JP2001512171A - Articles with improved grip - Google Patents

Abstract

  (57) [Summary] The present invention provides that at least a portion of the article designed to be in contact with the hand contains an effective amount of an additional backbone, perfluoroalkyl and alkyl side groups, preferably at 25-45 ° C. Relates to articles having an improved grip, coated with a polymer having a melting temperature in the range of 25-37 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an article having improved gripping properties and a method for manufacturing the article. The term "grip" of an article by a person (or, equivalently, the term "grip by hand") refers to the impact and / or force of a person by means of one or two hands, typically including a constant force greater than 1N. Or to convey various movements to the article. This force is increased by the force associated with the acceleration a person desires to impart to the article, or the weight of the article or gripping the article for the purpose of ensuring that the article is in proper balance. It may be a tensile force exerted by a person. In all these situations, due to the contact between the article and one or both hands of the person holding or gripping the article, improving the human grip of the article and the risk of slipping of the human hand It is important that this is facilitated by certain attachments that limit the Thus, "gripping an article by hand" means that a person squeezes the article with one of its parts, i.e., the part and the hand achieved by the inside of the person's hand, including the palm, or through gloves. It should be understood that it should be understood to mean the contact between

[0002] Examples of situations in which it is important to have good grip of the article can be given, in which the field of tool handling and the grip of the article by the appropriate hands ensure good results. Most importantly, all sport areas that require movement of articles (tennis, golf, windsurfing, water skiing) are included. This fact will be more fully appreciated when referring to special sports such as tennis or golf. In this sport, a leather or rubber cover on the racket or club grip should be used to ensure that the player has the best grip.
It is understood that you must not slip. As an example of an article to be gripped by a person, a part of a sailboat called a wishbone is also described for the purpose of ensuring a proper balance.

In such a case, in order to obtain good adhesion, several methods have been conventionally proposed, and a surface treatment has been developed. For example, Patent Application WO 94/1941
No. 4 recommends the use of blends formed from ethylene-vinyl acetate copolymers, natural or synthetic lubricants and tackifiers.

[0004] Emulsions containing a polyolefin-based tackifying resin (JP 08-17356) or acrylic polymers (France Patent 2,192,56)
No. 7) was also proposed for surface treatment.

[0005] From a different perspective, the production of artificial leather based on leather powder, binders and tackifying resins has also been considered. For example, in Japanese Patent No. 04-077250,
It has been proposed to produce reconstituted leather containing 60% leather powder and 40-95% synthetic resin.

[0006] In all cases, these formulations improve adhesion to the substrate,
It has a number of disadvantages, especially those related to storage of the equipment in question. For example, these formulations can cause problems such as dust sticking, accelerated fouling of the substrate, or unwanted adhesion of the treated article to other articles stored with it.

Further, it has been proposed to use additives of the semi-crystalline acrylic polymer type in pressure sensitive adhesives (PSAs) (eg, US Pat. No. 5,412,035 and R).
. Clarke et al., Adhesive Age, 36, 39, 1993.
September). By including, in these systems, semi-crystalline acrylic polymers having side groups containing long alkyl chains (the number of carbon atoms of which are 12 or more), the temperature range from 0 to 60 ° C. It is possible to obtain a melting point. Above this melting point, the polymer adheres. Below this temperature, the polymer does not adhere. This type of PSA, having a melting point of about 30 ° C., is used, for example, for fixing bandages to the skin. The bandage is then simply removed by lowering the temperature below 30 ° C.

[0008] However, these documents, whether the article is a tennis racket grip or a sailboard wishbone, do not suggest any problem of hand grip of the article as described above. Furthermore, the chemical structures used have the disadvantage that they are not sufficiently water-resistant to be usefully used. Similarly, weak resistance to perspiration, body fluids or solvents limits its benefits in possible applications other than in the medical field. In the field of sports, a wet environment can be wet, whether due to sweating of a sportsman or in the case of outdoor sports, whether due to rain or other things, in the case of a sailboard, due to splashes. It is important to ensure proper hand grip of the article, including the condition.

