perfluoromethylvinyl ether (MVE), trifluoroethylene (TrFE)) As well as mixtures thereof, and mixtures thereof,

All the above% by moles refer to the total moles of recurring units of the polymer (F).

9. Composition (C) according to any one of the preceding claims, wherein polymer (M) is chosen from homopolymers of methyl methacrylate and C₂-C₆Copolymers of alkyl acrylates, wherein the methyl methacrylate content of these copolymers is at least about 55% by weight and preferably at least about 60% by weight, relative to the total weight of polymer (M); this content generally does not exceed about 90% by weight; in most cases, this content does not exceed 80% by weight.

10. the composition (C) according to any one of the preceding claims, wherein:

-the amount of polymer (F-TPE) in the composition (C) is at least 60% wt, most preferably at least 70% wt, relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M); and/or advantageously at most 97% wt, preferably at most 95% wt, more preferably at most 94% wt; and/or

-the amount of polymer (F) in the composition (C) is at least 3% wt, preferably at least 5% wt, more preferably at least 6% wt, relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M); and/or is at most 50% wt, preferably at most 40% wt, more preferably at most 30% wt; and/or

-the amount of polymer (M) is at most 25% wt, preferably at most 20% wt, more preferably at most 15% wt, relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M).

11. The composition (C) of claim 10, which does not comprise any polymer (M) and comprises:

From 50 to 97% wt, preferably from 60 to 95% wt, more preferably from 70 to 94% wt of a polymer (F-TPE), and

from 3 to 50% wt, preferably from 5 to 40% wt, more preferably from 6 to 30% wt of polymer (F),

wherein% wt is defined with respect to the total weight of polymer (F-TPE) and polymer (F).

12. the composition (C) according to claim 10, comprising: relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M),

-from 50 to 96% wt, preferably from 60 to 92% wt, more preferably from 70 to 89% wt of a polymer (F-TPE);

-from 3 to 45% wt, preferably from 5 to 35% wt, more preferably from 6 to 25% wt of polymer (F); and

from 1 to 25% wt, preferably from 3 to 20% wt, more preferably from 5 to 15% wt of polymer (M).

13. A process for manufacturing a composition (C) as claimed in any one of claims 1 to 12, wherein it comprises at least one step of mixing a polymer (F), a polymer (F-TPE), and possibly a polymer (M).

14. A method of making a shaped part, the method comprising molding the composition (C) of any one of claims 1 to 12, wherein the molding is by at least one of compression molding, extrusion molding, injection molding, and transfer molding.

15. A shaped part made from the composition (C) according to any one of claims 1 to 12, wherein the shaped part is a component intended to be connected to at least one of a peripheral device, an accessory and a device of a mobile electronic device.

16. The molded part of claim 15, selected from the group consisting of:

Wrist bands, chest bands and other appendages intended for use in securing an electronic device to a specific part of the human body;

-components of a signal transmission cable, including a cable for transmitting/receiving electrical signals generated in an acoustic system or an imaging system;

-a protective casing designed to receive and house a portable electronic device;

-parts of earplugs, including those intended to be connected to a portable electronic device.

Technical Field

The present invention relates to a fluoropolymer composition having advantageous properties, including an improved compromise between flexibility and stiffness, and suitable for notably use in the manufacture of parts and accessories for mobile electronic devices; a method of making the composition; and a method of manufacturing the part from the composition, and a mobile electronic device using the part.

Background

today, mobile electronic devices, such as mobile phones, Personal Digital Assistants (PDAs), laptop computers, MP3 players, heart rate monitors, etc., are widely used around the world. For even greater portability and convenience, mobile electronic devices are becoming smaller and lighter, while at the same time becoming more and more capable of performing more advanced functions and supplementing connection services and peripherals, all due to the development of devices and network systems.

wrist bands, chest bands and other attachments have been developed for securing electronic devices to specific parts of the human body. In most cases, these are made of elastomeric polymer materials. For example, wristbands have been disclosed, for example, in EP 2468127B (biwis.a.), which relates to an article of jewelry made from a composition comprising an elastomeric matrix having dispersed therein a reinforcing filler selected from the group consisting of microfibers, polytetrafluoroethylene nanoparticles, and mixtures thereof; similarly, GB 2460890 (event LTD) discloses a strap comprising a protective portion housing an electronic tag and a second portion forming a strap to be worn by a person, wherein the strap material may be an elastomeric material such as rubber, in particular silicone rubber, and the protective portion may be made of metal or nylon.

In addition, a signal transmission cable for transmitting/receiving an electrical signal generated in an acoustic system or an imaging system may be connected to the portable electronic product for use with an earphone, a headphone, a speaker, or an image display device. All these cables have an outer sheath, also called "cable jacket" or "outermost coating", which surrounds all the components of the cable and protects them from the external environment, while at the same time it provides easy handling, flexibility and mechanical strength. Cables of this type have been disclosed, for example, in US 2014041897 (johnston LTD) and US 2011051973 (TSINGHUA UNIVERSITY (tsingua UNIVERSITY), hong HAI PRECISION INDUSTRY LTD).

Furthermore, solutions have been devised to protect portable electronic devices and to withstand the rigors of frequent use (including dropping and impact) based on protective enclosures designed to receive and house them.

