ITTO940791A1 - ADHESIVE COMPOSITION. - Google Patents

Abstract

The invention relates to hot melt adhesive compositions comprising at least one thermoplastic elastomer and at least one tackifier type resin, the thermoplastic elastomer (elastomers) being a styrene / butadiene / styrene (SBS) copolymer or a styrene / butadiene / styrene mixture with styrene / isoprene / styrene (SIS), in which SIS is present in an amount equal to or less than 50% by weight of the total block copolymer, the composition being characterized in that: a) it is able to bind, when it is applied in the molten state, to plastic and / or cellulosic materials with a peel at 90 ° of not less than 0.5 N / cm; b) it has a retention of the tensile strength after 50 cycles of at least 40%; and c) has a viscosity of 120,000 cps or less at 180 ° C and under a shear stress of 80 sec-1. Hot melt adhesives have elastic properties in the solid state, but their elasticity in the molten state is very low. They can be used for the elasticization of structures as absorbent articles to which they can be applied without the use of any glue.

Description

DESCRIPTION of the industrial invention entitled: "Adhesive composition",

DESCRIPTION

The present invention relates to an adhesive composition. More specifically, the invention refers to a hot melt adhesive which also has elastic properties in the solid state, while its elasticity in the melt state, as indicated by its essentially Newtonian behavior at the working (application) temperature, is very low and in many cases negligible.

In the preparation of many different types of articles, it is necessary to bond an elastic material to a non-elastic substrate. One example is the preparation of disposable nappies, in which elastic strips are used to provide stretch around the legs and waist. Typically, the elastic strips are formed by rubber bands fixed to the body of the diaper-panty by means of layers of adhesive, for example a hot melt adhesive, applied to both surfaces.

This arrangement entails numerous drawbacks. For example, the elastic strip is often covered with an anti-blocking agent, such as talc, during processing to prevent adhesion of the strip to itself. However, this anti-blocking agent can, in turn, make joining the elastic strip to the body of the article more difficult. Furthermore, since the hot melt adhesives used do not have true elastic properties per se, the application of adhesive tends to affect the elongation of the part of the elastic to which it is applied. Finally, the use of the two materials, rubber and adhesive, is expensive.

A composition having adhesive properties when applied in the melt and preferably also pressure adhesive properties, and an elasticity comparable to that of rubber, which also possesses rheological properties suitable for melt processability, is highly desirable, as it could be in capable of replacing the rubber band and adhesive currently used and could represent a considerable improvement in the preparation of items such as diapers-panties. This composition could also find numerous other applications in many different fields.

Many types of compositions are used commercially as hot melt adhesives, and a much greater range of compositions have been suggested for use in this field. A hot melt adhesive can be defined as a composition which exhibits adhesive properties when applied to a substrate in the molten state. This does not preclude that the composition also exhibits adhesive properties at room temperature, e.g. pressure adhesive properties. In general, hot melt adhesives are formulated to obtain properties such as adhesion to various surfaces, heat stability and processing properties rather than elasticity and any attempt to improve elasticity has a negative effect on the adhesion and other desirable properties of the composition. Furthermore, no hot melt adhesive composition on the market combines good adhesion with elastic properties comparable to those of rubber.

Natural rubber is generally too viscous to be used as a base for hot melt adhesives and vulcanized rubber cannot be melted. Many hot melt adhesives are based on block thermoplastic elastomers, as these can be melted. Many of these elastomers, with various properties, are commercially available. For use as an adhesive, thermoplastic block elastomers are generally mixed with "resin tackifier" type agents to improve adhesion. Other additives such as plasticizers may also be needed, depending on the application.

Some prior art proposals have attempted to provide hot melt adhesives which also exhibit elastic properties. For example US-A-4 418 123 has sought to provide a self-adhesive rubber band having a combination of elastic and adhesive properties. The composition is defined, in very broad terms, as a combination of a block copolymer comprising at least one substantially amorphous rubbery intermediate polymer block, and at least two poly (vinyl arene) glassy end blocks, together with a resin compatible with the intermediate block and a resin. compatible with terminal blocks. All specific examples (with the exception of a comparative example with unsatisfactory properties) are based on styrene-isoprene-styrene block copolymers. Notwithstanding the claims that have been made, to the best of the present applicants' knowledge, none of the exemplified compositions in US-A-4 418 123 exhibit true elastic properties comparable to those of rubber, together with good adhesion and workability (see Example Comparative A below).

Similarly, EP - A - 0 424 295 (HB Fuller France SARL) refers to a thermoplastic elastic, intended in particular for the elasticization of diapers-panties, which includes:

a) at least one synthetic rubber which is of the block copolymer type, comprising at least one intermediate rubber block and at least two glass end blocks;

b) between 20 and 150% by weight, on the basis of the block copolymer, of at least one resin of the "tackifier" type, which is compatible with the intermediate block of the copolymer;

c) between 10 and 50% by weight, on the basis of the block copolymer, of at least one resin of the "tackifier" type which is compatible with the terminal blocks of the copolymer; And

d) between 5 and 35%, based on the weight of the composition, of a mineral oil.

The exemplified compositions in EP-A-0 424 295 are generally based on SIS (styrene-isoprenestyrene) and an example of composition based on SBS (styrene-butadiene-styrene) exhibits unsatisfactory properties (see Comparative Example B below). We have now found that, with careful selection of components, hot melt adhesives can be produced with the desired combination of properties mentioned above, for example good melt adhesion (and in many embodiments even at room temperature), comparable elastic properties. to those of rubber and good machinability in the molten state.

The present invention provides a hot melt elastomeric adhesive composition, comprising at least one thermoplastic elastomer and at least one tackifier resin, the thermoplastic elastomer (s) being a styrene / butadiene / styrene (SBS) block copolymer, or a mixture of styrene / butadiene / styrene with styrene / isoprene / styrene (SIS) in which SIS is present in an amount equal to or less than 50% by weight of the total block copolymer, the composition being characterized by:

a) ability to bond, when applied in the molten state, to plastic and / or cellulosic materials with a peel force under an angle of 90 ° of not less than 0.5 N / cm (as defined below);

b) retention of tensile strength after 50 cycles (as defined below) of at least 40%; And

c) viscosity of 120,000 cps or less at 180 ° C and under a shear stress of 80 sec <1>.

Characteristic a) indicated above refers to the adhesive properties of the composition and in all cases the composition should have the properties of a hot melt adhesive which is capable of binding to appropriate substrates, typically plastic and / or cellulosic materials, when applied in the molten state. In particular, "capable of binding" indicates that the composition is capable of exhibiting sufficient adhesion on plastic and / or cellulosic materials, especially for application in the preparation of sanitary absorbent articles.

When applied in the molten state between two substrates of plastic and / or cellulosic materials, the composition leads to a bond strength, measured as a peel at 90 °, of not less than 0.5 N / cm. The composition, in a grammage of 5 g / m <2>, is applied melted between the substrates and 48 hours after the formation of the bond the resistance to peel under a release angle of 90 ° is measured at 23 ° C, with a separation speed of 300 mm / min.

As described in more detail below, many compositions according to the invention bond appropriately to substrates even at room temperature and can exhibit pressure adhesion properties.

The aforementioned characteristic b) refers to the elastic properties of the composition. The test used is described in more detail below and consists of measuring how the elastic properties are maintained after 50 cycles of stretching and relaxation. The percentage of elongation to which the composition is subjected is in relation to the modulus of the composition and similar to the degree of elongation to which the composition is subjected during use. The retention value of 40% for the tensile strength indicates that the elastic properties of the composition are comparable to those of natural rubber and are preferably superior to these. Preferably the retention for the tensile strength is at least 50%, more preferably at least 60%.

Characteristic c) above refers to the workability of the composition and a viscosity of 120,000 cps or less at 180 ° C (shear stress 80 sec <-1>) and indicates that the composition can be applied using conventional equipment used with adhesives hot melt. Preferably the viscosity is 60,000 cps or less, more preferably 30,000 cps or less. It is also highly desirable that the composition according to the invention exhibit a substantially Newtonian rheological behavior, in particular the viscosity must not vary significantly as the shear stress varies. As described in more detail below, many compositions according to the invention exhibit Newtonian behavior at processing temperatures, for example around 180 ° C.