[0009] It has been found that it is possible to obtain an article which has improved gripping properties even when the article is used in wet conditions and which exhibits outstanding stain resistance properties.

Thus, the subject of the present invention is that at least a part thereof, intended to be in contact with the hand, contains an effective amount of perfluoroalkyl and alkyl side groups off the main chain. And coated with an effective amount of polymer having a melting point of 25-45 ° C, preferably 25-37 ° C, and exhibiting improved hand grip.

[0011] The melting points described herein can be obtained from the following cycles: increasing the temperature from -30 ° C to + 130 ° C, all at a rate of 10 ° C / min, raising the temperature from + 130 ° C to -130 ° C.
Measured by Differential Scanning Calorimetry using lowering again to 80 ° C. and raising the temperature a second time from −80 ° C. to + 130 ° C. This melting point is
Measured during the second temperature rise. In the context of this specification, the melting point is the lowest temperature observed corresponding to the minimum of the endothermic peak.

The article according to the invention is distinguished by a good adhesion between a human hand or a gloved human hand and the relevant part of the article, whether wet or raining. Provides grip. When the human hand separates from the article, there is advantageously no trace of any adhesive on the human hand and the article no longer exhibits adhesive properties. Thus, the article according to the invention exhibits very good resistance to contamination, especially against dust, when the article is not gripped by hand.

[0013] The structure of the main chain of the polymer may vary greatly, especially polysiloxanes, poly (
It may be of the (meth) acrylic, polyvinyl, polystyrene, polyester, polyphosphazene, polyamide or poly (meth) acrylamide type.

As the main chain, a poly (meth) acryl type chain is preferred.

[0015] The length of the perfluorinated side groups is advantageously of 5 to 20, preferably 7 to 15 carbon atoms.

A perfluorinated side group is attached to the polymer backbone by a divalent group — (CH ₂ ) _m — where m is an integer from 1 to 12, preferably equal to 2. Are preferred.

The alkyl side groups have a length of 12 to 30, preferably 14 to 20, carbon atoms.

Furthermore, it is possible to introduce into the main chain of the polymer used a unit having no side-chain group, such as a unit of the N-methylolacrylamide, ethylene or vinyl chloride type.

According to a preferred embodiment of the article according to the invention, the proportion of perfluoroalkyl-type side groups (expressed as% of the total number of side groups) of some of the articles intended to come into contact with the hand is It is covered with 20-70%, preferably 30-60%, of a polymer.

Finally, the polymer used advantageously has a sticking energy measured at 35 ° C. of 1 to 1000 J / m ² , preferably 10 to 100 J / m ² . The term "cohesive energy" refers to two pieces brought into contact through an adhesive in a short time, typically within a few seconds, under a few pressures, typically several tenths of a megapascal. Should be understood to mean the energy (per unit area) required to separate the surface of This energy determines, at a fixed temperature, the energy required to separate the aluminum plate treated with the polymer, which was previously in contact with the prism by applying a pressure of 0.35 MPa for 1 second. It is measured by a prism pegometer.

The articles according to the invention are preferably tools and tennis rackets, table tennis rackets,
It is selected from sporting goods such as squash rackets, badminton rackets, golf clubs, sailboard wishbones and automobile steering wheels. Often the part of these articles that is intended to be in contact with the hand is a grip or handle.

Golf clubs are most particularly preferred.

The polymers used in the articles according to the invention are manufactured using methods known to those skilled in the art. Using a solution or emulsion copolymerization or grafting technique of appropriate monomers to introduce fluoroalkyl and alkyl side groups,
Particular mention is made of chemical modification of the polymer backbone.

The amount of polymer coating the part of the article intended to be in contact with the hand
Can be varied over a wide range of limits. This depends on the area in question
About 0.05 to 100 g / m², Preferably 0.25 to 20 g / m ² It is.