Enclosures for portable electronic devices have been disclosed in several patents and patent applications, such as, for example, WO 2011/053740(BENLKIN interaction, INC.), WO 2013/043462 (speech PRODUCT DESIGN, LLC.), WO 2014/145262(MAV IP LLC.), and US 2015097009 (blue organic solvents, INC.). Enclosures for portable electronic devices are typically made of hydrogenated thermoplastic polyurethane polymers because of their durability, rubber behavior and tear resistance, but solutions based on silicone or hydrocarbon rubbers are also sought.

While conventional headsets have relatively large ear cups, smaller headsets, known as ear buds, have become the solution of choice for electronic device users to play audio. These earplugs have elastomeric earpieces that carry suitable speakers within the ear canals of the user. These parts need to be durable enough to withstand rough handling and also have wearing comfort and significant stain resistance.

While all of these different parts, accessories and devices as listed above, which are typically connected to mobile electronic products, can be considered different and unconnected, they share very similar requirements for the materials used for their manufacture. The material should be easy to process into complex geometric parts, should ensure electrical insulation/barrier between the components, should provide excellent durability and wear resistance, should enable unlimited aesthetic possibilities (due to its colorability), should be endowed with excellent weather/stain protection, and should also have an excellent mechanical properties/flexibility balance.

Furthermore, although it has been found that rubbers (e.g. silicone rubbers) are used, they also have the disadvantage of their inherent thermoset character, thus making typical easy thermoplastic processing impossible, requiring extended curing times, and resulting in the loss of scrap and decorations (which cannot be reprocessed).

efforts are underway to provide materials capable of handling all of the above requirements in this field of use, and while various plastic-based solutions have been attempted, continued improvements are needed to meet the unmet challenges.

Disclosure of Invention

within this framework, the present invention aims to provide a solution based on a specific combination of fluorinated polymers, and more specifically a combination of certain fluorinated thermoplastic elastomers and certain thermoplastic fluoropolymers, with the aim of achieving a good stiffness/flexibility property compromise, yet maintaining all the advantageous behaviour of the fluorinated thermoplastic elastomers.

More specifically, in a first aspect, the present invention relates to a fluoropolymer composition [ composition (C) ] comprising:

-at least one thermoplastic elastomer [ polymer (F-TPE) ], comprising:

(i) At least one elastomeric block (A) consisting of a sequence of repeating units comprising repeating units derived from at least one fluorinated monomer, said block (A) having a glass transition temperature of less than 25 ℃ as determined according to ASTM D3418, and

(ii) At least one thermoplastic block (B) consisting of a sequence of repeating units comprising repeating units derived from at least one fluorinated monomer,

Wherein the crystallinity of said block (B) and its weight fraction in the polymer (F-TPE) is such as to provide the polymer (F-TPE) with a heat of fusion (Δ H) of at most 20J/g, when determined according to ASTM D3418_f)；

-at least one thermoplastic vinylidene fluoride (VDF) polymer [ polymer (F) ]]Comprising recurring units derived from VDF in an amount of at least 85% moles with respect to the total moles of recurring units of polymer (F) having a heat of fusion (Δ H) of the polymer (F-TPE) of at least 25J/g, when determined according to ASTM D3418_f) (ii) a And optionally

-at least one methyl methacrylate polymer [ polymer (M) ] in an amount of up to 25% wt,

The% wt refers to the sum of the weights of polymer (F), elastomer (F-TPE) and polymer (M).

The applicant has surprisingly found that, thanks to the combination of the characteristics of polymer (F-TPE) and polymer (F) as detailed above, composition (C) as detailed above provides a particularly advantageous combination of characteristics making these compositions particularly suitable for making different parts, accessories and devices intended to be used in connection with mobile electronic devices. In particular, thanks to the intermixing of polymer (F-TPE) and polymer (F) as detailed above, the parts made from said composition (C) have an excellent balance of mechanical characteristics, durability and abrasion resistance and elastomeric characteristics that can be easily adjusted (depending on the intended use) over the whole composition range, and at the same time have an improved resistance to staining, providing an uneconomical aesthetic appearance even after prolonged use and exposure to stains typical of normal household environments.

Detailed Description

Fluorinated thermoplastic elastomer [ Polymer (F-TPE) ]

For the purposes of the present invention, the term "elastomer" when used in combination with "block (a)" is intended to mean in particular a polymer segment which, when taken alone, is substantially amorphous, that is to say has a heat of fusion, as measured according to astm d3418, of less than 2.0J/g, preferably less than 1.5J/g, more preferably less than 1.0J/g.

For the purposes of the present invention, the term "thermoplastic" when used in conjunction with "block (B)" is intended to mean, inter alia, a polymer segment that is semicrystalline when taken alone and has a detectable melting point with an associated heat of fusion of more than 10.0J/g as measured according to ASTM D3418.

The fluorinated thermoplastic elastomer of the composition (C) of the invention is advantageously a block copolymer, typically having a structure comprising at least one block (a) alternating with at least one block (B), that is to say that the fluorinated thermoplastic elastomer typically comprises, preferably consists of, one or more repeating structures of the type (B) - (a) - (B). In general, the polymer (F-TPE) has a structure of types (B) - (a) - (B), i.e., comprises a central block (a) having two ends connected at both ends with side blocks (B).

alternatively, block (a) is often referred to as soft block (a); alternatively, block (B) is often referred to as hard block (B).

the term "fluorinated monomer" is hereby intended to mean an ethylenically unsaturated monomer containing at least one fluorine atom.

