WO2003003825A1

WO2003003825A1 - Flexible fishing lures

Info

Publication number: WO2003003825A1
Application number: PCT/FR2002/002284
Authority: WO
Inventors: Franck Jousse; Philippe Labbe; Philippe Mazabraud; Alain Delalande
Original assignee: Commissariat A L'energie Atomique; Delalande Peche Sa
Priority date: 2001-07-03
Filing date: 2002-07-01
Publication date: 2003-01-16
Also published as: FR2826835B1; FR2826835A1

Abstract

The invention concerns a flexible fishing lure made of a material comprising at least a thermoplastic elastomer (TPE), such as a styrene thermoplastic elastomer (STP). The fishing lure exhibit enhanced swimming behaviour and is easy to produce, is recyclable, non-toxic and biodegradable.

Description

SOFT FISHING LURES

DESCRIPTION

The present invention relates to flexible fishing lures, in particular flexible plastic fishing lures.

Currently, the majority of plastic fishing lures are made of poly (vinyl chloride) ("PVC"). This thermoplastic polymer being intrinsically rigid, it is highly plasticized during its implementation and we then speak of plastisol. Fishing lures made from this polymer are relatively flexible, namely with a shore A hardness around 30, and have no shape memories due to implementation or to elastic mechanical stress.

However, given the chemical nature of the polymer used, these fishing lures have many disadvantages, in particular:

- they contain almost 10% by mass of the chlorine element. Due to the presence of this halogen, in large quantities, they are therefore not very environmentally friendly; - they are most often plasticized with phthalates (such as dioctyl phthalate, for example), the toxicity of which is recognized. Thus, they may present risks of ecotoxicity or of human toxicity in the event of excessive release of the plasticizer by the material; - they are not biodegradable and have lifetimes of several tens of years in the event of release into the environment; they cannot be implemented in a simple manner, by injection for example, because their plasticization requires a gel time prior to their molding, as well as a final heat treatment;

- despite their flexibility, they do not provide a soft, pleasant touch ("soft"). They may even have an “oily” appearance to the touch because their release from the mold requires the use of oil, for example vaseline oil, and a small amount of plasticizer exudes on the surface.

Furthermore, some fishing lures can be made of vulcanized elastomer, that is to say of rubber, which gives them a fairly good flexibility with a shore A hardness close to 50, possibly without shape memory. However, the properties sought in terms of recyclability, biodegradation or ease of implementation are not satisfactory. In addition, their touch is not sufficiently soft and pleasant and their coloring does not allow sufficiently nuanced shades.

Finally, known fishing lures, whether made of PVC or rubber, often have unsatisfactory swimming behavior.

There is therefore a need for a flexible fishing lure, which does not present a danger to the environment during its use and during its disposal, which presents no risk of toxicity, both to humans and animals, which is easily biodegradable and recyclable, which can be manufactured in a simple, reliable and low cost, which gives the touch a soft and pleasant sensation, which has an attractive appearance and which can, in particular, take on many colors, shades, tints, and shapes. There is still a need for a fishing lure which, while fulfilling the criteria listed above, has superior swimming qualities or at least equivalent to those of existing lures.

The object of the present invention is to provide a flexible fishing lure, which meets, among other things, these needs.

This object, and others still, are achieved, according to the invention by a flexible fishing lure, characterized in that it is made of a material comprising at least one thermoplastic elastomer ("TPE").

It is, first of all, to note that the thermoplastic elastomers have never been used to make fishing lures and that their use for this purpose is never mentioned or suggested in the prior art.

Thermoplastic elastomers (ThermoPlastic Elastomer or “TPE”, in English) have been used in the industry for about thirty years, but their use in the field of fishing and, in particular, fishing lures has never been mentioned. The thermoplastic elastomer which enters the material of the lure of the invention can consist of a flexible phase, dispersed in a continuous rigid phase. However, advantageously, according to the invention, said thermoplastic elastomer consists of an alternation of segments, flexible sequences and of segments, rigid sequences.

Surprisingly, the fishing lures according to the invention, which are made of a material comprising at least one thermoplastic elastomer, meet, among other things, all of the needs, criteria and requirements mentioned above, and provide a solution to the problems posed by fishing lures of the prior art, and greatly improve the properties and performance of these fishing lures.