The present invention also relates to a method intended to improve the hand grip of an article, wherein said article is intended to bring an effective amount of a polymer as defined above into contact with the hand. And a method characterized by applying the method to

The polymers can be applied in a number of ways, which vary depending on the properties of the support to be treated. Polymers provided in the form of a solution or emulsion include:
In particular, it can be deposited on a support by spraying it, applying it using a brush or dipping it into a bath. For some supports, more specialized methods can be used, such as, for example, foaming or depositing in the case of textiles or crimping in the case of leather. Generally, a drying operation is required, and this drying operation can be performed at a temperature within a range from an ambient temperature to 200 ° C., but it is preferable to dry at an ambient temperature.

The polymer is generally applied by means of a liquid containing 0.5 to 10% by weight of the polymer.

If the performance is substantially reduced, the process can be completely regenerated by a new application.

Various supports can be treated. For example, metal, woven fabric, non-woven fabric, plastic, leather, paper, construction materials, and wood can be mentioned.

Without limiting the scope, the invention is illustrated by the following examples. In the examples, the parts given are expressed as parts by weight unless otherwise indicated.

In these examples, the water resistance and oleophobicity of the treated support are evaluated by the following tests.

Water resistance test “American Association of Textile Dyeing (American Association of
Textile Chemists and Colorists (AAT
The resistance of the treated fabric to wetting by water is determined by the tests described in the CC) Technical Manual, Test Method 22 (1992), standard. This includes
From a height of 15 cm, via a funnel ending with an aluminum spray head, pour 250 ml of water onto a cloth specimen stretched on a 15.2 cm diameter frame inclined at 45 ° It is included. When all the water has been poured, dab the frame over a solid surface to remove excess water and reduce the level of wetting with respect to a series of six values shown in the photographic standards published in the standard. , Visually. The table below shows the grades in the test as a function of the wetting level.

[0033]

[Table 1] The oleophobicity test is described in the "AATCC Technical Manual", Test Method 118 (1992), the standard, which determines the non-wetting of a substrate on a woven fabric by a series of reduced surface tension oily liquids. Measure by test. The grade of the treated substrate is 30
It is defined as the maximum value of the test liquid that does not wet the support after a contact time of seconds. The test liquids used in this determination are listed in the table below.

[0034]

[Table 2] Example 1 1000 parts by volume heated with a thermostated jacket, anchor-type stirring
425 parts of butyl acetate, -47 parts of the general formula: C_nF_{2n + 1}C₂H₄O-CO-CH = CH₂  (In each weight ratio of 63, 25, 10 and 2, n is 8, 10, 12 and 14
Of fluorinated acrylate) and -28 parts of stearyl methacrylate.

After inerting with nitrogen and heating to 70 ° C., the polymerization was started by adding 1.5 parts of 2,2′-azobis (isobutyronitrile). After polymerizing for 6 hours, the mixture was allowed to cool to give a clear solution (S1) containing 15% by weight of the copolymer according to the invention.

[0036] This copolymer has an adhesive energy of 0 J / ^{m 2} at a and 30 ℃ 16J / ^{m 2} at 35 ° C.. It has a melting point of 35 ° C.

For comparison, a stearyl methacrylate homopolymer was produced under the same synthesis conditions to obtain a homopolymer solution (Sa). The melting point of poly (stearyl methacrylate) is 33.6 ° C., which is comparable to the melting point of the above copolymer.

Solutions (S1) and (Sa) are applied in an amount of 10 g / m ² of polymer by spraying them onto the rubber cover of a golf club. It has been found that the grip is effectively improved.

The solution (S1) is applied in a quantity of 10 g / m ² to a 100 cm ² rubber sheet. The rubber sheet is brought into contact with the normally dusty floor surface. The rubber sheet is found to be almost free of soiling.

