阅读说明：本技术 共聚酰胺、包含这样的共聚酰胺的组合物及其用途 (Copolyamide, composition comprising such a copolyamide and use thereof ) 是由 P.布隆德尔 T.布里福德 于 2013-08-27 设计创作，主要内容包括：本发明涉及包括至少两种不同的重复单元的具有以下通式的共聚酰胺：A/X.Y,其中A是选自得自至少一种氨基酸的单元和得自至少一种内酰胺的单元的脂族重复单元,和X.Y是得自至少一种脂环族二胺和至少一种二羧酸的缩聚的重复单元。根据本发明,单元A的重量比例大于或等于91％。本发明还涉及包含这样的共聚酰胺的组合物及其用途,特别是在运动鞋的鞋底中的用途。(The invention relates to copolyamides comprising at least two different recurring units having the general formula: a/x.y, wherein a is an aliphatic repeat unit selected from the group consisting of a unit derived from at least one amino acid and a unit derived from at least one lactam, and x.y is a repeat unit derived from the polycondensation of at least one cycloaliphatic diamine and at least one dicarboxylic acid. According to the invention, the proportion by weight of units A is greater than or equal to 91%. The invention also relates to compositions comprising such copolyamides and to the uses thereof, in particular in the soles of sports shoes.)

1. Copolyamides comprising at least two different recurring units corresponding to the general formula:

A/X.Y

wherein:

■ A is an aliphatic repeat unit selected from the group consisting of a unit derived from at least one amino acid and a unit derived from at least one lactam, and

■ X.Y. denotes recurring units resulting from the polycondensation of at least one cycloaliphatic diamine and at least one dicarboxylic acid comprising from 4 to 36 carbon atoms and advantageously from 6 to 18 carbon atoms,

characterized in that the weight proportion of units A in the copolyamide A/X.Y is in the range from 92.5% to 93.1% and the copolyamide corresponds to the formulae 11/B.T, 11/B.I, 12/B.T, 12/B.I, 11/P.T, 11/P.I, 12/P.T, 12/P.I, 11/IPD.T, 11/IPD.I, 12/IPD.T and 12/IPD.I.

2. Copolyamide according to claim 1, characterised in that the recurring units a are derived from 11-aminoundecanoic acid (11).

3. Copolyamide according to claim 1, characterised in that the recurring units a are derived from laurolactam (12).

4. A copolyamide according to any one of claims 1-3, characterised in that the dicarboxylic acid of the unit x.y is isophthalic acid (I).

5. Process for the preparation of a copolyamide according to any one of claims 1-4, characterised in that it comprises the step of polycondensing comonomers which give rise to repeating units A and X.Y.

6. Composition comprising at least one copolyamide according to any one of claims 1-4.

7. Composition according to claim 6, characterized in that it further comprises at least one additive chosen from fillers, fibers, dyes, stabilizers, in particular UV stabilizers, plasticizers, impact modifiers, surfactants, pigments, optical brighteners, antioxidants and natural waxes, and mixtures thereof.

8. Use of a copolyamide according to any one of claims 1-4 or of a composition according to claim 6 or 7 for the manufacture of at least one layer of a single-layer structure or a multi-layer structure.

9. Use according to claim 8, characterized in that the structure is in the form of a fibre, film, sheet, tube, hollow body, moulded part or injection moulded part.

10. Use of a polyamide according to any of claims 1 to 4 or of a composition according to claim 6 or 7 for the manufacture of transparent moulded articles such as shoe soles or elements of shoe soles, in particular of sports shoes.

11. Footwear, in particular sports footwear, comprising a sole, which is wholly or partly made of a copolyamide according to any one of claims 1-4 or of a composition according to claim 6 or 7.

[ technical field ]

The present invention relates to copolyamides, to a process for preparing them and to their use, in particular in the manufacture of various articles which combine transparency, ease of decoration and mechanical strength against repeated (repetitive) stresses. Among these articles, mention may be made of common consumer products such as sports articles and more particularly sports shoes.

The invention also relates to a composition comprising such a copolyamide and to the use of this composition, in particular in the manufacture of all or part of the above-mentioned articles.

Finally, the invention relates to footwear, and in particular athletic footwear, using the copolyamide or the composition.

[ background and technical problems ]

In the field of footwear and in particular in the field of sports, it is currently sought to make soles that are relatively rigid: it meets the fatigue test known as the "materials for soles Flex (Ross Flex)" test, and it is also transparent.