The compositions according to the invention can be formulated with any desired form, depending on the desired end use. However, the modulus has effect on the main properties of the composition and it is convenient to divide the composition according to the invention into low modulus and high modulus compositions.

Low modulus compositions are defined as compositions having a modulus of 0.5 MPa or less than 500% elongation (six times the initial sample length), measured at 23 ° C, with an elongation rate of 500 mm / minute . Generally the low modulus compositions have a modulus comprised between 0.05 and 0.5 MPa, preferably between 0.05 and 0.3 MPa. The low modulus compositions generally exhibit good adhesive properties at room temperature and can also be pressure adhesives. These compositions are normally stretched immediately after their formation, for example after extrusion from the melt as a strip or wire. The elongation can take place immediately prior to or during application to an article, so that the compositions are effectively applied in the elongated state. The low modulus compositions are typically used with an elongation between 400 and 1000%.

Since low modulus compositions will normally be able to be stretched immediately after extrusion, it is desirable that they have a relatively high solidification point, so that they can solidify quickly after extrusion. Preferably, the solidification point (measured by the dynamic-mechanical analysis procedure, described in more detail below) is at least 80 ° C, more preferably at least 100 ° C.

High modulus compositions are defined as compositions having a modulus greater than 0.5 MPa at an elongation of 500% (six times the initial length of the sample) measured at 23 ° C, with an elongation rate of 500 mm / minute . Preferably, the high modulus compositions have a modulus comprised between 1 MPa and 10 MPa. Since the pressure adhesive characteristic is generally inversely proportional to modulus, high modulus compositions are often applied in the melt state, although some may retain a sufficient pressure adhesive characteristic to be applied at room temperature. Application in the molten state implies that the composition is applied without prior elongation, said elongation generally occurring during use and this particularly applies to compositions with a modulus of 1 MPa or greater. For this reason, the high solidification temperature is less critical for high modulus compositions, but, for convenience, these are also preferably formulated to have a solidification point of at least 80 ° C, more preferably of at least 100 ° C. High modulus compositions are generally used with a lower degree of elongation. They are capable of having sufficient spring force with low deformation (typically not more than 50%). However, in cases where the compositions maintain a characteristic of sufficient adhesiveness under pressure, so that they can be applied at room temperature in the elongated state, they can be used with an elongation of up to 400%.

The essential components of the composition according to the invention are a thermoplastic elastomer and a "tackifier" type resin, which will now be described in general terms.

Thermoplastic elastomers are a very interesting technological and chemical class of polymers, which are distinguished by their behavioral characteristics. At room temperature they behave like vulcanized rubbers, exhibiting high elasticity, but, unlike vulcanized rubbers, they can be melted and reworked in the same way as a thermoplastic material.

This behavior is obtained with a particular chemical structure. Most thermoplastic elastomers are block copolymers, that is, their molecules are formed from blocks of different nature, bonded together. The different blocks may alternate along the chain as relatively short blocks (multi-block structure of the type A-B-A-B-A etc.}; or the molecules may have a three-block structure of the type A-B-A, where A are the terminal blocks and B is the central block of different nature (linear three-block copolymers); or the molecules may have a "radial" or "star" structure represented as (AB) X, in which all intermediate blocks B are chemically bonded together at a central point, and the blocks terminals A are arranged radially, each at the end of a block B. The structures formed by only two blocks (diblock) of the AB type are ineffective as thermoplastic elastomers from the point of view of their elastic behavior.

The chemical nature of the various blocks can be different, and the copolymers obtained can be classified, for example, as polyurethanes, polyesters, polyethers, poly-ether-esters amides, etc. However, a common feature is the following: the different blocks are physically incompatible, just as they are mutually insoluble. The material can therefore be considered as a heterogeneous system in which different blocks, even if chemically linked in the same molecule, exist as separate entities. Blocks A of different molecules tend to associate together in microscopic regions or "domains", and the same occurs for blocks B. The material thus obtained has a heterogeneous structure of domains A and B, each well separated, with the one present in lower quantity microscopically dispersed in the other, which constitutes a continuous phase. This continuous phase is generally formed by "soft" or rubbery blocks B., which impart its elastic properties to the material, while the dispersed phase A is formed by "rigid" non-elastomeric blocks. Below the glass transition temperature or softening point of the rigid blocks, each molecule of the copolymer has its A blocks fixed in at least two points, ie they are "confined" to the rigid domains. Consequently, the rubbery part of the molecule can be subjected to elongation, but without sliding with respect to the other molecules and when the external elongation force is released it returns to its initial position due to the entropic effect.

Hence, in thermoplastic elastomers, rigid blocks act as physical vulcanization and the advantages of this process are evident. The chemical bonds that form the vulcanized structure of a standard rubber cannot be destroyed by heating and, at a sufficiently high temperature, the rubber simply begins to decompose.

On the other hand, in thermoplastic elastomers heat can actually melt the rigid domains; the material can then be melted and processed, but the rigid domains that recreate the pseudo-vulcanization are formed again simply by cooling the material. It is clear from the foregoing explanation that diblocks, which contain only one hard and one soft block, do not contribute to the elastic properties.

Diblocks can improve workability, but their quantity in the material must be contained within certain limits, so that they do not reduce the elasticity to an unacceptable value. Also, the total amount of hard blocks is important; a content that is too low will lead to poor elastic properties (analogous to an insufficiently vulcanized rubber), while a content that is too high will make the material behave as super-vulcanized rubber, very rigid, still with very low elasticity.

Among the block thermoplastic elastomeric copolymers, the so-called styrenic block copolymers (SBCs) are well known and widely used in many applications, thanks to their excellent properties. Styrenic block copolymers as a class are for example described in Thermoplastic Elastomers: A Comprehensive Review, Legge, Holder & Schroeder (Ed.), Hauser Publisher (1987), Chap. 3, 4 and 12 (1). They can have the structures already mentioned above, such as:

- multiblock A-B-A-B-A-B -... etc.

- linear triblock A-B-A

- radial or "star" polymers (AB) X, where x> 2. A represents a "rigid" block of a polymerized vinyl-arenic monomer, generally styrene or À-methyl styrene; and B represents a "soft intermediate block", generally formed from a rubbery monomer such as polybutadiene, polyisoprene, polyethylene-butylene or polyethylene-propylene.

The content of diblock molecules A-B in these materials can reach up to 80% by weight, and in special commercial products it can also form the whole of the polymer. The latter materials are used for particular applications since, for the reasons discussed above, they have no or very poor elasticity. The diblocks can aid workability and improve adhesive properties, but to maintain good elastic characteristics their content in the thermoplastic elastomeric block copolymer must be kept below 40% by weight.

SBCs are widely used as substitutes for vulcanized rubbers, being their hardness, modulus and general mechanical and elastic characteristics, strictly related to the content of rigid blocks, especially formed from polystyrene. They have also been used as base polymers for hot melt adhesives for their generally good mechanical characteristics, for the ease of developing adhesive properties in their rubbery intermediate blocks and for the good thermal stability which makes them superior to traditional hot melt bases such as ethylene-vinyl acetate copolymers. However, the main purpose of the standard compositions is to optimize the adhesive properties since the maintenance of at least some elastic properties, typical of the base polymer, is not sought.

Block elastomeric thermoplastic copolymers known as SBCs typically have the following characteristics:

- They consist of two types of monomers, each polymerized into blocks of the same monomer units, the blocks being distinct even if chemically bonded within the copolymer molecule. Furthermore, the two types of blocks must be mutually incompatible.

- The structure according to which the two types of blocks present are united in the molecule can be:

- alternating multi-block, such as ... A-B-A-B-A-B. ..

- linear triblock, such as A-B-A

- radial or star structure, such as (A-B) x, where x> 2.

- "A" represents blocks of a polymer obtained from a vinyl-arene monoromer, typically styrene or α-methyl-styrene. They are called rigid blocks because at room temperature these polymeric specirs are rigid, glassy and brittle materials, being below their glass transition temperature (Tg). Typically, constituents useful for rigid blocks have Tg well above room temperature and preferably above 90 ° C.

