阅读说明：本技术 用于使聚酰胺质地化的方法 (Method for texturing polyamides ) 是由 T.蒙塔纳里 C.雷科奎尔 于 2020-04-07 设计创作，主要内容包括：本发明涉及用于制备包含至少一个膜(F)的物体的方法,所述膜(F)包含至少一个层(1),所述层(1)包括包含至少一种半结晶聚酰胺(Psc)的组合物,所述半结晶聚酰胺(Psc)具有在25J/g和75J/g之间的熔融焓(根据ISO11357-3:2013的以40℃/min的第一DSC加热),所述膜在其表面的至少一个的全部或部分上具有质地化元件(T)的质地,其特征在于,该方法包含以下步骤:a.提供模具(M),其被设置到小于或等于120℃、特别地在20℃和90℃之间的温度；b.将至少一个质地化元件(T)施加至模具的壁,并且至少部分地具有质地化的表面,所述质地化的表面在与面向模具的面相反的面上；c.将至少一个膜(F)施加至质地化元件(T)的质地化的表面,所述膜(F)包含至少一个层(1),所述层(1)旨在与质地化元件(T)的质地化的表面接触,所述层(1)的厚度为至少10μm；d.将至少一种加热方式(H)施加至步骤(c)的所述膜,以在面向质地化媒介物(T)的膜的侧面上达到温度(TT),温度(TT)在组合物(CPO)的Tg和熔融温度(Tm)减15℃之间,并且用在1.5和2000bar之间的压力,持续在0.1s和5h之间的时间t,将压力方式(P)施加至所述膜,以使其与质地化元件(T)接触；e.从模具移出并且获得物体,该物体包含所述半结晶聚酰胺膜(Psc)、并且在其表面的至少一个的全部或部分上具有所述质地化元件(T)的质地。(The invention relates to a process for preparing an object comprising at least one film (F) comprising at least one layer (1), said layer (1) comprising a composition comprising at least one semi-crystalline polyamide (Psc) having a melting enthalpy between 25J/g and 75J/g (first DSC heating at 40 ℃/min according to ISO11357-3: 2013), said film having the texture of a texturing element (T) on all or part of at least one of its surfaces, characterized in that it comprises the steps of a. providing a mould (M) set to a temperature less than or equal to 120 ℃, in particular between 20 ℃ and 90 ℃; b. applying at least one texturizing element (T) to a wall of the mold and having at least in part a texturized surface on a face opposite to a face facing the mold; c. applying at least one film (F) to the textured surface of the texturing element (T), said film (F) comprising at least one layer (1), said layer (1) being intended to be in contact with the textured surface of the texturing element (T), the thickness of said layer (1) being at least 10 μ ι η; d. applying at least one heating means (H) to the film of step (c) to reach a temperature (TT) on the side of the film facing texturing medium (T), temperature (TT) being between Tg and melting temperature (Tm) of Composition (CPO) minus 15 ℃, and applying a pressure means (P) to the film to bring it into contact with texturing element (T) with a pressure between 1.5 and 2000bar for a time T of between 0.1s and 5H; e. removing from the mould and obtaining an object comprising said semi-crystalline polyamide film (Psc) and having the texture of said texturisation elements (T) on all or part of at least one of its surfaces.)

1. Process for the preparation of an object comprising at least one film (F) comprising at least one layer (1), said layer (1) comprising a composition comprising at least one semi-crystalline polyamide (Psc) having a melting enthalpy during first DSC heating of between 25J/g and 75J/g at 40 ℃/min according to ISO11357-3:2013, said film having the texture of a texturizing element (T) on all or part of at least one of its surfaces,

the method is characterized by comprising the following steps:

a. providing a mould (M) set to a temperature of less than or equal to 120 ℃, in particular between 20 ℃ and 90 ℃,

b. applying at least one texturing element (T) to the wall of the mould, the texturing element (T) preferably having a thickness of between 20 and 2000 μm, preferentially between 50 μm and 1000 μm, in particular between 50 μm and 500 μm, in particular being in a planar form, and at least partially having a textured surface on the face opposite to the face facing the mould,

c. applying at least one film (F) to the textured surface of the texturing element (T), said film (F) comprising at least one layer (1), said layer (1) comprising a Composition (CPO) comprising at least one semi-crystalline polyamide (Psc), said layer (1) being intended to be in contact with the textured surface of the texturing element (T), said layer (1) having a thickness of at least 10 μm, in particular between 10 and 1000 μm,