The fluorinated monomer may further comprise one or more other halogen atoms (Cl, Br, I).

Any of the one or more blocks (a) and (B) may further comprise repeating units derived from at least one hydrogenated monomer, wherein the term "hydrogenated monomer" is intended to mean an ethylenically unsaturated monomer comprising at least one hydrogen atom and no fluorine atoms.

The elastomeric block (a) may further comprise recurring units derived from at least one bis-olefin [ bis-Olefin (OF) ] having the formula:

R_AR_B＝CR_C-T-CR_D＝R_ER_F

Wherein R is_A、R_B、R_C、R_D、R_EAnd R_FAre the same or different from each other and are selected from the group consisting of H, F, Cl, C₁-C₅Alkyl and C₁-C₅(per) fluoroalkyl and T is a linear or branched C optionally comprising one or more than one ether oxygen atom, preferably at least partially fluorinated₁-C₁₈Alkylene or cycloalkylene, or (per) fluoropolyoxyalkylene.

The bis-Olefin (OF) is preferably selected from the group consisting OF those having any one OF the formulae (OF-1), (OF-2) and (OF-3):

(OF-1)

wherein j is an integer comprised between 2 and 10, preferably between 4 and 8, and R1, R2, R3 and R4, equal to or different from each other, are selected from the group consisting of H, F, C₁-C₅Alkyl and C₁-C₅(per) fluoroalkyl groups;

(OF-2)

Wherein each a is the same or different from each other and, at each occurrence, is independently selected from the group consisting of H, F and Cl; each B is the same OR different from each other and, at each occurrence, is independently selected from the group consisting of H, F, Cl and OR_BGroup of (I) wherein R_BIs a branched or straight chain alkyl group which may be partially, substantially or fully fluorinated or chlorinated, E is an optionally fluorinated divalent group having 2 to 10 carbon atoms which may be interrupted by ether linkages; preferably E is- (CF)₂)_m-a group in which m is an integer comprised between 3 and 5; a preferred bis-olefin OF the type (OF-2) is F₂C＝CF-O-(CF₂)₅-O-CF＝CF₂；

Wherein E, A and BHaving the same meaning as defined above, R5, R6 and R7, equal to or different from each other, are selected from the group consisting of H, F, C₁-C₅Alkyl and C₁-C₅(per) fluoroalkyl groups.

If the block (a) consists OF a sequence OF recurring units further comprising recurring units derived from at least one bis-Olefin (OF), said sequence typically comprises recurring units derived from said at least one bis-Olefin (OF) in an amount comprised between 0.01% and 1.0% by moles, preferably between 0.03% and 0.5% by moles, more preferably between 0.05% and 0.2% by moles, based on the total moles OF recurring units OF the block (a).

The polymer (F-TPE) typically comprises, preferably consists of:

-at least one elastomeric block (a) selected from the group consisting of:

(1) Vinylidene fluoride (VDF) -based elastomer block (A) consisting of a sequence of repeating units_VDF) Said sequence comprising recurring units derived from VDF and recurring units derived from at least one fluorinated monomer different from VDF, typically selected from the group consisting of:

(a)C₂-C₈Perfluoroolefins, such as Tetrafluoroethylene (TFE), Hexafluoropropylene (HFP);

(b) Hydrogen-containing C other than VDF₂-C₈Fluoroolefins, e.g. vinyl fluoride, trifluoroethylene (TrFE), Hexafluoroisobutylene (HFIB), of formula CH₂＝CH-R_f1Wherein R is_f1Is C₁-C₆A perfluoroalkyl group;

(c)C₂-C₈Chlorine-and/or bromine-containing fluoroolefins, such as Chlorotrifluoroethylene (CTFE);

(d) having the formula CF₂＝CFOR_f1perfluoroalkyl vinyl ethers (PAVE) of (A), wherein R_f1is C₁-C₆Perfluoroalkyl radicals, e.g. CF₃(PMVE)、C₂F₅Or C₃F₇；

(e) Having the formula CF₂＝CFOX₀perfluoroalkyloxy vinyl ethers of (i) wherein X₀Is C containing one or more than one ether oxygen atom₁-C₁₂Perfluoroalkoxyalkyl, notably including those having the formula CF₂＝CFOCF₂OR_f2In which R is_f2Is C₁-C₃Perfluoro (oxy) alkyl, e.g. -CF₂CF₃、-CF₂CF₂-O-CF₃and-CF₃(ii) a And

(f) (per) fluorodioxoles having the formula:

wherein R is_f3、R_f4、R_f5And R_f6Each of which is the same or different from each other, is independently a fluorine atom, C optionally containing one or more oxygen atoms₁-C₆perfluoro (oxy) alkyl, e.g. -CF₃、-C₂F₅、-C₃F₇、-OCF₃or-OCF₂CF₂OCF₃(ii) a And

(2) Tetrafluoroethylene (TFE) -based elastomer blocks (A) consisting of a sequence of repeating units_TFE) Said sequence comprising recurring units derived from TFE and recurring units derived from at least one fluorinated monomer different from TFE, typically selected from the group consisting of those of classes (b), (c), (d), (e) as defined above;

-at least one thermoplastic block (B) consisting of a sequence of repeating units comprising repeating units derived from at least one fluorinated monomer.