- "B" represents blocks of a rubbery polymer having a Tg <0 ° C and preferably <-40 ° C. Typically these "soft" blocks are formed from rubbers, such as polybutadiene and polyisoprene.

In the common technological lexicon, the block thermoplastic elastomeric copolymers thus formed are often indicated with the abbreviations SBS and SIS, respectively. As already indicated in terms of the mechanism of generation of elastic properties in these types of polymers, and particularly about the function of the rigid blocks in obtaining a physical polymerization of the polymer, useful SBCs contain at least two rigid "A" blocks per molecule and at least one soft block "B". The molecules formed by a block A and a block B (so-called diblocks) should, for use in the present invention, be kept below 40% by weight in the base polymer.

It is widely recognized in the literature that there are differences between SIS and SBS copolymers which are relevant in the formulation of hot melt adhesives. SBS copolymers generally cost less than similar SIS copolymers and SBS copolymers can be synthesized to exhibit better elasticity than similar SIS copolymers. However, it has not so far been possible to take advantage of these potentially advantageous properties of SBS copolymers, as a result of the fact that SBS copolymers generally do not have adequate adhesive properties and SIS copolymers are much more easily modifiable to develop good adhesive properties. For this reason, hot melt adhesives have generally been formulated using SIS copolymers as the predominant SBC. Both US-A-4418123 and EP-A-0424295, which have been described above, clearly prefer SIS as the SBC, upon which the compositions are based, and neither document describes an SBS-based composition which exhibits satisfactory properties.

It has been found according to the present invention that compositions in which the SBS copolymers constitute the main styrene block copolymer (s) can be produced with satisfactory adhesive properties while at the same time maintaining the typical advantages of SBS copolymers, as regards the elasticity as mentioned above. Therefore, compared to compositions based on other SBCs, according to the present invention it is possible to formulate compositions with better elastic properties, faster elastic recovery, flatter stress / strain diagrams, even with elongations> 1000% and obtain compositions that can be processed more easily {behavior more Newtorian rheological). However, it should be noted that a direct comparison between SIS and SBS-based compositions is very difficult, since the compositions have to be formulated by different processes. Consequently, it is generally not possible to simply replace an SBS copolymer with a SIS copolymer in a hot melt composition, achieving satisfactory properties and other modifications must be made to the formulation based on the nature of the SBC, in order to achieve optimal results. The way in which the compositions according to the present invention can be formulated, obtaining the desired properties, is described in more detail below.

Therefore, the compositions according to the present invention are based on SBS copolymers or a mixture of SBS / SIS, in which the SIS is present in an amount equal to or less than 50% by weight of the total copolymer.

All thermoplastic elastomers can be processed in the molten state using various technologies and various equipment, showing in any case properties similar to a vulcanized rubber in the solid state. Virtually all thermoplastic elastomers can be made adhesive. Some adhere sufficiently in the molten state to different substrates. However, it is clearly highly desirable to obtain thermoplastic elastomers which are capable of adhering at room or only moderately elevated temperatures to various substrates.

Therefore, while pure thermoplastic elastomers have a certain adhesiveness at elevated temperatures, this adhesiveness can be conveniently increased both in terms of the strength of the bonds formed with different substrates, and in terms of the temperature range at which resistant bonds are formed.

This improvement is achieved by using at least one suitable tackifier type resin. More particularly, much better adhesive properties and also self-adhesive properties at room temperature (pressure tack behavior) can be achieved by mixing thermoplastic elastomers with materials known as "tackifier" type resins, which, as a class, are well known in the literature.

When thermoplastic elastomers are used at room temperature (for example because it is desired to pre-extend them to the solid state and apply them under tension), they must exhibit the typical behavior of true pressure adhesives and this generally requires a blend of a thermoplastic elastomer to blocks and a "tackifier" type resin. It should be noted that, in order to improve the adhesive properties of the thermoplastic elastomer (both at high temperature and at room temperature), only the soft (rubbery) blocks of its molecule must be modified with the "tackifier" type resin. Therefore, only the interaction between the soft (rubbery) blocks and a resin, substantially compatible with them, causes the generation of adhesiveness; while the possible modification of the rigid blocks with a resin will never lead to the development of an adhesive behavior.

Not only do the rigid blocks have no adhesive activation, but their eventual modification with a "tackifier" resin could "soften" their mechanical strength. This risks damaging their ability to serve as "physical vulcanization centers" for the elastomer, resulting in the destruction of the elastic behavior.

Now, for the various thermoplastic block elastomers, depending on the chemical nature of their soft and rigid blocks, suitable "tackifier" type resins can be identified which must be compatible (i.e. soluble and capable of making the appropriate physical modification of the system ) only with soft or rubbery blocks, while compatibility with rigid blocks must be as low as possible or even zero, in order to maintain the primary elastic properties of the polymer as much as possible. However, the amount of tackifier type resin must be controlled, as the addition of too high amounts of tackifier type resin (or resins), even if the tackifier type resin is only compatible with blocks intermediate (soft blocks) and completely incompatible with rigid blocks, it could however damage the elastic properties of the obtained formulation. In any case, the addition of the resin constitutes a dilution of the concentration of the rigid block domains, weakening their ability to function as "physical crosslinking" centers for the elastomer. Therefore, both the content of the rigid domains in the base block thermoplastic elastomer, and the content of the elastomer in the final formulation, must be such as to ensure a sufficient final concentration of rigid domains in the formulation, to maintain an appropriate level of "physical vulcanization" "and, therefore, elastic properties.

Therefore, on the one hand, it is important to check the final concentration of the rigid blocks in the composition. On the other hand, the addition of a resin (or resins) compatible only with rigid blocks and their domains, is completely ineffective in developing and / or improving the adhesive properties. The resins compatible with the rigid blocks, by swelling the rigid domains, will make the composition rigid, increasing the modulus and (in comparison with similar quantities of tackifier type resins compatible with the intermediate block) will tend to increase the viscosity. In a system that already contains a tackifier type resin compatible with soft domains, adding resins compatible with hard domains will also decrease adhesiveness. Consequently, in general terms, only limited quantities of resins compatible with the "rigid blocks" can be used without damaging too much the general properties of the elastic hot melt adhesive. Generally, they will be used only in particular cases, for example if it is necessary, for some applications, a further increase of the module; or (using resins compatible with rigid blocks with a high softening point) if a higher solidification temperature or better temperature resistance is desired.

The compositions according to the invention can be used to elasticize the structures in which they are applied, without using any glue, for example structures in which the elasticization is conventionally obtained by means of a vulcanized rubber elastic. A single material (the hot melt elastic adhesive) can replace two materials in use (the rubber elastic and the glue to fix it) with a substantial cost saving. Normally rubber bands are covered with talc to prevent the bands from sticking to themselves in the package. Talc can generate problems in the adhesion phase with glues.

Furthermore, the elastic, thermoplastic, hot melt adhesive can be extruded into various geometric shapes directly during the construction of the product to be elasticized. They can be extruded as wires or strands, such as strips, films, etc. Structures such as strips or films can also be expanded prior to extrusion, resulting in particularly soft stretch structures. The elasticization can also be applied according to non-linear (curved) geometries, which makes the anatomical adaptability of the elasticized product to the user's body particularly good. This is very difficult to achieve with standard rubber bands. Under the different geometric shapes, the hot melt elastic adhesive can be applied in an already stretched or non stretched state. In the first case, the extrudate is cooled immediately after the extrusion die and stretched to the desired length. In this case it should have the following properties:

- a relatively high solidification point, so that it solidifies immediately after extrusion and can be stretched elastically. An elastic stretch can only be achieved with a solid material, as any force applied to a molten or semi-solid material will only cause a plastic stretch along the direction of the force, without any elastic tension.

- good pressure adhesion properties, as the hot melt adhesive elastic will come into contact with the substrate (or substrates) when it is already cold, for example at room temperature.