d. applying at least one heating means (H) to the film of step (c) to reach a temperature (TT) on the face of the film facing the texturing medium (T), The Temperature (TT) being between Tg and the melting temperature (Tm) of the Composition (CPO) minus 15 ℃, Tm being measured according to ISO11357-3:2013 and a pressure means (P) is applied to the film to bring it into contact with the texturing element (T) with a pressure between 1.5 and 2000bar, in particular between 5bar and 1000bar, for a time T between 0.1s and 5H, preferentially between 3s and 10min,

e. removing from the mould and obtaining an object comprising said film comprising a Composition (CPO) comprising at least a semi-crystalline polyamide (Psc) and having the texture of said texturising elements (T) on all or part of at least one of its surfaces.

2. The method according to claim 1, characterized in that said temperature (TT) of said film (F) comprising the Composition (CPO) is between Tg and Tm-15 ℃ over a thickness of at least 10 μm.

3. Method according to one of claims 1 or 2, characterized in that said heating means (H) and pressure means (P) consist of: injecting the molten polymer (I) at a temperature Tinj of between 150 ℃ and 350 ℃ onto the face of the film (F) of step (c) opposite to the face intended to come into contact with the texturizing element (T) for a time of between 0.1s and 15min, preferentially between 1s and 15min, more preferentially between 1s and 10min, in particular between 3s and 2min, and at a pressure of between 1.5 and 2000bar, in particular between 5bar and 1000bar, more advantageously between 50bar and 500 bar.

4. A method according to claim 3, characterized in that the molten polymer (I) adheres to the layer (1).

5. Method according to claim 4, characterized in that said film (F) is a single-layer film (F1) consisting of a layer (1), said layer (1) comprising a composition comprising at least one semi-crystalline polyamide (Psc), said layer (1) having a thickness of at least 10 μm, in particular between 10 and 1000 μm.

6. Process according to one of claims 4 or 5, characterized in that the molten polymer (I) is a polyamide.

7. Process according to claim 3, characterized in that the molten polymer (I) lacks adhesion to the semi-crystalline polyamide (Psc).

8. The process according to claim 7, characterized in that the film (F) is a multilayer film (F2) comprising at least one layer (1), the layer (1) comprising a composition comprising at least one semi-crystalline polyamide (Psc), the layer (1) having a thickness of between 20 μm and 1000 μm, in particular between 50 μm and less than 200 μm.

9. The process according to claim 8, characterized in that said multilayer film (F2) comprises at least two layers, a layer (1) and a layer (2), the two layers (1) and (2) being adhered to each other and the layer in contact with the texturing element (T) being the layer (1) comprising the composition comprising said semi-crystalline polyamide (Psc).

10. Method according to claim 9, characterized in that said molten polymer (I) adheres to a layer (2), said layer (2) being located on the opposite face to the layer (1) in contact with the texturizing element (T).

11. The process according to claim 8, characterized in that said multilayer film (F2) comprises at least two layers (1) and (2), the layer in contact with the texturing element (T) being the layer (1) of said semi-crystalline polyamide (Psc), the two layers (1) and (2) being devoid of adhesion to each other and comprising between them at least one third layer (3), this third layer (3) allowing adhesion between the layers (1) and (2).

12. Method according to claim 11, characterized in that said molten polymer (I) adheres to a layer (2), said layer (2) being located on the opposite side to the layer (3) in contact with the layer (1), the layer (1) being in contact with the texturing element (T).

13. Method according to one of claims 1 to 12, characterized in that, during step d, the layer (1) intended to be in contact with the texturing element (T) is, on the face facing the texturing medium (T), at a temperature (TT) between the Tg and Tm-15 ℃ of the composition of the layer (1), and preferably between the Tg and Tm-15 ℃ of the semi-crystalline polyamide (Psc)), the Tg being determined according to ISO 11357-2:2013, and the Tm being determined according to ISO11357-3:2013, over a thickness of between 5 and 50% of the film.

14. Method according to one of claims 1 to 13, characterized in that the composition of the layer (1) has such a transparency: the transmission at 560nm on a plate having a thickness of 1mm is greater than or equal to 80%, in particular greater than or equal to 88%, determined according to standard ISO 13468-2: 2006.