One or more blocks (A)_VDF) And (A)_TFE) Any of which may further comprise repeating units derived from at least one hydrogenated monomer, which may be selected from the group consisting of: c₂-C₈Non-fluorinated olefins such as ethylene, propylene or isobutylene, and may further comprise repeat units derived from at least one bis-Olefin (OF) as detailed above.

Preferably the elastomeric block (A) is a block (A) as detailed above_VDF) The block (A)_VDF) Typically consisting of a sequence of repeating units comprising, preferably consisting of: relative to block (A)_VDF) The total moles of repeating units of the sequence of (a),

-from 45% to 80% by moles of recurring units derived from vinylidene fluoride (VDF),

-from 5% to 50% by moles of recurring units derived from at least one fluorinated monomer different from VDF,

-optionally up to 1.0% by moles OF recurring units derived from at least one bis-Olefin (OF) as detailed above; and

-optionally up to 30% by moles of recurring units derived from at least one hydrogenated monomer.

Block (B) may consist of a sequence of repeating units comprising:

-recurring units derived from one or more than one fluoromonomer, preferably selected from the group consisting of:

(a)C₂-C₈perfluoroolefins, such as Tetrafluoroethylene (TFE), Hexafluoropropylene (HFP);

(b) Containing hydrogen C₂-C₈Fluoroolefins, such as vinylidene fluoride (VDF), vinyl fluoride, trifluoroethylene (TrFE), Hexafluoroisobutylene (HFIB), of formula CH₂＝CH-R_f1wherein R is_f1Is C₁-C₆a perfluoroalkyl group;

(c)C₂-C₈Chlorine-and/or bromine-containing fluoroolefins, such as Chlorotrifluoroethylene (CTFE);

(d) Having the formula CF₂＝CFOR_f1Perfluoroalkyl vinyl ethers (PAVE) of (A), wherein R_f1Is C₁-C₆perfluoroalkyl radicals, e.g. CF₃(PMVE)、C₂F₅Or C₃F₇；

(e) Having the formula CF₂＝CFOX₀Perfluoroalkyloxy vinyl ethers of (i) wherein X₀Is C containing one or more than one ether oxygen atom₁-C₁₂perfluoroalkoxyalkyl, notably including those having the formula CF₂＝CFOCF₂OR_f2In which R is_f2Is C₁-C₃perfluoro (oxy) alkyl, e.g. -CF₂CF₃、-CF₂CF₂-O-CF₃and-CF₃(ii) a And

(f) (per) fluorodioxoles having the formula:

wherein R is_f3、R_f4、R_f5And R_f6Each of which is the same or different from each other, is independently a fluorine atom, C optionally containing one or more oxygen atoms₁-C₆Perfluoro (oxy) alkyl, e.g. -CF₃、-C₂F₅、-C₃F₇、-OCF₃or-OCF₂CF₂OCF₃(ii) a And

-optionally, recurring units derived from one or more than one hydrogenated monomer as detailed above, notably comprising ethylene, propylene, (meth) acrylic acid monomers, styrene monomers.

more specifically, block (B) may be selected from the group consisting of:

-block (B)_VDF) Consisting of a sequence of recurring units derived from vinylidene fluoride and optionally one or more than one additional fluorinated monomer different from VDF, such as HFP, TFE or CTFE, and optionally a hydrogenated monomer, such as a (meth) acrylic monomer, as detailed above, wherein the amount of recurring units derived from VDF is based on the block (B)_VDF) 85 to 100 mol% of the total moles of recurring units of (a);

-block (B)_TFE) Consisting of a sequence of recurring units derived from tetrafluoroethylene and optionally an additional perfluorinated monomer different from TFE, wherein the amount of recurring units derived from TFE is from 75 to 100% by moles, based on the total moles of recurring units of block (B)A step of;

-block (B)_E/(C)TFE) Consisting of a sequence of recurring units derived from ethylene and recurring units derived from CTFE and/or TFE, possibly in combination with additional monomers.

The weight ratio between block (a) and block (B) in the fluorinated thermoplastic elastomer is typically comprised between 95:5 and 10: 90.

According to certain preferred embodiments, the polymer (F-TPE) comprises a major amount of blocks (a); according to these examples, the polymer (F-TPE) used in the process of the invention is characterized by a weight ratio between block (a) and block (B) of from 95:5 to 65:35, preferably from 90:10 to 70: 30.

the crystallinity of the block (B) and its weight fraction in the polymer (F-TPE) are such as to provide the polymer (F-TPE) with a heat of fusion (Δ H) of at most 20J/g, preferably at most 18J/g, more preferably at most 15J/g, when determined according to ASTM D3418_f) (ii) a On the other hand, the polymer (F-TPE) combines thermoplastic and elastomeric characteristics so as to have a certain crystallinity, providing a heat of fusion of at least 2.5J/g, preferably at least 3.0J/g.

Preferred polymers (F-TPE) are those comprising:

At least one elastomeric block (A) as detailed above_VDF) And an

At least one thermoplastic block (B) as detailed above_VDF) And is and

Wherein the crystallinity of said block (B) and its weight fraction in the polymer (F-TPE) is such as to provide the polymer (F-TPE) with a heat of fusion of at most 15J/g, when determined according to ASTM D3418.

Polymer (F)

The expressions vinylidene fluoride polymer and polymer (F) are used within the framework of the present invention to indicate a polymer essentially consisting of recurring units, more than 85% by moles of which are derived from vinylidene fluoride (VDF).