When the material is applied without any prior elastic stretching and directly in contact with the substrate (or substrates) to which it must adhere, at the exit of the extrusion die, the pressure adhesive behavior is less important, since the bond is achieved when the material is still above room temperature. In this case, in addition to the aforementioned geometric shapes, the material can be applied to the substrate (or substrates), for example by spraying, in the form of short fibers, a similar process, obtaining a network of short interconnected fibers, or a network of fibers having length indefinite which can have both a random and geometrically regular reticular structure (for example each fiber can form a spiral).

All these characteristics are particularly suitable for the elasticization of sanitary absorbent articles, although the potential of the materials according to the invention is clearly not limited to these applications. The use of materials applied in pre-stretched form can replace all rubber elastics currently used in diapers-panties for both children and adults, in sanitary pads, etc. when it is desired to have parts of the product already under elastic tension which offer, as a result of their extreme versatility, the possibility of new stretch structures of practically infinite varieties. In this case, another advantage of hot melt elastic adhesives over rubber bands is noteworthy. As will be described in more detail below, the preferred hot melt elastic compositions have a stress / strain pattern that is flatter than a rubber band; i.e. even if the material is already under tension, further stretching (for example due to the movements of the wearer of the absorbent article) causes a very small increase in modulus and tensile strength that is perceived by the wearer . This is especially true for low modulus compositions.

The compositions according to the invention which are most conveniently applied in the unstretched state are typically used to give elastic recovery to structures / products only when the whole final product / structure is subjected to some deformation during use. Normally in this case the typical deformations to which the absorbent article is subjected are very limited, for example of the order of 5-50%. Consequently, it is necessary that the hot melt elastic adhesive contained in these structures is able to respond with a sufficient elastic return force to external deformations, even to these small elongations. For these applications, it will generally be more convenient to use higher modulus formulations.

In summary, the use of block thermoplastic elastomers, in different physical forms and with different application processes, for the elasticization of structures, and in particular of hygienic articles, is very advantageous.

The compositions according to the present invention in the form of threads or strips and processes for their preparation, form the subject of an application filed by us on the same date, entitled "Adhesive composition, relative process and apparatus".

The compositions according to the present invention in the form of foams and processes for their preparation, form the subject of an application filed by us on the same date, entitled "Adhesive composition and relative preparation process".

The use of compositions according to the present invention in the elasticization of absorbent articles, such as nappies-panties and sanitary napkins, form the subject of an application filed by us on the same date, entitled "Absorbent article".

The formulations of the present invention exhibit optimal properties, typical of hot melt, ranging from compositions which can more conveniently be strongly bonded to substrates at elevated temperatures, between the melting point and about 50 ° C, to compositions which maintain a strong adhesiveness. permanent on many substrates even at room temperature, being authentic pressure adhesives. Furthermore, the compositions are characterized by the maintenance of excellent elastic properties deriving from the basic thermoplastic block copolymer, which exhibits all the typical behaviors that define an elastomeric material in the technological sense.

Then, when they are stretched to the solid state and when the stress is released, they will quickly return to their initial length, with only minimal permanent (plastic) deformation. Preferably, the formulations which have a distinct character of pressure adhesive, can also be applied at room temperature for elasticization, both in the non-stretched state and, preferably, in the stretched state, under different geometric shapes, in various articles, and in particular absorbent hygienic products such as diapers-panties for children and adults, or products for incontinent adults other than diapers-panties or feminine pads. The compositions having lower pressure adhesive characteristics will be more conveniently applied at temperatures above 50 ° C, in stretched or, more preferably, non-stretched form, for the elasticization of the same structures or products. In particular, when applied in the unstretched state, they will work under limited deformations, for example up to 50% (i.e. a final stretched length = 1.5 times the initial length).

In order to present a net elastic return force even at these low elongations, these formulations will generally have a higher modulus than the first, the two types of material being in fact the extremes of a field of formulations in which all are excellent hot melt adhesives and maintain excellent elastic properties, the transition from one to the other being gradual.

As already indicated, the compositions according to the invention can be divided into "low modulus" and "high modulus" formulations, this distinction being based on the value of their modulus and on their behavior as pressure adhesives.

Therefore, the present invention refers to a family of compositions based on at least one elastic block thermoplastic copolymer in which the SBS copolymers are the main polymer (or polymers) and at least one "tackifier" type resin, essentially compatible with soft blocks. (gummy) of the aforesaid copolymer, the tackifier type resin being mainly used to develop the adhesiveness, both at high temperature and at room temperature, of the aforesaid copolymer. The compositions are extrudable and in the solid state they maintain a net elastic behavior, typical of the elastomers from which they derive. As typical examples, and without any limitation, these compositions can be extruded and applied in the form of threads, strands, strips, continuous films, fiber grids both continuous and with finite length and in which the fibers have both a random orientation and a geometric conformation. regular, etc. As examples of application in the field of absorbent articles, they can be used for the elasticization around the legs of diapers-panties, as elastic at the waist of the same, for the elasticization of sanitary pads and incontinent adult products other than diapers-panties. , for the internal elasticization of structures of all the aforesaid products, to reinforce their absorbent cores under mechanical stress and to give them stretchability and elasticity, etc.

Generally a lower modulus indicates that adhesive materials have more aggressive adhesiveness, so low modulus formulations generally have a higher tackiness typical of pressure adhesives. They are able to form very strong bonds with many substrates by simple contact, even at room temperature or, in any case, below 50 ° C.

The relationships between hard and soft blocks in the case of a thermoplastic elastomeric copolymer are very important for determining the elastic behavior, and the mechanical and adhesive properties.

Generally, the higher the content of rigid blocks (which is conventionally referred to as "styrene content") and the higher the modulus, the more evident the elastic properties, the faster the springback after the release of the traction, but the lower the adhesiveness and above all the behavior as a pressure adhesive. All this is true, as long as the quantity of rigid blocks does not become so high as to form the continuous phase, whereby the material becomes rigid and no longer elastic.

Useful SBCs may contain 10 to 50% styrene by weight. However, when they are modified with a "tackifier" type resin, the behavior of the obtained composition will be clearly controlled, in terms of all the above properties, by the resulting styrene content, that is, from that of the rigid blocks in the composition; whereby the behavior is determined both by the amount of styrene in the base copolymer (or copolymers), and by the content of copolymer (or copolymers) in the final composition. Too low a quantity of block styrene in the final material will lead to poor '' elastic properties. Too high an amount increases the modulus and decreases adhesiveness in an unacceptable way. Increasing the final amount of styrene in the composition with increasing the content of copolymer (or copolymers) will excessively increase viscosity and decrease processability. Thus, both the amount of copolymer (or copolymers) in the composition and the styrene content must be chosen in order to optimize the final amount of styrene and therefore all the aforementioned properties. Optimal intervals will be indicated below.

If desired, the rubbery portion of the SBC can itself be vulcanized (in a manner analogous to the vulcanization of synthetic or natural rubbers) using suitable chemical or physical means, especially known vulcanization systems for synthetic rubber which are not activated. from the temperature. This will lead to an increase in the form in the final composition.

The tackifier resin is added mainly to improve the adhesive properties of the base copolymer (or copolymers), even up to the limit of the typical behavior of a pressure adhesive. Furthermore, it improves the workability of the thermoplastic elastomer, giving the composition both absolute lower viscosity values (compared to the pure block copolymer) and a rheological behavior which, with the indicated quantities of resin, is practically Newtonian, i.e. such that the viscosity depends only on the temperature and does not change with the applied stress, a property which is very advantageous for the ease of processing. It is known that SBCs which have several very interesting characteristics can be difficult to machine as a result of non-Newtonian melt behavior as pure materials. This means that they not only have a very high viscosity, but also that, under the influence of temperature alone, they seem not to melt even at very high temperatures, close to 200 ° C. They can also begin to thermally decompose, before presenting a distinct fluid state. To make them fluid and thus workable, it is necessary to heat them and apply a high mechanical stress. In any case, the workability of pure SBC is difficult, the viscosities are high and very dependent on the combination of temperature and stress applied.

The basic compositions of SBC and of "tackifier" type resin according to the present invention are able to give materials which, while maintaining very good elastic and adhesive properties, are also easily workable, since they have a relatively low viscosity and a rheological behavior. practically Newtonian (or acceptably similar to Newtonian). The latter property is measured as a constant temperature (180 ° C) change in viscosity by applying two shear stresses, 20 and 80 sec1. The ratio of these two viscosities is hereinafter referred to as the "Newtonian Index" (N.I.).