The fishing lures according to the invention in TPE are as flexible, or even more flexible than the fishing lures in plasticized PVC or in vulcanized elastomer, because the TPEs can have hardnesses SHORE A measured according to ISO R 868, for example from 5 to 30. This great flexibility is combined in particular with an absence of shape memory, a high elongation at break, for example from 500 to 1500% measured according to ISO 37, and with a lower density, for example close to 0 9.

It is these properties, but not only, which give the fishing lure according to the invention an improved swimming behavior.

Swimming behavior is a subjective property, difficult to assess for non-fishermen, which accounts in particular for buoyancy, capacities of the lure to have movements, an appearance reproducing at best those of a prey, such as a fish, amphibian or other.

The influence of the material constituting the lure on the swimming properties of the lure is completely unpredictable. According to the invention, completely unexpectedly, it has been demonstrated that the use of at least one thermoplastic elastomer in the material constituting the lure leads to excellent and improved swimming behavior, compared to lures of the art anterior, not comprising a thermoplastic elastomer ("TPE").

In addition, the implementation and manufacture of the lures according to the invention are easy and they can be manufactured industrially, according to conventional technologies such as injection, and they can be easily colored, both in the mass and on the surface. .

The lures according to the invention also have a clear advantage over the lures of the prior art, without a thermoplastic elastomer, as regards respect for the environment, in particular as regards their recyclability, their absence of toxicity and their biodegradability / biodegradation. . Indeed, most VSEs and in particular the

TPE styrenics do not contain halogen elements, such as chlorine and they do not require the use of toxic phthalate plasticizers. Thus, the fishing lures according to the invention are more respectful of the environment because they are recyclable and completely non-toxic. In addition, thermoplastic elastomers are for the most part intrinsically biodegradable.

In addition to the advantageous properties listed above, it has been found that only the lures according to the invention, due to the presence of at least one thermoplastic elastomer, have a soft and pleasant feel, not sticky and non-oily, at the contrary to the lures of the prior art. Finally, on the contrary, existing lures, the lures according to the invention can have a wide variety of colors, shades, shades, reflections, and shapes. They can be adapted exactly to the requirements of each fisherman in each fishery.

More specifically, the TPE (s) is (are) generally present (s) in the material in an amount of 10 to 70% by weight, preferably from 20 to 50% by weight.

Preferably, the TPE is advantageously a "food" quality TPE, which further reduces the possible risks of toxicity.

Said at least one thermoplastic elastomer is preferably a styrenic thermoplastic elastomer ("TPS").

Advantageously, said styrenic thermoplastic elastomer (“TPS”) comprises an alternation of segments, flexible sequences and of segments, rigid sequences.

The rigid blocks are chosen from styrene blocks, and the flexible blocks are chosen from polybutadiene, poly (ethylene butylene) and polyisoprene blocks. When the rigid segments are made of polystyrene and soft segments consist of poybutadiêne, TPS is named "SBS" SBS are particularly available from Atofina ^® Company, under the name FINAPRENE ^®.

When the rigid segments are made of polystyrene, and the soft segments consist of poly (ethylene butylene), the TPS is called "SEBS" SEBS are in particular available from Shell Chemicals ^®, under the trademark KRATON ^® G .

When the rigid segments are made of polystyrene and the flexible segments are made of polyisoprene, the TPS is called "SIS". Due to the properties sought for the lure, in terms of flexibility and absence of shape memory, whatever the nature of the styrenic elastomer (s) used, it or these will preferably comprise (have) from 15 to 50% by mass of sequences, polystyrene segments.

The TPEs and in particular the TPSs can have a radial, linear, branched or star structure, these polymers then generally form a three-dimensional network, with a matrix for example made of elastomeric polybutadiene and nodes, nodules, formed, for example, of polystyrene.

Preferably, the TPE (s), in particular the TPS (for example SBS), used will have (have) a radial, branched, or star structure, because such a structure allows in particular to include more load, d antioxidant, and oil in the material and to obtain VSEs that are easier to handle, to process, to implement ("better processing").

Among GST and FINAPRENE ^® products, already mentioned above, the preferred products will e.g. FINAPRENE ^® 401, which is a radial SBS styrene content 22% by weight, of low molecular weight (about 200,000), and FINAPRENE ^® 411 or 411 X with a styrene content of 31% and a high molecular weight (around 300,000). FINAPRENE ^® 411 X contains 5 phr of oil.