15. Process according to one of claims 1 to 14, characterized in that the composition of layer (1) and optionally the semi-crystalline polyamide (Psc) have a melting enthalpy (first DSC heating at 40 ℃/min according to ISO11357-3: 2013) between 30 and 50J/g.

16. Process according to one of claims 1 to 15, characterized in that the Composition (CPO) and optionally the semi-crystalline polyamide (Psc) of the layer (1) are such that: its glass transition temperature (Tg) is between 30 and 120 ℃, preferably between 60 ℃ and 90 ℃, determined according to ISO 11357-2:2013, and its melting temperature (Tm) is between 150 ℃ and 330 ℃, preferably between 150 and 200 ℃, determined according to ISO11357-3: 2013.

17. Process according to one of claims 1 to 16, characterized in that the layer (1) of the mono-layer film (F1) or multi-layer film (F2) consists of a transparent composition comprising, by weight, the following, the sum being 100%:

5 to 40% of an amorphous polyamide (B) resulting essentially from the condensation of:

or at least one diamine chosen from cycloaliphatic diamines and aliphatic diamines and at least one diacid chosen from cycloaliphatic diacids and aliphatic diacids, at least one of the diamine or diacid units being cycloaliphatic,

or an alicyclic alpha-omega-aminocarboxylic acid,

or a combination of these two possibilities, or,

and optionally at least one monomer selected from alpha-omega-aminocarboxylic acids or optionally matched lactams, aliphatic diacids and aliphatic diamines,

from 0 to 40% of a flexible polyamide (C) selected from polyamides and polyether block copolymers and copolyamides,

0 to 20% of a compatibilizing agent (D) of (Psc) and (B),

0 to 40% of a flexibility Modifier (MS),

with the proviso that (C) + (D) + (MS) is between 0 and 50%,

to 100% of the remaining amount of a semi-crystalline polyamide (Psc) being the main component with respect to the sum of (Psc) + (B) + (C) + (D).

18. Process according to one of claims 1 to 17, characterized in that the layer (1) of the mono-layer film (F1) or multi-layer film (F2) consists of a transparent composition comprising, by weight, the following, the sum being 100%:

5 to 40% of an amorphous polyamide (B) substantially resulting from the condensation of at least one diamine, optionally an alicyclic diamine, of at least one aromatic diacid and of at least one monomer chosen from:

alpha-omega-aminocarboxylic acids and their use as stabilizers,

an aliphatic diacid(s),

an aliphatic diamine, which is a diamine having at least one of,

from 0 to 40% of a flexible polyamide (C) selected from polyamides and polyether block copolymers and copolyamides,

0 to 20% of a compatibilizing agent (D) of (Psc) and (B),

(C) + (D) is comprised between 0 and 50%

With the proviso that (B) + (C) + (D) is not less than 30%,

to 100% of the remaining amount of a semi-crystalline polyamide (Psc) being the main component with respect to the sum of (Psc) + (B) + (C) + (D).

19. Process according to claim 17 or 18, characterized in that the polyamide (Psc) is selected from PA11, PA12, PA1012, PA1010, PA612 and PA610, in particular from PA11 and PA12, especially the polyamide (Psc) is PA 11.

20. Method according to one of claims 1 to 19, characterized in that between the first texturing element (T) and the mould there is a second texturing element (T) different from the first texturing element, said second texturing element (T) at least partially covering said first texturing element (T).

21. The process according to one of claims 1 to 20, characterized in that, optionally, the object obtained in step e as defined in claim 1 is coated with a structural substrate on its side comprising the molten polymer (I).

22. Object obtained by a method according to one of claims 1 to 21.

23. A part comprising at least one object as defined in claim 22.

Drawings

FIG. 1 depicts a general diagram of the method of the invention with a mold (M), a texturing medium (T), a film (F), a pressure regime (H) and Temperatures (TI) and (TT), (TI) being the temperature on the surface of the film on the side opposite to the side to be textured, (TT) being defined beforehand.