An ideal Newtonian fluid would have N.I. = 1, while a pure SBC can have, under the same conditions, a N.I. also> 6; that is, the viscosity variation, due only to the variation of the shear stress from 20 to 80 sec-1, is greater than 6 times, which can cause serious problems for the regularity and ease of processing. For easy workability it is necessary that the compositions have only limited variations in viscosity at constant temperature when the applied shear stress is varied.

More particularly, according to the present invention, it is preferred that the compositions exhibit a Newtonian or, almost Newtonian, rheological behavior referred to the molten material at 180 ° C, comparing the viscosities under a shear stress of 20 and 80 seconds. The preferred compositions do not exhibit viscosity variations greater than 50%, i.e. a viscosity ratio (N.I.) not exceeding 1.5.

It has been found that the most preferred compositions based on SBS, have a nearly ideal Newtonian behavior, with an N.I. not exceeding 1.05.

In order to sufficiently maintain the elastic properties of the base polymer, it is necessary that the tackifier type resin is compatible mainly and preferably essentially only with the rubbery soft blocks of the block copolymer and does not significantly interfere with the rigid blocks. This depends on both the chemical nature of the resin and its molecular weight. The compatibility of the resin with the rubber blocks and its incompatibility with the rigid blocks can be measured, for example, by determining the variation in Tg of the soft and rigid blocks resulting from the addition of resin. In particular, the incompatibility with rigid blocks is considered satisfactory if their Tg (originally at 100 ° C if formed from polystyrene) does not change by more than 15 ° C by adding 100 parts of resin to 100 parts of copolymer. The measurement of the two Tgs requires appropriate equipment. Consequently, both the experience of the formulators and the technical literature of the resin suppliers must be taken into account to determine which tackifier type resins are chemically compatible with the soft blocks and incompatible with the rigid blocks of SBC. As used herein, the expression "essentially compatible only with soft blocks" indicates that a "tackifier" type resin is compatible with soft copolymer blocks and is incompatible with hard blocks so that the Tg of the blocks rigid does not change significantly and, more preferably, does not decrease more than 15 ° C, by mixing 100 parts of tackifier resin with 100 parts of copolymer. Preferably, the Tg of the rigid blocks does not decrease at all.

More specifically, a suitable tackifier type resin will be selected from the following chemical groups, which have high compatibility with SBC's soft blocks and low or no compatibility with its hard blocks;

hydrocarbon resins

- aliphatic resins

- polyiterpene resins

- phenol-terpene resins

- C5 synthetic resins

- synthetic resins C5 / C9

- rosin and rosin esters

as well as their totally or partially hydrogenated derivatives. They can be used as pure resin or even in blends.

When more than one resin is used, the main tackifier resin system, defined as the fundamental resin / mixture of resins present in an amount of at least 50% of the total amount of resins, is characterized by having a point of softening between 85 and 150 ° C and, more preferably, between 100 and 140 ° C (all the softening points are measured with the well-known process called "Ring & Ball" (R & B)).

It is believed that the "tackifier" type resins which have a softening point of less than 85 ° C have a prevalent plasticizing effect which can in any case be important for the development of good adhesive and elastic properties, but which must be distinguished from "Tackifier" effect. This is due to the fact that in the processing of the elastic hot melt compositions according to the present invention a rapid solidification of the material after extrusion is desirable, especially for compositions that need to be stretched before application to the substrate, which it is clearly possible only with solid materials For this reason, it is desirable that the solidification point of these compositions is not less than 80 ° C and, more preferably, greater than or equal to 100 ° C.

The solidification point is most accurately determined using the technique known as dynamic-mechanical analysis under sinusoidal stress, which is well known in the science and technology of polymers and adhesives. According to this technique, the three main rheological parameters of the material are determined as a function of temperature:

- elastic or accumulation modulus Gf

- viscous modulus or dissipation modulus G ''

- the angle 8 (delta) and its tangent, this angle δ being the phase shift between G 'and G'.

G 'is greater than G' 'when the material is solid. When the material is fluid, G '' becomes greater than G '. Of course, G 'is greater at low temperatures and smaller at high temperatures. The crossing temperature between G 'and G' 'is taken as the real rheological solidification (or melting) point of the material.

For use according to the present invention, it is preferable that the crossing temperature for the composition is greater than or equal to 80 ° C and, more preferably, greater than or equal to 100 ° C.

The location of the cross point depends on many physical parameters of the hot melt. However, it has been found that the major influence is the softening point of the main tackifier resin and a secondary influence is the content and molecular weight of the copolymer. Therefore, the "tackifier" type resin should preferably have a softening point between 85 and 150 ° C and, more preferably, between 100 and 140 ° C, provided that in any case the total composition has a real rheological solidification temperature of at least 80 ° C and, more preferably, at least 100 ° C.

In addition to the block thermoplastic elastomeric copolymer and the main tackifier type resin, the compositions may contain other components which enhance specific properties. A more detailed description of the compositions and their main properties is given below.

For practical reasons and clarity of description, the following description will refer specifically to "low modulus" and "high modulus" compositions.

The low modulus compositions are elastic, extrudable, adhesive and based on at least one thermoplastic elastomeric copolymer in blocks, suitably modified with the addition of at least one "tackifier" type resin essentially compatible with its soft blocks. The polymer, or at least the polymer present in greater quantity, is a polystyrene / polybutadiene block copolymer. In this embodiment, the compositions according to the invention have a modulus of 0.5 MPa or less, essentially between 0.05 MPa and 0.5 MPa and, preferably, less than or equal to 0.3 MPa; the modulus is measured at 23 ° C at an elongation of 500% (six times the initial length of the sample), with an elongation rate of 500 mm / minute. Further, the compositions have viscosities at 180 ° C and under an 80 sec 1 shear stress of 120,000 centipoise (cps) or less and preferably 60,000 cps or less and more preferably 30,000 cps or less.

The low modulus compositions will typically contain between 10 and 80% by weight and more preferably between 15 and 50% by weight, of SBC, or a mixture of SBC having the following characteristics: - a molecular structure which can be multiblock, linear or radial (star), provided that it contains, per molecule, at least two rigid blocks formed by a vinyl arene polymer and preferably polystyrene or poly-a-methyl styrene, and at least one soft or rubbery block, the soft block of the SBC, or of the SBC present in a higher quantity, being polybutadiene. The diblock content in the SBC (s) must be kept below 40% by weight. - the aromatics content (conventionally referred to hereafter as "block styrene content") in the SBC (s) can vary between 10 and 50% by weight and, preferably, between 20 and 50% by weight.

However, in order to maintain significant elastic properties, both the amount of SBC in the final composition and its content of styrene blocks should be chosen so as to obtain a final content of block styrene in the composition between 3 and 17. % by weight and preferably between 6 and 15% by weight.

The composition also contains a "tackifier" type resin or a mixture of resins, essentially compatible with the soft blocks of SBC. The preferred resins belong to the chemical groups known as:

- hydrocarbon resins

- aliphatic resins

- polyiterpene resins

- phenol-terpene resins

- C5 synthetic resins

- synthetic resins C5 / C9

- rosin and rosin esters

as well as their totally or partially hydrogenated derivatives.

The tackifier resin or mixture of resins has (or has) an R & B softening point of between 85 and 150 ° C and preferably between 100 and 140 ° C. The amount of this resin or mixture of resins in the composition can be comprised between 20 and 90% by weight. However, in a preferred embodiment, the aforementioned resin or mixture of resins content is between 30 and 55% by weight, while the remainder is formed by additional components described below, which improve the elastic and / or adhesive properties. .

In any case, both the quantity and the softening points of the tackifier resin or mixture of resins, as well as that of the additional components described below, will be chosen so that the final composition has a real rheological solidification temperature ( measured as the crossing temperature of G 'and G'1), not lower than 80 ° C and preferably not lower than 100 ° C.

It has also been found that the adhesive and / or elastic and / or mechanical properties of the tackifier binary SBC / resin mixtures can be improved by using additional components.