The composition may comprise only one TPE, preferably styrenic TPE or TPS, but it may also be advantageous to use several TPEs, preferably TPS (for example SBS), for example up to 10 TPE, preferably TPS , preferably 2 or 3, which differ in their molecular mass and / or their content, for example in styrene and / or their structure, etc.

Thus, a mixture of a high molecular weight TPS and a lower molecular weight TPS can be used.

A particularly interesting mixture is a mixture of FINAPRENE ^® 411 or 411 X and FINAPRENE ^® 401.

Preferably, in order to obtain low hardnesses compatible with the desired application, it may be necessary to add, in addition, to the material a non-toxic oil, such as a paraffinic oil, in a proportion, for example, from 0.5 to 2, preferably from 1.0 to 1.7, in mass equivalent with respect to the TPE (s), such as TPS or TPS. In addition, in order to facilitate the implementation and to increase the biodegradation / biodegradability, it is advantageous to add to the material a flexible polymer, unsaturated, and incompatible with the rigid phase, for example the rigid phase, polystyrene (when the

TPE is a TPS).

This polymer can be, for example, a thermoplastic polymer or an elastomer or a thermoplastic elastomer, the latter being different from the TPE, already mentioned above, for example TPS.

This polymer can be chosen, for example polybutadienes, such as polybutadiene available under the name Buna ^®, eg quality

CBHX 530 S, from the company BAYER ^® . This polymer is generally added in an amount of 10 to 40% by mass, relative to the (x) TPE, for example TPS.

Optionally, it is also possible to add a biodegradable filler, for example starch; when it is present, this biodegradable charge is in an amount of 5 to 20% by mass relative to the (x) TPE, for example TPS.

Said biodegradable filler is generally used combined with a plasticizer (plasticized biodegradable filler), preferably a non-toxic plasticizer, preferably natural, such as glycerol.

When present, such a plasticizer is in an amount of 50 to 100% by mass relative to the biodegradable filler. It is preferable and this is particularly the case when the TPE is a styrenic TPE (TPS), such as an SBS, that the material additionally comprises one or more antioxidant (s). The chemical nature and the content of the antioxidant (s), whether they are so-called processing antioxidants or aging antioxidants, are adapted so that the formulated mixture can be transformed without being degraded, without thereby excessively increasing the life of the fishing lure, that is to say slowing down its degradation including its biodegradation.

The antioxidant (s) may be chosen, for example, from phosphite antioxidants and phenolic antioxidants.

Phosphite antioxidants are available from the company CIBA SPECIALTY CHEMICALS ^® , under the name IRGAFOS ^® , among which mention may be made, for example, of IRGAFOS ^® 168. Phenolic antioxidants are available from the company CIBA SPECIALTY CHEMICALS ^® , under the name IRGANOX ^® , among which mention may be made, for example, of IRGANOX ^® 1010.

It is possible to use a combination of two or more antioxidants, for example a mixture of a phenolic antioxidant and a phosphite antioxidant may be used.

The total content of antioxidant (s) is generally 0.2 to 2% by mass relative to the TPE (s), for example TPS. Other fillers can, moreover, also be incorporated into the material, these fillers can in particular be chosen from silica fillers, which allow an aid to the implementation.

Finally, the material generally comprises, in addition, one or more dye (s) and / or pigment (s) to give it the desired color, tint, shade.

The fishing lure according to the invention can take any color, shade, shade, desired. In particular because of the transparency of the styrenic thermoplastic elastomers TPS, these can take all the colors, shades and colors desired, it follows that the fishing lure can have a pleasant, varied, attractive appearance, never obtained with lures of the prior art, which are not made of a material comprising a TPE, such as a TPS.

The dyes and / or pigments are generally present in a proportion of 1 to 20% by mass relative to the total mass of the material.

The material may also comprise additives with an optical effect, such as nacres or flakes, for example metallic, or others to give the material optical properties of light reflection or other optical effects, such effects are not or little obtained with the lures of the prior art.

The lures according to the invention, in all fishing conditions (nature of the water, lighting, depth of the water, turbidity, color of the water, etc.), will have the desired appearance and the desired attractiveness for the fish.