In the present description, the term "sole" means a sole in its generally accepted sense, as well as elements of footwear and elements of shock-absorbing systems, and in particular a midsole or an outsole.

A variety of thermoplastic polymers are currently available on the market for making athletic shoe soles. Among these polymers, polyamides, in particular amorphous polyamides, are generally used.

Such polyamides are particularly advantageous because they have very good mechanical properties and they are also transparent. However, they do not meet the "sole material flex" fatigue test and therefore cannot be used to manufacture parts that are subject to repeated flexing.

Other transparent polymers that also meet fatigue testing are commonly used to make athletic shoe soles: these are copolymers containing polyamide blocks and polyether blocks, known by the trade nameAre known. However, these polymers are too flexible for the required requirements.

Therefore, there is a real need to find polymers that can simultaneously meet the three criteria mentioned above, namely:

is sufficiently rigid and has a flexural modulus (measured according to the standard iso.. to) between 1000MPa and 1500MPa,

is transparent, i.e. has an optical transmission coefficient (measured at a wavelength of 560nm and for a sheet thickness of 2 mm) greater than or equal to 75%, and

-satisfying the "sole material flex" fatigue test, as will be detailed later.

Document US 2008/0119632 describes a transparent composition comprising a copolyamide for the manufacture of printable transparent articles. More particularly, these articles are in the form of films intended to make ski shoe uppers (ski uppers). The copolyamide of the composition comprises:

-from 65 to 99 mol% of an equimolar mixture of a linear aliphatic diamine and a linear aliphatic dicarboxylic acid, the mixture comprising an average number of carbon atoms between 8 and 12,

-1 to 35 mol% of an equimolar mixture of a cycloaliphatic diamine and a dicarboxylic acid.

Such copolyamides meet the three criteria of rigidity, transparency and fatigue mentioned above. However, the conversion or shaping of such copolyamides by moulding is not entirely satisfactory. In particular, not only is bubble formation observed in the moulding compound (molded mass), but also the demoulding operation is difficult, since the copolyamide sticks to the walls of the mould. The use of such copolyamides for the manufacture of shoe soles by moulding is therefore not envisaged.

The object of the present invention is therefore to propose such polymers: the polymers simultaneously satisfy the above three criteria of rigidity, transparency and fatigue and can be easily used by moulding, in particular for the manufacture of moulded articles such as shoe soles.

[ summary of the invention ]

This object is achieved by a copolyamide comprising at least two different recurring units corresponding to the general formula:

A/X.Y

wherein:

■ A is an aliphatic repeat unit selected from the group consisting of a unit derived from at least one amino acid and a unit derived from at least one lactam, and

■ X.Y. denotes recurring units resulting from the polycondensation of at least one cycloaliphatic diamine and at least one dicarboxylic acid comprising from 4 to 36 carbon atoms and advantageously from 6 to 18 carbon atoms.

According to the invention, the proportion by weight of units A in the copolyamide A/X.Y is greater than or equal to 91%.

In particular, it was observed that the rigidity, transparency and fatigue criteria were reached when the content by weight of recurring units a in the copolyamide a/x.y was 91% and higher than 91% (recurring units a and x.y are as defined above), regardless of the conversion conditions. In particular, the implementation by molding is entirely satisfactory: no warpage (thermal deformation) of the molding compound was observed. On the other hand, for a weight content of less than 91%, it was observed that the copolyamide no longer satisfies the "flex on sole material" fatigue test.

Other features, aspects, subjects, and advantages of the present invention will become even more apparent upon reading the description and examples that follow.

In particular, the invention also relates to a process for preparing copolyamides, to the use thereof, and to compositions comprising such copolyamides and to the use of such compositions.

The invention also relates to footwear, and in particular to athletic footwear.

It is noted that the terms "between" and "including" used in the preceding paragraphs and in the rest of the specification are to be understood as including each of the noted limitations.

The invention comprises the following contents:

embodiment 1. a copolyamide comprising at least two different repeat units corresponding to the general formula:

A/X.Y

wherein:

■ A is an aliphatic repeat unit selected from the group consisting of a unit derived from at least one amino acid and a unit derived from at least one lactam, and

■ X.Y. denotes recurring units resulting from the polycondensation of at least one cycloaliphatic diamine and at least one dicarboxylic acid comprising from 4 to 36 carbon atoms and advantageously from 6 to 18 carbon atoms,

characterized in that the proportion by weight of units A in the copolyamide A/X.Y is greater than or equal to 91%.