The adhesive properties can be improved by adding limited quantities of high molecular weight rubbers, such as polyisoprene, polybutadiene, polyisobutylene, natural rubber, butyl rubber, Styrene / butadiene rubber (SBR) or styrene / isoprene rubber (SIR) and their mixtures. These polymers have a high viscosity and, in the uncured state, have poor elastic properties. However, by adding them in quantities up to 15% by weight of the formulation and using polymers with Mooney ML viscosity (1 + 4) at 100 ° C between 30 and 70, the obtained compositions exhibit improved pressure adhesive properties, while still maintaining viscosity. final within a useful range and without any detrimental effect of the final elastic properties. A particularly suitable SBR is the product sold by Enichem under the trade name EUROPRENE SOL 1205 and by Fina under the trade name FINAPRENE 1205. This product is described as an SBR in which styrene is partially distributed in blocks. Of the total styrene content, equal to 25% by weight, between 15 and 18% has a block structure, and the remainder is randomly copolymerized with butadiene.

Plasticization of the composition can have very good effects not only on adhesive properties and viscosity, but can also improve elastic behavior by reducing internal (molecular) friction which dissipates elastic energy during stretching and subsequent release. In general, the composition can contain up to 40% by weight of plasticizer (or plasticizers).

In a preferred embodiment, the compositions contain at least one of the following plasticizers:

- up to 40% by weight of a tackifier resin with a softening point between 50 and 85 ° C,

- up to 20% by weight, and preferably up to 15% by weight, of a liquid hydrocarbon resin, rosin ester or polytherpene resin with a softening point not exceeding 30 ° C,

- between 3 and 30% by weight, and preferably between 5 and 15% by weight, of a paraffinic or naffenic mineral oil, having an aromatic content lower than 10% by weight in order not to interfere with the styrene domains,

- up to 15% by weight of a liquid polyisoprene or depolymerized natural rubber or polyisobutylene, polybutenic or polypropylene oils and their liquid copolymers, for example PARAPOL (Exxon) or LIR (by KURARAY).

The quantity of plasticizer should be such that the solidification temperature is not lower than the limit mentioned above. In a preferred embodiment, the total plasticizer content in a low modulus formulation is not less than 10% by weight and not more than 40% by weight.

In low modulus compositions, it is generally undesirable to use aromatic resins, which have no effect on the adhesive properties, which interfere with the rigid blocks of SBC and which stiffen the composition and tend to increase the viscosity, and the preferred amount of aromatic resins is zero. However, limited amounts of an aromatic resin or a blend of aromatic resins, for example 20% by weight or less, more preferably 10% by weight or less, can be used as a reinforcement for compositions that have a low total content of styrene (i.e. up to 6%), or comprise significant amounts of SIS, for example 30% by weight or more, relative to the total SBC. In fact, SIS copolymers, especially those with an ironing content of less than 30% by weight, when diluted in the composition with resin and other additives, may exhibit an inadequate (too low) modulus and modest springback characteristics, as a result of both of the inherently low modulus of the SIS, and of the low concentration of styrene, which acts as a physical curing agent. In this case, the aromatic resin can increase the modulus to a useful value and increase the density of the rigid domains, which are swollen by the resin. The useful aromatic resins have a softening point between 115 and 160 ° C and are chemically identified as derivatives of styrene, α-methyl-styrene, vinyl toluene, coumaroneindene and their copolymers; alkyl-aryl resins, etc.

In addition to the above components, the compositions can contain the normal additives such as antioxidants, U.V. inhibitors, pigments and coloring products, mineral fillers, etc., generally in a total quantity up to 20% by weight.

Without wishing to limit the most suitable processing and use range, the low modulus formulations are typically used in the stretched state, at typical levels of extension between 400 and 1000%. They are characterized by a very high elongation at break (over 1100% and often over 1400%) and very good adhesiveness, often with pressure adhesive properties.

To simulate the application of the composition to an absorbent article, the pressure adhesive properties are measured as tack values ("Loop tack" or "Quick Stick Tack") and as a 90 ° peel value according to standard FINAT Test methods Method N ° 9 for the loop tack and FINAT Test Method N ° 2 for the 90 ° peel, modified as described below. - For both tests the compositions are applied on a polyester film with a grammage of 80 g / m2.

- The adhesive properties, both as a loop tack and as a 90 ° peel, are determined on a polyethylene film fixed on the standard plate.

- Loop tack values are determined as peak values, ignoring the initial peak.

- The 90 ° peel is evaluated after a compression with a 400g roller passed back and forth, i.e. with two passes, one in each direction, and the measurements are performed 20 minutes after the establishment of the contact between the adhesive and the polyethylene. The compositions according to the invention generally have a loop tack greater than 5 N / cm and a 90 ° peel greater than 7 N / cm (separation speed = 300 mm / min). Materials that can usefully be adhered and applied at room temperature in a hygienic product are considered to be those that have a loop tack greater than 2.5 N / cm on polyethylene and a 90 ° peel greater than 3 N / cm.

The high modulus formulations are elastic, adhesive, extrudable, similar to those described above, and have the following characteristics:

1) have a modulus greater than 0.5 MPa and more preferably not less than 1 MPa, and up to 10 MPa.

2) At 180 ° C and applying a shear stress of 80 sec'1, they have viscosities of 80,000 cps or less, preferably 50,000 cps or less and, more preferably, 35,000 cps or less.

3) They are based on the same types of SBCs indicated above, but have a final content of styrene blocks in the composition comprised between 15 and 30% by weight, and preferably between 15 and 25% by weight.

4) The SBC or SBC mixture that is used has a diblock content not higher than 25%, and preferably not higher than 10%. The most preferred polymers are those that do not contain diblocks, such as those marketed by DEXCO Co., under the trade name of VECTOR.

5) The preferred SBC contains between 20 and 50% by weight of styrene and the preferred amount of SBC or mixture of SBC in the composition is between 35 and 75% by weight, provided that it is the styrene content of the SBC that its quantity in the composition is such as to satisfy the requirement of point 3) above as the final quantity of styrene.

6) The resin or the mixture of "tackifier" resins has (or has) the same chemical and physical characteristics already discussed above. However, the preferred content is between 20 and 40% by weight.

7) The content of high molecular weight rubbers such as polyisoprene, polybutadiene, polyisobutylene, natural rubber, butyl rubber, SIR and SBR should not exceed 10% by weight, and preferably be less than 5% by weight, based on the total composition .

8) The total amount of plasticizers, as described above, should not exceed 25% by weight.

9) Aromatic resins or their mixtures should preferably be avoided due to their negative effect on adhesive properties and stress / strain correlation (steeper stress / strain diagrams; appearance of a yield point and consequently of permanent plastic deformation). However, as in the previous case, these materials can be present in the composition in quantities up to 20% by weight with acceptable properties, provided that the non-elastomeric / non-adhesive part of the composition does not exceed 50% by weight of the total composition. This non-adhesive / non-elastomeric part is formed by the sum of the total amount of styrene in the composition and the amount of resin / aromatic resins.

Other characteristics and other possible components and additives remain the same. In particular, it is still necessary that the real rheological solidification temperature (measured as the crossing point between G 'and G' ') is not lower than 80 ° C and, preferably, not lower than 100 ° C.

Still without wanting to limit the most suitable processing and use range, these high modulus compositions are often applied in the unstretched state, especially those having modulus greater than 1 MPa. This preferred use is due to the fact that they are able to give a sufficient spring back force, even with small deformations (typically not exceeding 50%) which often occur during the use of deformable hygienic articles which can, in this way , conveniently be made elastic and resilient. This is also partly due to the fact that the application of the composition in the stretched state implies the need to apply it at approximately room temperature, and so it needs to adhere firmly to the substrates even in these conditions (pressure adhesive properties). The pressure-sticking characteristics of adhesives tend to be inversely proportional to their elastic modulus.

However, some of the high modulus compositions according to the invention still maintain a clear and useful pressure adhesive behavior (loop tack on PE> 2.5 N / cm; 90 ° peel on PE> 3 N / cm), and they can also be applied at room temperature and in the stretched state, with typical elongation up to 400%, being the elongation at break of these compositions typically higher than 900%.