Preferred materials for manufacturing the fishing lures according to the invention will have the following composition:

- styrenic thermoplastic elastomer (s) (TPS) with radial, branched or star structure, such as SBS: 10 to 70% by weight, preferably 20 to 50% by weight;

- flexible, unsaturated polymer, incompatible with the polystyrene phase, such as polybutadiene: 10 to 40% by mass relative to (x) TPS; - non-toxic oil, such as a paraffinic oil: 0.5 to 2, preferably from 1.0 to 1.7 relative to the (x) TPS;

- antioxidant (s): 0.2 to 2% by mass relative to (x) TPS; - optionally, dye or pigment: 1 to

2% by mass relative to the total mass of the material;

- optionally, biodegradable charge: 5 to 20% by mass relative to the (x) TPS, associated with a non-toxic plasticizer: 50 to 100% by mass relative to the biodegradable charge;

- possibly, additive with optical effect.

Preferably, the styrenic thermoplastic elastomer component is a mixture of two or more styrenic elastomers (for example SBS) of which one has a high molecular weight and the other has a lower molecular weight.

Preferably, the antioxidant component is a mixture of two or more antioxidant compound (s), one of which is, for example, a phenolic antioxidant and the other is a phosphite antioxidant.

The fishing lure according to the invention can also be defined as being a fishing lure having the following properties: - shore A hardness according to ISO R 868: 5 to 30, preferably 15 to 25;

- density according to ISO 1183: 0.8 to 1.2, preferably 0.9 to 1.0;

- maximum stress according to ISO standard 37: 1.5 to 4 MPa, preferably around 3 MPa; elongation at break according to ISO standard 37: 500 to 1,500%, preferably approximately 1,000%; possibly biodegradation according to European Commission Directive 92/69 / EEC,

C.4-C, July 31, 1992, and OECD Directive no. 301 B of July 17, 1992: 50 to 90%, preferably about 70%.

The method for preparing the fishing lure according to the invention is conventional. The various polymers, including TPE, with the oils, antioxidants and, optionally, fillers are previously compounded in an internal mixer or an extruder.

The “compound” obtained, which is preferably in the form of granules, is then used to manufacture fishing lures by molding, for example by molding by injection. Dyes, pigments and / or flakes, nacres can be added either during the compounding phase or during the molding phase.

The lures of the invention can take any desired shape suitable for all types of fishing, while presenting a soft appearance, pleasant to the touch and with the same qualities.

The invention will now be described with reference to the following example, given by way of illustration and not limitation.

Example 1

Fishing lures according to the invention, flexible, non-toxic and environmentally friendly, have been made of SBS base elastomeric thermoplastic material, the composition of which is as follows:

100 g of styrenic TPE composed of 20 g of food quality (grade) FINAPRENE ^® (trade mark) 411 X (quality, trade grade) manufactured by the company ATOFINA ^® and 80 g of food quality FINAPRENE ^® (trade mark) 401 (commercial grade) manufactured by the company ATOFINA ^® ;

- FINAPRENE ^® 401 is an SBS with a radial structure having a styrene content of 22% and a molecular weight of approximately

200,000; - FINAPRENE ^® 411 X is an SBS with a radial structure having a styrene content of 31% and a molecular weight of about 300,000 and an oil content of 5 phr;

- 15 g of BUNA ^® polybutadiene (commercial brand) of grade CBHX 530 S (commercial grade) manufactured by the Company

BAYER ^® ;

- 165 g of paraffinic oil;

- 0.5 g of phosphite antioxidant IRGAFOS ^® (trademark) of grade 168 (commercial grade) manufactured by the company CIBA

SPECIALTY CHEMICALS ^® ;

- 0.5 g of phenolic antioxidant IRGANOX ^® (trademark) grade 1010 (commercial grade) manufactured by the company CIBA SPECIALTY CHEMICALS ^® .

All these polymers and fillers were previously mixed in a single screw extruder, then granules at the outlet. The granules of the compound were introduced into an injection press to mold fishing lures.

Fishing lures have a shore A hardness (ISO standard R 868) of 17, a density (ISO standard 1183) of 0.89, a maximum stress (ISO standard 37) of 2.9, an elongation at break (ISO 37) of 940% and biodegradation (Commission Directive 92/69 / EEC C.4-C, 31th July, 1992 and OECD guideline no. 301B, 17 ^th July 1992) of 70%. Their touch appearance is soft and pleasant and they exhibit improved swimming behavior.