Polymer (F) has substantially crystalline characteristics and a heat of fusion (. DELTA.H) of more than 25J/g, preferably more than 27J/g, more preferably more than 30J/g, as determined according to ASTM D3418_f)。

The vinylidene fluoride polymer [ polymer (F) ] is preferably a polymer comprising:

(a') at least 85% by moles of recurring units derived from vinylidene fluoride (VDF);

(b') optionally from 0.1% to 15%, preferably from 0.1% to 12%, more preferably from 0.1% to 10% by moles of recurring units derived from a fluorinated monomer different from VDF; and

(c') optionally from 0.1 to 5% by moles, preferably from 0.1 to 3% by moles, more preferably from 0.1 to 1% by moles of recurring units derived from one or more hydrogenated comonomers,

all the above% by moles refer to the total moles of recurring units of the polymer (F).

Said fluorinated monomers are advantageously chosen in the group consisting of: vinyl Fluoride (VF)₁) (ii) a Trifluoroethylene (VF)₃) (ii) a Chlorotrifluoroethylene (CTFE); 1, 2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro (alkyl) vinyl ethers such as perfluoro (methyl) vinyl ether (PMVE), perfluoro (ethyl) vinyl ether (PEVE), and perfluoro (propyl) vinyl ether (PPVE); perfluoro (1, 3-dioxole); perfluoro (2, 2-dimethyl-1, 3-dioxole) (PDD). Preferably, the possible additional fluorinated monomers are selected from Chlorotrifluoroethylene (CTFE), Hexafluoropropylene (HFP), trifluoroethylene (VF3) and Tetrafluoroethylene (TFE).

The choice of the hydrogenated comonomer or comonomers is not particularly limited; alpha-olefins, (meth) acrylic monomers, vinyl ether monomers, styrene monomers; however, in order to optimize chemical resistance, embodiments are preferred in which the polymer (F) is substantially free of repeating units derived from the hydrogenated comonomer(s).

Thus, the vinylidene fluoride polymer [ polymer (F) ] is more preferably a polymer consisting essentially of:

(a') at least 85% by moles of recurring units derived from vinylidene fluoride (VDF);

(b') optionally from 0.1% to 15%, preferably from 0.1% to 12%, more preferably from 0.1% to 10% by moles of a fluorinated monomer different from VDF; said fluorinated monomers are preferably selected in the group consisting of: vinyl Fluoride (VF)₁) Chlorotrifluoroethylene (CTFE), Hexafluoropropylene (HFP), Tetrafluoroethylene (TFE), perfluoromethylvinyl ether (MVE), trifluoroethylene (TrFE), and mixtures thereof,

all the above% by moles refer to the total moles of recurring units of the polymer (F).

In addition to the repeating units, defects, terminal chains, impurities, chain inversions or branches and the like may additionally be present in the polymer (F) without these constituents substantially altering the behaviour and characteristics of the polymer (F).

as non-limiting examples of polymers (F) useful in the present invention, mention may be made notably of homopolymers of VDF, VDF/TFE copolymers, VDF/TFE/HFP copolymers, VDF/TFE/CTFE copolymers, VDF/TFE/TrFE copolymers, VDF/CTFE copolymers, VDF/HFP copolymers, VDF/TFE/HFP/CTFE copolymers and the like.

VDF homopolymers are particularly advantageous for use as polymer (F) in the composition (C).

The melt index of polymer (F) is advantageously at least 0.01g/10min, preferably at least 0.05g/10min, more preferably at least 0.1g/10min and advantageously less than 50g/10min, preferably less than 30g/10min, more preferably less than 20g/10min, when measured according to ASTM test number 1238 at 230 ℃ under a piston load of 2.16 kg.

the melt index of the polymer (F) is advantageously at least 1g/10min, preferably at least 2g/10min, more preferably at least 5g/10min and advantageously less than 70g/10min, preferably less than 50g/10min, more preferably less than 40g/10min, when measured according to ASTM test number 1238 at 230 ℃ under a piston load of 5 kg.

The polymer (F) advantageously has a melting point (T) advantageously of at least 120 ℃, preferably at least 125 ℃, more preferably at least 130 ℃ and at most 190 ℃, preferably at most 185 ℃, more preferably at most 180 ℃ as determined by DSC with a heating rate of 10 ℃/min according to ASTM D3418_m2)。

Polymer (M)

with respect to the expression "methyl methacrylate polymer" or "polymer (M)", these terms are used herein to denote methyl methacrylate homopolymers and methyl methacrylate copolymers having a predominant methyl methacrylate content and small amounts of other monomers selected from alkyl (meth) propionate, acrylonitrile, butadiene, styrene and isoprene.

with homopolymers of methyl methacrylate and C₂-C₆Copolymers of alkyl acrylates have achieved advantageous results. With homopolymers of methyl methacrylate and C₂-C₄Copolymers of alkyl acrylates such as butyl acrylate give excellent results. The methyl methacrylate content of these copolymers is generally at least about 55% by weight, and preferably at least about 60% by weight. This content generally does not exceed about 90% by weight relative to the total weight of polymer (M); in most cases, this content does not exceed 80% by weight.

advantageously, the polymer (M) may contain 0 to 20 percent and preferably 5 to 15 percent by weight of the polymer (M) of at least one of methyl acrylate, ethyl acrylate and butyl acrylate.