Adhesive properties are measured under the same conditions used for low modulus compositions.

The unexpected good level of elasticity of the compositions according to the invention can be measured as retention of the tensile strength after cyclic deformation. This is a test that simulates the conditions of use in a hygienic article, in which the movements of the wearer can cause further and subsequent elongation of the elasticized parts which, for optimal behavior, must return to their initial length with only modest decays. of the tensile strength. All the compositions are tested from an already stretched state and undergo a further elongation of about 15% of the initial stretched length, so as to simulate the movements of the user. The compositions are cyclically stretched and released 50 times from the initial stretch to the stretch obtained for further stretch.

The percentage retention of the tensile strength at an elongation equal to the initial one after 50 elongation cycles at a speed of 500 mm / minute, with respect to the initial tensile strength, is taken as a measure of the elasticity of the materials. The tests are carried out at room temperature, on 2.54 cm wide strips.

- The low modulus compositions are stretched to an initial elongation typical of the expected applications of 800% and then are again stretched cyclically and released for 50 times, between 800 and 920% (i.e. between 9 and 10.2 times the initial sample length).

- The high modulus compositions are tested with the same procedure, but with an initial elongation typical of the expected applications of 300%, under 50 elongation and release cycles, between 300 and 345%.

The term "retention of tensile strength after 50 cycles" as used herein refers to the above test. An elastic in vulcanized natural rubber produced by the company JPS Elastomerics that is used in the elasticization around the legs of nappies-panties and applied with an initial stretch of 220%, is taken as a reference and is cyclically deformed 50 times between 220 and 255%. It has been found that under these conditions the vulcanized natural rubber elastic, after 50 cycles, has an average retention of the tensile strength equal to 47% of the initial tensile strength at 220%. This retention level of tensile strength is considered indicative of good elastic behavior.

More generally, it has been observed that materials which do not lose more than 60% of their initial tensile strength under these test conditions exhibit good elastic behavior. Tensile strength retention of less than 40% represents unsatisfactory elasticity, as indicated by slow return to initial length after release of tension, high permanent plastic deformations, etc.

As it will be noted from the following examples, the compositions according to the invention, both with high and low modulus, exhibit a good elastic behavior, at the same level, or better, than a vulcanized natural rubber elastic.

More specifically, the high modulus compositions maintain up to 67.5% of their initial tensile strength and the low modulus compositions up to 59.8%.

The elastic properties are also evaluated with the following procedure: the compositions in the form of 2.54 cm wide strips are tested at 23 ° C and with an elongation rate of 1000 mm / minute, with 3 elastic hysteresis cycles between 0 and the typical elongation during use, i.e. 800% for low modulus compositions and 300% for high modulus ones. The elastic energy of each cycle, evaluated as the area of the cycle, is recorded and the ratio between the elastic energy of the third and the first cycle is determined as elastic energy retention after 3 hysteresis cycles. For good elastic behavior, it is believed that under these test conditions, an elastic energy retention of not less than 30% is required.

The invention is illustrated with the following examples which are not to be considered in any way limitative of the invention. In the case of commercial products, the details of their nature and composition are those provided by the manufacturer.

The compositions of all Examples 1 to 5, when applied in the molten state, between plastic and / or cellulosic materials in an amount corresponding to 5 g / m2, have a bond strength well above 0.5 N / cm, measured as peel at 90 °.

EXAMPLE 1

An SBC polymeric system based on SBS (styrene-butadiene-styrene block copolymer), is formulated as follows:

CARIFLEX TR-4113 S 36% by weight EUROPRENE SOL 1205 8%

DERCOLYTE A 115 45.8%

FORAL 85-E 6%

HERCOLYN D-E 4%

IRGANOX 1010 0.2%

in which:

- CARIFLEX TR-4113 S is an SBS copolymer diluted with oil, produced by SHELL Co, which contains:

68.5% by weight of a linear triblock SBS having a styrene content of 35% by weight and with a diblock content <20% by weight

31.5% by weight of a naphthenic mineral oil, which acts as a plasticizer, containing less than 5% aromatics.

- EUROPRENE SOL 1205 is a styrene / butadiene rubber (SBR) produced by ENICHEM. (You can also use the FINAPRENE 1205 product manufactured by FINA which is analogous). It is described as a solution polymerized SBR having a Mooney ML viscosity (1 + 4) at 100 ° C equal to 47 and a total styrene content of 25% by weight. This styrene is partially (typically between 15 and 18%) distributed in blocks, with the remainder being randomly copolymerized with butadiene. This randomly copolymerized styrene imparts the chemical structure of an amorphous SBR to the rubbery parts of the molecule, which contributes to the development of particularly good pressure-sticking characteristics.

- DERCOLYTE A 115 (the main tackifier type resin) is produced by DRT. It is a polyterpene resin derived from α-pinene, having a softening point of 115 ° C.

- FORAL 85-E is a "tackifier" resin composed of a hydrogenated glyceric ester of rosin, produced by HERCULES Co .. It has a softening point of 85 ° C.

- HERCOLYN D-E is a liquid methyl ester of rosin produced by Hercules.

- IRGANOX 1010 is a phenolic antioxidant, produced by CIBA-GEIGY.

The composition was found to exhibit the following properties:

- total content of styrene = 10.6% by weight, of which 10.1% in blocks.

- viscosity at 180 ° C at 80 sec <-1> = 20.520 cps

- modulus at 500% elongation = 0.182 MPa {low modulus)

- elongation at break> 1400% (1400% is the maximum measurable elongation with the equipment used for this determination)

- rheological solidification temperature (crossing point between G 'and G <1>') = 125 ° C.

- loop tack on PE = 8.5 N / cm

- 90 ° peel on PE = 16.3 N / cm

- retention of tensile strength after 50 cycles between 800% and 920% = 59.8%

- retention of elastic energy after 3 hysteresis cycles between 0 and 800% = 57.7%

- Newtonian index (N.I.) = 1.05.

The composition has extremely good elastic and adhesive properties and is considered completely suitable for the elasticization of structures, in particular absorbent hygienic articles. It is easily workable, that is extrudable, has a rapid solidification (ironable in line) and good characteristics as a pressure adhesive, which allow the formation of strong bonds by simple contact with many substrates, even at room temperature. EXAMPLE 2

The formulation is:

CARIFLEX TR-4113 S 38.8% by weight

FINAPRENE 1205 8.9%

DERCOLYTE A 115 26%

FORAL 85-E 26%

IRGANOX 1010 0.3

The following properties are measured:

- total content of styrene = 11.5% by weight, of which 10.9% in blocks.

- viscosity at 180 ° C at 80 sec <1> = 28.180 cps

- modulus at 500% elongation = 0.188 MPa (low modulus)

- elongation at break> 1400%

- rheological solidification temperature = 120 ° C.

- loop tack on PE = 8.6 N / cm

- 90 ° peel on PE = 10.4 N / cm

- retention of tensile strength after 50 cycles between 800 and 920% = 59.1%

- retention of elastic energy after 3 hysteresis cycles between 0 and 800% = 48.3%

- Newtonian index (N.I.) = 1.01.

The composition is similar to that of Example 1, the main variation consisting in the fact that about 50% of the high softening point "tackifier" resin is replaced with a low softening point resin and the only plasticizer is the oil contained in CARIFLEX TR-4113 S (12.2% by weight of the composition). Nevertheless it has been found that the composition still maintains a very high solidification temperature, fast solidification, as well as excellent elastic properties and pressure adhesiveness and excellent workability, whereby it is possible to extrude it easily and immediately stretch it even by 800%, in the form of very thin threads (diameter = 0.4 mm) which can be applied for the lateral elasticization of an absorbent product.