Examples

Example 1: representative general method in case of monolayer film

Example 1-a: fabric texturing medium

The temperature of the injection screw was set to 250 ℃ in the last heating zone of the screw using a 350 ton injection press. Polyamide PA12 with an intrinsic viscosity of 1.0 was injected into a mould (M) corresponding to the inner panel of the back door, the intrinsic viscosity being measured in M-cresol, according to standard ISO 307:2007 but using M-cresol instead of sulfuric acid, at a temperature of 20 ℃ and at a concentration of 0.5% by weight.

Step (a):

the mold was first set to 60 ℃.

Like all injection molds, this mold consists of 2 parts:

the stationary part, the part closest to the injection screw, which is also the part where the injection point is located,

the movable part of the mold, the part that allows the mold to be opened, this part being the farthest from the injection screw.

This part is typically the part that makes it possible to mould the front side of the part (which will be visible: the interior panel of the vehicle). This part of the mould is the part associated with the mould (M).

Step (b):

instead of injecting the polymer into the mould immediately as during a conventional injection cycle, a texturing medium (T) is placed at the bottom of the mould (M) (and therefore in its movable part), this texturing medium (T) being a piece of fabric having a planar shape and having a thickness of about 0.5 mm. The fabric is cut so that it can decorate the entire surface of the movable part of the mould (M).

Step (c):

a single-layer film (or sheet) (F) having a thickness of 150 μm comprising a composition CPO consisting of:

65% by weight of PA12 Mw 45000 to 55000,

25% by weight of CoPA IPD.10/12 (weight ratio: 80/20),

10% of PA11 having Mw 45000 to 55000 and containing 0.3% of phosphoric acid.

The film has been obtained beforehand by implementation on a conventional film-rolling line consisting of an extruder heated to 240 ℃, the molten polymer at the exit of the extruder being shaped into a film by the action of a calendering roller heated to 40 ℃.

The film is also cut so that it protrudes a few mm from the joining plane so that it can later cover at least the entire surface of the mould during the injection process.

Step (d):

the mold was then closed and used 385cm³The flow rate/s PA12 with an intrinsic viscosity of 1.0 was injected into the mold and the injection screw was set to an upper temperature limit of 250 ℃. Once the mould is filled, pressure is applied for a period of 10s, this pressure being 250 bar. This pressure presses the film (F) onto the texturing medium (T), both of which are pressed against the bottom of the mould (M). Film (F) and texturing medium (T) match the shape of the mold, while film (F) matches and reproduces the texture of texturing medium (T).

The mould is then allowed to cool for 40s, which is the end of step (d).

A step (e):

after cooling, the mold is opened.

The retrieved object "interior panel of the back door" consists of PA12 (now solid, with a thickness of 1.5 mm) covered by a film (F). The film (F) is rigidly connected to the part made of PA12, since the adhesion between them is good.

Texturing medium (T) does not adhere to film (F), it falls off by itself, or can be easily removed by hand. The texturing medium T has left its impression on the visible side (outer side) of the film F and it reproduces in this way its appearance and more particularly its tactile feel, which gives the object "inner panel of the tailgate" the appearance of no longer a typical plastic object, but of a high-quality object that appears to be decorated or covered with real fabric.

Example 1-b:

a variant of example 1 consists of a previous visual decoration of the film (F) (after it has been produced by calendering and before it is placed in the mould of the injection press) by sublimation or screen printing techniques consisting of: the image (visual decoration) is transferred onto the face of the film (F), which is preferably the face opposite to the one intended to be textured. The image may be an image corresponding to a photograph of the fabric constituting the texturing medium (T).

1-b-1：

The texturing medium may be, for example, a colored printed fabric. Not only the tactile impression of the texturing medium but also its visual appearance will be reproducible on the object, since the film (F) is decorated (visually) beforehand with an image of this fabric. The visual and tactile appearance of the fabric texturing medium will be reproduced. Thus, a more complete tactile sensation will be obtained. The advantage over real fabrics is the durability of the film (F), which is physically and chemically much greater than that of fabrics.

1-b-2：

There may also be a visual wood decoration on the film, and a texturising vehicle that is a wood chip is used for this purpose.

The result is an object that resembles wood in both visual and tactile aspects.