The polymer (M) may be functionalized, that is to say it contains, for example, acid chloride, alcohol or anhydride functional groups. These functional groups may be introduced by grafting or by copolymerization. Advantageously, this is the acid functionality provided by the acrylic comonomer. Two adjacent acrylic functional groups may lose water to form an anhydride. The proportion of functional groups may be between 0 and 15 percent by weight of the polymer (M) containing optional functional groups.

The polymer (M) advantageously has a glass transition temperature of at least 80 ℃, preferably at least 85 ℃, more preferably at least 100 ℃ when measured according to ASTM D3418.

According to certain preferred embodiments, the polymer (M) is a polymethyl methacrylate homopolymer.

Composition (C)

The composition (C) comprises as main component the polymer (F-TPE), that is to say that the amount of polymer (F-TPE) in the composition (C) is generally at least 50% wt, preferably at least 60% wt, most preferably at least 70% wt, relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M); and/or advantageously at most 97% wt, preferably at most 95% wt, more preferably at most 94% wt.

The amount of polymer (F) in the composition (C) is at least 3% wt, preferably at least 5% wt, more preferably at least 6% wt, relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M); and/or is at most 50% wt, preferably at most 40% wt, more preferably at most 30% wt.

However, as explained, the presence of the polymer (M) in the composition (C) is not mandatory, that is to say its amount may be zero, the upper limit of the amount of polymer (M) being generally defined as follows: the amount of polymer (M) in the composition (C) is generally at most 25% wt, preferably at most 20% wt, more preferably at most 15% wt, relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M).

According to certain embodiments, the composition (C) does not comprise any polymer (M) as detailed above. According to these embodiments, a preferred composition (C) comprises:

From 50 to 97% wt, preferably from 60 to 95% wt, more preferably from 70 to 94% wt of a polymer (F-TPE), and

from 3 to 50% wt, preferably from 5 to 40% wt, more preferably from 6 to 30% wt of polymer (F),

wherein% wt is defined with respect to the total weight of polymer (F-TPE) and polymer (F).

According to certain other embodiments, the polymer (M) is present in the composition. According to these embodiments, the preferred composition (C) comprises, relative to the total weight of polymer (F), polymer (F-TPE) and polymer (M):

-from 50 to 96% wt, preferably from 60 to 92% wt, more preferably from 70 to 89% wt of a polymer (F-TPE);

-from 3 to 45% wt, preferably from 5 to 35% wt, more preferably from 6 to 25% wt of polymer (F); and

From 1 to 25% wt, preferably from 3 to 20% wt, more preferably from 5 to 15% wt of polymer (M).

In addition to polymer (F), polymer (F-TPE) and possibly polymer (M), composition (C) may further comprise one or more additives, notably one or more additives selected from the group consisting of pigments, processing aids, plasticizers, stabilizers, mold release agents and the like.

when present, the additives are generally included in the composition (C) in an amount not exceeding 10 parts, preferably not exceeding 5 parts, per 100 parts by weight of polymer (F), polymer (F-TPE) and polymer (M).

Preferred embodiments are those wherein composition (C) consists of polymer (F), polymer (F-TPE), polymer (M) and optionally from 0 to 10 parts by weight of one or more additives per 100 parts by weight of polymer (F), polymer (F-TPE) and polymer (M).

For aesthetic purposes, it is generally understood that the composition will comprise at least one additive selected from pigments.

pigments useful in composition (C) are generally selected from oxides, sulfides, hydroxides, silicates, sulfates, titanates, phosphates, carbonates and mixtures thereof.

In the composition (C), a white inorganic pigment is preferable for the purpose of providing white parts.

among the white pigments suitable for the composition of the invention, mention may be made of TiO₂Pigments (e.g., rutile, anatase), zinc oxide (ZnO) pigments (e.g., zinc white, chinese white, or spangle), zinc sulfide (ZnS) pigments, lithopone (a mixed pigment made of zinc sulfide and barium sulfate) pigments, lead white pigments (basic lead carbonate), barium sulfate, and corresponding complex pigments obtained by coating the above pigments on a suitable inorganic carrier (e.g., silicate, aluminum silicate salt, mica, and the like).

particularly preferred pigments are the already proven zinc oxide and zinc sulfide pigments which, when incorporated in the composition (C), give molded parts with excellent whiteness.

as noted above, in certain instances it may be desirable to add a small amount of color pigment in combination with any of the white pigments mentioned above in order to adjust the color coordinates for the target white color, and/or to reduce yellowness for any other reason.

the colored pigments useful in composition (C) notably comprise or will comprise one or more of the following: art blue (Artic blue) #3, Topaz blue (Topaz blue) #9, olympic blue (olympic blue) #190, Kingfisher blue (Kingfisher blue) #211, navy blue (undersign blue) #214, russet brown (russet brown) #24, walnuts brown (Walnut brown) #10, gold brown (Golden brown) #19, Chocolate brown (Chocolate brown) #20, iron ore (Ironstone brown) #39, Honey yellow (honeyyellow) #29, woodford green (shewn) #5, and soot black (jeep) 1, available from shepherd color company (Shepard color company), Cincinnati, Ohio, USA; black F-2302, blue V-5200, Gerstallose F-5686, Green F-5687, Brown F-6109, light yellow F-6115, chestnut brown V-9186, and yellow V-9404, available from Philippine corporation (Ferro Corp.) of Cleveland, Ohio, USA, available from Englehard Industries, Inc (Englehard Industries, N.J., USA), Edison, N.J., USAA pigment; ultramarine blue #54 and ultramarine violet #5012 are commercially available from Hollidays Pigments International.

in this context, therefore, preferred embodiments are those in which composition (C) consists of polymer (F), polymer (F-TPE), polymer (M) and from 0.01 to 10 parts by weight, per 100 parts by weight of polymer (F), polymer (F-TPE), polymer (M), of one or more than one additive, at least one of which is a pigment as detailed above, used in an amount of from 0.01 to 5, preferably from 0.01 to 3 parts by weight, per 100 parts by weight of polymer (F), polymer (F-TPE), and polymer (M).