Claims

1. Soft fishing lure, characterized in that it is made of a material comprising at least one thermoplastic elastomer ("TPE").

2. Lure according to claim 1, in which the TPE (s) is (are) present in the material in an amount of 10 to 70% by weight, preferably from 20 to 50% by weight.

3. Lure according to claim 1, in which the TPE (s) is (are) one (s) of food grade TPE.

4. Fishing lure according to claim 1, wherein the thermoplastic elastomer consists of a flexible phase dispersed in a continuous rigid phase.

5. Fishing lure according to claim 1, in which the thermoplastic elastomer consists of an alternation of segments, sequences, flexible and of segments, sequences, rigid.

6. Fishing lure according to claim 5, in which the thermoplastic elastomer is a styrenic thermoplastic elastomer (“TPS”).

7. Fishing lure according to claim 6, in which the blocks, flexible segments of the thermoplastic elastomer are polystyrene blocks and the blocks, flexible segments are chosen from the polybutadiene blocks (“SBS” thermoplastic elastomer), poly (ethylene butylene) ) ("SEBS") and poly (isoprene) ("SIS").

8. Fishing lure according to claim 6 or claim 7, wherein the styrenic thermoplastic elastomer comprises from 15 to 50% by mass of polystyrene blocks.

9. Lure according to any one of claims 6 to 8, in which the styrenic thermoplastic elastomer has a radial, branched or star structure.

10. Lure according to any one of claims 6 to 9, in which the material comprises several thermoplastic elastomers, preferably styrenic ("TPS"), for example SBS, which differ in their molecular mass and / or their content, for example in styrene and / or their structure.

11. Lure according to any one of claims 6 to 10, in which the material further comprises a flexible polymer, unsaturated and incompatible with the rigid phase, for example the rigid polystyrene phase, such as polybutadiene in a proportion of 10 to 40% by mass relative to (T) TPE, for example TPS.

12. A lure according to any one of claims 1 to 11, in which the material further comprises a non-toxic oil, such as a paraffinic oil in a proportion of 0.5 to 2, preferably 1.0 1.7, by mass equivalent with respect to the thermoplastic elastomer or to thermoplastic elastomers, such as the TPS (s).

13. A lure according to any one of claims 1 to 12, in which the material further comprises a biodegradable filler, by example starch, in an amount of 5 to 20% by mass relative to (T) TPE, for example TPS, said biodegradable filler being associated with a non-toxic plasticizer, preferably natural, such as glycerol, in an amount of 50 to 100% by mass relative to said biodegradable charge.

14. A lure according to any one of claims 1 to 13, in which the material also comprises one or more antioxidant (s) chosen, for example, from phenolic antioxidants and phosphite antioxidants.

15. Lure according to any one. of claims 1 to 14, in which the material also comprises other fillers chosen in particular from silica fillers.

16. Lure according to any one of claims 1 to 15, in which the material further comprises one or more dyes and / or pigments.

17. Lure according to any one of claims 1 to 16, wherein the material further comprises one or more additive (s) with optical effect, such as nacres or flakes, for example metallic.

18. Soft fishing lure made of a material comprising the following composition: styrenic thermoplastic elastomer (s) (TPS) with radial structure, branched or in a star, such as SBS: 10 to 70% by weight , preferably 20 to 50% by weight; - flexible, unsaturated polymer, incompatible with the polystyrene phase, such as polybutadiene: 10 to 40% by mass relative to (x) TPS; - non-toxic oil, such as a paraffinic oil: 0.5 to 2, preferably from 1.0 to 1.7 relative to the (x) TPS;

2% by mass relative to the total mass of the material;

- possibly, additive with optical effect.

19. Fishing lure according to any one of claims 1 to 18, having the following properties:

- Shore A hardness according to ISO R 868: 5 to 30, preferably 15 to 25;

- density according to ISO standard 1183: 0.8 to 1.2, preferably 0.9 to 1.0;

- maximum stress according to ISO standard 37: 1.5 to 4 MPa, preferably around 3 MPa;

- elongation at break according to ISO standard 37: 500 to 1,500%, preferably approximately 1,000%; - possibly biodegradation according to

European Commission Directive 92/69 / EEC,

C.4-C, July 31, 1992, and OECD Directive no. 301 B of July 17, 1992: 50 to 90%,

Preferably about 70%.