Examples 1 to c

For even better durability, we can consider the example of a 600 μm film instead of 150 μm. This thickness can make matching the shape of the mold more difficult. To better match the shape of the thick film to the shape of the mold, the thick film may be pre-shaped to roughly pre-match the shape of the mold. For this purpose, after placing and adhering the texturing medium (T) and the film (F) (i.e. after step (c)) and before closing the mould to inject PA12, a step consisting of: an infrared heating bar is provided for heating the film (F) above its Tg during 3s (i.e. 100 ℃ (measured by infrared thermometer)) and then a vacuum pump is used to apply a negative pressure to the bottom of the mold, thereby sucking the softened film (F) at least roughly or partially onto the bottom of the mold.

Subsequently, the process returns to its course, closing the mould, injecting molten PA12 and it can be done pushing the film onto the bottom of the mould so that it perfectly matches the mould, as already described, during which the film will match the texturing medium (T) and reproduce its texture.

Example 1-d;

texturing vehicle: blotting paper.

Example 1-a was reproduced using a blotter textured vehicle having a thickness of 0.3 mm.

Examples 1 to e

Texturizing agents plants, e.g. leaves

Example 1-a was reproduced using a leaf texturing medium having a thickness of about 6mm at its thickest part.

Example 1-f

Two texturing vehicles: plants, e.g. leaves, on blotting paper

Example 1-a was reproduced using the leaf texturing vehicle of example 1e with a second blotter texturing vehicle.

Leaf (texturizing medium n)^o1) On blotting paper (texturing Medium n)^o2) Above, the leaves are placed on the face of the membrane. Thus obtaining a reproduction of the leaves on a background of blotter paper.

Example 2: representative general method in the case of a multilayer film comprising a layer (1) and a layer (2)

Example 2-a: adhered layer (1) and layer (2)

Example 1-a was reproduced with the difference that, in step (c), a multilayer film (F) comprising a layer (1) and a layer (2), the layer (1) comprising the composition CPO as defined in example 1 but having a thickness of 50 μm, the layer (2) consisting of pure polyamide PA12 and having a thickness of 100 μm, was placed in the mould and above the fabric (texturing medium T), the layer (1) being in contact with the texturing medium T.

Steps (d) and (e) were the same as in example 1-a.

Example 2-a: non-adhered layer (1) and layer (2)

Example 1-a was reproduced with the difference that, in step (c), a multilayer film (F) comprising a layer (1) and a layer of an adhesive was placed in the mould and above the fabric (texturing medium T), layer (1) comprising the composition CPO as defined in example 1, but having a thickness of 50 μm, the adhesive consisting of PE grafted with 0.6% maleic anhydride (density 0.96 g/cm)³MFI (melt flow index) of 2, measured at 190 ℃ under 2.16kg according to standard ASTM 1238), layer (1) is contacted with texturing medium T.

In step (d), HDPE in the molten state, having a density of 0.96 and an MFI of 2, measured at 190 ℃ under 2.16kg according to standard ASTM 1238, was injected under the same conditions as PA12 of example 1a (step d).

Example 3: compression mould

A compression mold having two heatable flat plates is used. The temperature of the plate was set to 150 ℃. The texturing vehicle and film of example 1a were included. The texturing medium was placed on the film and both were placed between two plates, which were subsequently placed under a pressure of 50bar during 1 minute. When the film is cold enough that it can be handled, the texturing medium is removed effortlessly. The impression of the fabric on the film was subsequently found, as well as a similar feel to the texturizing vehicle.

Comparative example 1: visual and tactile structure of fabric

The skilled person has tried to reproduce the visual and tactile structure of the fabric of page 24 of WO 06/008358.

The only information provided are temperature (110 ℃), pressure (20bar) and time (5 minutes).

The thickness of the texturing medium is not given.

The composition of the polyamide is not given.

The thickness of the film is not given.

The skilled person cannot use the data given for the parameters of the method described in this example to obtain an object as claimed in WO 06/008358.

Comparative example 2:

inventive example 3 was reproduced except that the temperature of the plate was set to 30 ℃. The impression of the fabric is then not reproducible and the feel of the film is hardly changed.

Comparative example 3:

inventive example 3 was reproduced except that the temperature of the plate was set to 250 ℃. The fabric is bonded to the membrane and it is impossible to separate it correctly from the membrane.

Comparative example 4:

example 1a of the present invention was reproduced except that the mold was set to 20 ℃ (step a) and the pressure was maintained only during 2 seconds in step d.

The result is then negative, so that the impression of the fabric cannot be reproduced and the feel of the film is hardly altered.