The invention further relates to a process for manufacturing the composition (C) as detailed above.

The process generally advantageously comprises at least one step of mixing the polymer (F), the polymer (F-TPE), and possibly the polymer (M). Mixing can be carried out using standard mixing equipment; mixing polymer (F), polymer (F-TPE) and polymer (M) (when present) generally in molten form; however, it is also possible to practice a process in which the polymer (F), the polymer (F-TPE) and the polymer (M), when present, are mixed in latex form and then co-coagulated and/or a process in which the polymer (F), the polymer (F-TPE) and the polymer (M), when present, are mixed in a suitable solvent, either as a solution or as a powder.

Mixing in the molten state is generally accomplished using an extruder apparatus, with a twin screw extruder being preferred.

It is therefore common practice to manufacture composition (C) in pellet form.

The composition (C) may be molded to provide a shaped part. The technique used for molding is not particularly limited; standard techniques including shaping the composition (C) in molten/softened form may be advantageously applied and notably include compression molding, extrusion molding, injection molding, transfer molding, and the like.

Yet another embodiment of the present invention is a method of making a shaped part comprising molding composition (C) as detailed above.

however, it is generally understood that injection molding techniques are most versatile and widely used, especially when the molded parts have complex designs.

According to this technique, a piston or screw-type plunger is used to force a portion of composition (C) in its molten state into the mold cavity, where it solidifies into a shape conforming to the contours of the mold. The mold is then opened and a suitable device (e.g., a series of pins, sleeves, stripper, etc.) is driven forward to demold the article. The mold is then closed and the process is repeated.

In another embodiment of the invention, the following steps may be used: machining a standard shaped article made of composition (C) so as to obtain said part having a different size and shape from said standard shaped article. Non-limiting examples of the standard shaped articles include notably plates, rods, slabs and the like. The standard-shaped parts can be obtained by any processing technique of the polymer composition (C), notably including extrusion or injection moulding.

However, especially when the target shaped part is a coated wire or a bundle of wires, the composition (C) can be shaped into a sheath or jacket form by an extrusion technique.

Whatever the processing technique, however, it is understood that the overall thermoplastic characteristics of composition (C) enable recycling and reprocessing of waste and decorations.

On the other hand, embodiments are also contemplated wherein the shaped part is subjected to conditions that result in at least partial curing or crosslinking of composition (C).

Still another object of the present invention is a shaped part made of the composition (C) of the present invention. The shaped parts of the invention are advantageously parts of different peripherals, accessories and devices intended to be connected to the mobile electronic device.

The molded parts may notably be wristbands, chest bands and other attachments which have been developed for securing electronic devices to specific parts of the human body.

The molded part may be a component such as a signal transmission cable for transmitting/receiving an electric signal generated in an acoustic system or an imaging system, which may be connected to a portable electronic product for use with an earphone, a headphone, a speaker, or an image display device. The shaped part may notably be a cable jacket or an outermost coating of the signal transmission cable, which advantageously surrounds all the components of the cable and protects them from the external environment, while at the same time it provides easy handling, flexibility and mechanical strength.

However, the molded part may be a protective enclosure designed to receive and house the portable electronic device.

Additionally, the molded part may be a component of an earplug, including those intended for connection to a portable electronic device.

If the disclosure of any patent, patent application, and publication incorporated by reference herein conflicts with the description of the present application to the extent that terminology may become unclear, the description shall take precedence.

the invention will now be illustrated with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention.

Raw material

6008/0001PVDF is commercially available from Suweit Polymers having a melt flow rate (ASTM D1238 at 230 ℃/2.16 kg) of about 5.5 to 11g/10min, a melt flow rate (230 ℃/5kg) of 16 to 30g/10min, a heat of fusion (Δ H) of about 63J/g_f) Low viscosity PVDF homopolymer (6008, infra).

CA51PMMA is a polymethyl methacrylate homopolymer (CA51, infra) commercially available from Plaskolate corporation having a melt flow rate (230 ℃/3.8kg, ASTM D1238) of about 15.0g/10 min.

HD-S white pigment is a synthetic, micronized, organic coated ZnS (ZnS:>98% wt, polycrystalline wurtzite form of predominantly ZnS); it is commercially available (ZnS, hereinafter) from sha har ben chemical limited (sachtleben chemie GmbH).