The water resistance and solvent resistance provided by (S1) and (Sa) are substantially different. The two solutions are applied by spraying them onto a polyamide / cotton blend. These solutions are diluted in butyl acetate until a polymer concentration of 1% is obtained, corresponding to an amount of polymer of 0.25 g / m ² .

After drying, the results described in the table below are obtained.

[0042]

[Table 3] Grade 0 in the oleophobic test means that the substrate is wetted by the eight test liquids,
It means that a substrate corresponding to this grade is less oleophobic than a substrate having a rating of 1-8.

Example 2 In the same reactor as in Example 1, -375 parts of demineralized water, -135 parts of acetone, -13.2 parts of oleyltrimethylammonium chloride, -12.1 Parts of a mixture of ethoxylated alkylphenols having an HLB of 15; 136.8 parts of a mixture of the same polyfluorinated acrylates as in Example 1; -130.7 parts of stearyl methacrylate; -14.9. Parts of N-methylolacrylamide as a 48% solution in water and -0.27 parts of n-dodecylmercaptan were introduced.

After inerting with nitrogen and heating to 65 ° C., the polymerization was started by adding 2 parts of azobis (amidinopropane) hydrochloride. After 3 hours of polymerization, the acetone was distilled off and the remaining mixture was diluted with water to give an emulsion with a solids content of 20%.

The copolymer synthesized in this way has a melting point of about 30 ° C.

The resulting coating has a tack energy of about 12 J / m ² for temperatures above 30 ° C., while it is zero for lower temperatures.

The emulsion is applied by spraying it onto the leather cover of the tennis racket grip. This is dried at room temperature for several minutes.

The tennis racket treated in this way has a very good grip, even in the rain, and has a very good resistance to dirt contamination when stored at room temperature. This racket grip is excellent in hydrophobicity and oleophobicity.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/04 C09D 201/04 D06M 15/277 D06M 15/277 (72) Inventor Dou Courvoisier, Guillaume France Country, F-75116 Paris, Lille Pergolaise, 42 (72) Inventor Colpar, Jean-Marc, France 4D075 CA12 DC38 4F006 AB24 CA00 DA04 4J038 CG141 CH011 CH251 GA12 PB02 4L033 AC03 AC04 CA22

Claims (11)

[Claims] At least a portion of an article intended to be in contact with a hand contains an effective amount of a perfluoroalkyl side-chain group and an alkyl side-chain group away from the main chain, and An article exhibiting improved hand grip, preferably coated with a polymer having a melting point of 25-37 ° C. 2. The article according to claim 1, wherein the main chain of the polymer is a poly (meth) acrylic type chain. 3. The length of the perfluorinated side group is 5 to 20, preferably 7 to 1.
3. Article according to claim 1 or 2, characterized in that it is 5 carbon atoms in length. 4. The method according to claim 1, wherein the perfluorinated side chain group is a divalent group — (CH ₂ ) _m —
Article according to any one of claims 1 to 3, characterized in that it is attached to the polymer backbone by an integer of from 1 to 12, preferably equal to 2. 5. Article according to claim 1, wherein the alkyl side groups have a length of 12 to 30, preferably 14 to 20, carbon atoms. . 6. The article according to claim 1, wherein the proportion of the perfluoroalkyl type side group is 20 to 70%, preferably 30 to 60%. 7. The polymer according to claim 1, wherein the polymer is 1 to 1000 J / m ² ,
Of 0 J / m ^2, and having an adhesive energy measured at 35 ° C., article according to any one of claims 1-6. 8. The amount of polymer coating the part of the article intended to be in contact with the hand is from 0.05 to 100 g / m ² , preferably 0.25 g / m ² , for the surface in question. characterized in that it is a to 20 g / ^{m 2,} article according to any one of claims 1 to 7. 9. The article according to claim 1, wherein the article is selected from tools and sports equipment. 10. The golf club according to claim 1, wherein: 11. A method intended to improve the grip of an article, comprising bringing an effective amount of a polymer according to any one of claims 1 to 7 into contact with a hand. To a part of the article intended.