Preparation examples

preparation example 1: production of Polymer F-TPE-1

PVDF-P (VDF-HFP) -PVDF (P (VDF-HFP) VDF 78.5% by moles, HFP 21.5% by moles

In a 7.5 liter reactor equipped with a mechanical stirrer operating at 72rpm, 4.5l of demineralized water and 22ml of microemulsion, obtained beforehand by mixing: 4.8ml of a perfluoropolyoxyalkylene having an acidic end group of the formula (having an average molecular weight of 600): CF (compact flash)₂ClO(CF₂-CF(CF₃)O)_n(CF₂O)_mCF₂COOH (where n/m is 10), 3.1ml of 30% v/v NH₄aqueous OH solution, 11.0ml demineralized water and 3.0ml of a solution of the formulaD02 perfluoropolyether (having an average molecular weight of 450): CF (compact flash)₃O(CF₂CF(CF₃)O)_n(CF₂O)_mCF₃(wherein n/m is 20).

heating and maintaining the reactor at a set point temperature of 85 ℃; a mixture of vinylidene fluoride (VDF) (78.5% by moles) and Hexafluoropropylene (HFP) (21.5% by moles) was then added to reach a final pressure of 20 bar. Then, 8g of 1, 4-diiodoperfluorobutane (C) as a chain transfer agent was introduced₄F₈I₂) And 1.25g of Ammonium Persulfate (APS) was introduced as an initiator. The pressure was maintained at the set point of 20 bar by continuously feeding a gaseous mixture of vinylidene fluoride (VDF) (78.5% by moles) and Hexafluoropropylene (HFP) (21.5% by moles) until a total of 2000 g. In addition, for every 5% increase in conversion, 0.86g of CH fed in 20 equal portions was introduced₂＝CH-(CF₂)₆-CH＝CH₂。

Once 2000g of the monomer mixture was fed to the reactor, the reaction was stopped by cooling the reactor to room temperature. The residual pressure was then vented and the temperature brought to 80 ℃. The VDF was then fed to an autoclave at a pressure up to 20 bar and 0.14g Ammonium Persulphate (APS) was introduced as initiator. The pressure was maintained at the set point of 20 bar by continuously feeding VDF until a total of 500 g. The reactor was then cooled, vented, and the latex recovered. The latex was treated with aluminium sulphate, separated from the aqueous phase, washed with demineralised water and dried in a convection oven at 90 ℃ for 16 hours.

The characterization data of the polymers thus obtained are reported in table 1.

TABLE 1

General procedure for preparing a composition for the manufacture of injection-molded parts

The ingredients as detailed in table 2 were compounded using a ZSK30 twin screw extruder in order to obtain pellets by extrusion at a temperature of about 200 ℃ at a screw speed of 200rpm at a throughput of 15 kg/h.

TABLE 2

						example 1C	Example 2	Example 3	Example 4
F-TPE-1	100	92.5	75	75
					6008	-	7.5	15	25
CA51	-	-	10	-

General procedure for injection molding parts

The pellets obtained as such by extrusion were fed into a Toshiba ISG-150N injection molding apparatus to produce injection parts having an ASTM tensile bar shape according to ASTM D638 and ASTM D790. The injection molding apparatus used is equipped with a barrel of a screw extruder and a mold with a clamping force of maximum 1000kN and a melt pressure control of maximum 2500 bar.

The injection molding conditions were such that the melt temperature was about 180-210 ℃ and the mold temperature was set to 35 ℃.

properties-mechanical Properties of injection molded samples

The injection molded samples were tested for their tensile strength (according to ASTM D638). The results are summarized in the following table.

TABLE 3

Property-flexural Properties of injection molded samples

the injection molded samples were tested for their flexural properties (according to ASTM D790). The results are summarized in the following table.

TABLE 4

Characteristic of injection-moulded samples-abrasion resistance

The samples obtained as detailed above were subjected to tests intended to operate with a 1cm stroke under a load of 1000g, a cycle speed of 30 cycles/minute, using a weerarser device, in order to determine their resistance to abrasion. The results summarized below provide weight loss and height loss after 100 cycles.

TABLE 5

	Example 1C	Example 2	example 3	Example 4
					Weight loss (%)	0.025	0.008	0.008	0.155
Height loss (%)	1.13	0.388	0.400	0.743

Properties-color/stain resistance of injection molded samples

The as-molded color of the molded samples was measured to evaluate the whiteness of the injection molded parts when applying a standard incident daylight type light (D65). Color is measured according to the CIE L-a-b coordinate standard (where L x coordinate represents the lightness (black to white) scale, a x coordinate represents the green-red chromaticity and b x scale represents the blue-yellow chromaticity) and according to the CIE L-C-h coordinate standard (where L x is as in the CIE L-a-b standard above, C x represents the chroma, and h is the hue angle). The samples as originally obtained were measured, as well as their color coordinates after exposure to certain staining agents (ketchup, mustard, sun screen, sebum, wet denim) and cleaning according to standardized procedures.

TABLE 6

The same results regarding the resistance to staining agents are expressed in the table below herein as the difference in singular coordinate values before and after the staining test (Δ L, Δ a, Δ b, Δ C, and Δ h), and Δ E and Δ 94, where Δ E [ Δ E ═ ((Δ L))²+(Δa*)²+(Δb*)²)^1/2]And Δ 94[ Δ 94 ═ ((Δ L))²+(ΔC*)²+(Δh*)²)^1/2]Is the distance in the corresponding color coordinate space.

TABLE 7

All the data contained above clearly demonstrate the surprising effect of improved stain resistance when vinylidene fluoride is added to fluorinated thermoplastic elastomers, where the distance (in terms of both Δ E and Δ 94) is smaller in the color space after exposure to the various stains listed above, which represent common agents to which mobile electronic products and their accessories may be exposed during their daily use, even in combination with PMMA to mitigate or counteract their sensitivity to certain stains.