EXAMPLE 3

A different system is tested, based on radial SBS, more precisely a mixture of an SBS with a relatively low hard block content and a SBS with a relatively high hard block content. The wording is as follows:

FINAPRENE 415 17.7% by weight

FINAPRENE 401 7.0%

FINAPRENE 1205 8.0%

ZONATAC 115 LITE 45.8%

FORAL 85-E 6.3%

HERCOLYN D-E 4.0%

SHELLFLEX 4510 FC 11.0%

IRGANOX 1010 0.2%

in which:

- FINAPRENE 415 and FINAPRENE 401 are radial SBS copolymers, produced by FINA. Both are believed to contain less than 20% diblock and have a "star" structure of four SB blocks chemically bonded at a central point by the butadiene blocks. FINAPRENE 415 contains 40% by weight of block styrene blocks and FINAPRENE 401 contains 22% block styrene.

- ZONATAC 115 LITE is a hydrocarbon modified "tackifier" type terpene resin with a softening point of 115 ° C, manufactured by Arizona Co. It is believed to be based on styrene modified limonene.

- SHELLFLEX 4510 FC is a naphthenic mineral oil, produced by SHELL, which is believed to have an aromatics content <5%.

The following properties were measured:

- total content of styrene = 10.6% by weight, of which 10.1% in blocks.

- viscosity at 180 ° C at 80 sec <-1> = 12.810 cps

- modulus at 500% elongation = 0.223 MPa (low modulus)

- elongation at break> 1300%

- rheological solidification temperature = 107 ° C.

- loop tack on PE = 6.4 N / cm

- 90 ° peel on PE = 14 N / cm

- retention of tensile strength after 50 cycles between 800 and 920% = 50%

- retention of elastic energy after 3 hysteresis cycles between 0 and 800% = 44.9%

- Newtonian index (N.I.) = 1.04.

The composition has excellent properties typical of an extrudable, elastic, and easily workable adhesive material.

EXAMPLE 4

A high modulus composition is prepared, according to the following formulation:

VECTOR 4461-D 44.8% by weight ZONAREZ 7115 LITE 37%

FORAL 85-E 5%

ZONAREZ ALPHA 25 3%

PRIMOL 352 10%

IRGANOX 1010 0.2%

m which:

- VECTOR 4461-D is a linear SBS copolymer containing 43% by weight of styrene and not containing diblocks, manufactured by DEXCO Co.

- ZONAREZ 7115 LITE is a polyterpenic "tackifier" type resin, having a softening point of 115 ° C, derived from limonene, produced by ARIZONA Co. - ZONAREZ ALPHA 25 is a liquid "tackifier" type resin (softening point = 25 ° C), derived from α-pinene, with a very good plasticizing effect. It is produced by ARIZONA Co.

- PRIMOL 352 is a plasticising paraffinic mineral oil, which is believed to contain no aromatics. It is manufactured by Exxon Company.

The following characteristics are measured: - total content of block styrene = 19.3%

- viscosity at 180 ° C at 80 sec <1> = 16,810 cps

- modulus at 500% elongation = 1.07 MPa (high modulus)

- elongation at break = 987%

- rheological solidification temperature = 111 ° C. - loop tack on PE = 4.3 N / cm

- 90 ° peel on PE = 6.5 N / cm

- retention of tensile strength after 50 cycles between 300 and 345% = 67.5%

- retention of elastic energy after 3 hysteresis cycles between 0 and 300% = 63.3%

- Newtonian index (N.I.) = 1.05.

The composition is a good elastic material, especially useful with low elongations. It has acceptable characteristics of semi-adhesive pressure, so as to bond to materials even at room temperature in the stretched state.

EXAMPLE 5

The formulation is:

VECTOR 4461-D 54, 8% by weight

ECR 368 35%

PRIMOL 352 10%

IRGANOX 1010 0.2%

in which:

- ECR 368 is a hydrogenated hydrocarbon tackifier resin produced by EXXON with a softening point of 100 ° C.

The following properties were measured:

- total content of block styrene = 23.56%

- viscosity at 180 ° C at 80 sec '<1> = 34,000 cps

- modulus at 500% elongation = 1.61 MPa (high modulus)

- elongation at break = 947%

- rheological solidification temperature = 114 ° C.

- loop tack on PE = 1.3 N / cm

- 90 ° peel on PE = 2.6 N / cm

- retention of tensile strength after 50 cycles between 300 and 345% = 62.3%

- retention of elastic energy after 3 hysteresis cycles between 0 and 300% = 38.3%

- Newtonian index (N.I.) = 1.05.

The composition was formulated to maximize modulus while still maintaining acceptable elasticity and good adhesiveness at temperatures above room temperature. This material is most conveniently applied in the unstretched state and bonded directly at a temperature> 50 ° C. It gives good springback forces even at very low elongations, for example the modulus at 20% elongation is 0.236 MPa. However, it also performs well in the stretched state, for example at an elongation of 300%, and has adhesive properties on PE that are not negligible even at room temperature. COMPARATIVE EXAMPLE A

The wording is

KRATON DI 107 40.2% by weight WINGTACK 95 32.9%

CI-145 26.5%

WESTON 618 0.2%

IRGANOX 1010 0.2%

in which:

- KRATON DI107 is a linear SIS block copolymer produced by SHELL, containing 14% by weight of styrene.

- WINGTACK 95 is a synthetic polytherpene resin, with a softening point of 95 ° C, produced by Goodyear Co.

- IC-145 is a coumarone-indene aromatic resin, with a softening point of 145 ° C, produced by the German company VFT.

- WESTON 618 is a phosphite based antioxidant, manufactured by Borg Warner Co.

- IRGANOX 1010 is as described in Example 1.

This formulation is prepared according to the teachings of US-A-4418 123 (Example IV). According to the US patent, the composition would exhibit completely favorable elastic, adhesive and processing properties. The formulation of Comparative Example A has the following differences with respect to Example IV of US-A-4418 123:

1) CUMAR LX-509 coumarone-indene resin is not readily available in Europe, and therefore the corresponding IC-145 resin was used. The resins are chemically similar, but IC-145 has a softening point of 145 ° C compared to the 155 ° C indicated for CUMAR LX-509 in the US Patent;

2) For practical reasons, the pigment (1.5% titanium dioxide) has been omitted. The pigment is presumably present in the original formulation to hide the slightly brown color and is assumed to have a negligible effect on the adhesive and elastic properties.

The main properties can be summarized as follows:

- total content of block styrene = 5.6% by weight

- viscosity at 180 ° C at 80 sec <'1> = 192,000 cps

- modulus at 500% elongation = 0.365 MPa (low modulus)

- elongation at break> 1400% (1400% is the maximum measurable elongation with the equipment used for this determination)

- rheological solidification temperature (crossing point between G 'and G' <1>) = 145 ° C.

- loop tack on PE = 5.3 N / cm

- 90 ° peel on PE = 15.7 N / cm

- retention of tensile strength after 50 cycles between 800 and 920% = 34.3%

- retention of elastic energy after 3 hysteresis cycles between 0 and 800% = 19.8%

- Newtonian index (N.I.) = 2.03.

The above formulation has been found to have good pressure adhesive characteristics as indicated by the U.S. Patent, and that as measured on PE under the above conditions, the loop tack is 5.3 N / cm and the 90 ° peel is of 15.7 N / cm. However, it has also been found that both the elastic and workability properties for an extrudable product are unsatisfactory. In particular:

- Machinability, especially application in thin strips or threads, is very difficult due to the extremely high viscosity and highly non-Newtonian rheological behavior.

- It has been found that the modulus at elongation of 500% is 0.365 MPa and the elongation at break greater than 1400%. However, the elastic properties are unsatisfactory. In particular, with the cyclic deformation test between 800 and 920%, the formulation loses 65.7% of its initial tensile strength after 50 cycles and loses 80.2% of its elastic energy after 3 cycles of hysteresis between 0 and 800%, making it unsuitable for the elasticization of products, such as sanitary absorbent articles, which are deformed many times during use with repeated stretching due to the movements of the user. It is noteworthy that 45% of the loss of tensile strength occurs between the first and second cycle, confirming an easy and permanent plastic deformation.

COMPARATIVE EXAMPLE B

The formulation is:

TUFPRENE A 30.0% by weight

ESCOREZ CR 368 55.0%

CATENEX P941 10.0%

KRISTALEX FI 00 5.0%

with the addition of 0.2 parts per 100 parts by weight of the aforementioned composition of the antioxidant IRGANOX 1010,

in which:

- TUFPRENE A is a linear SBS copolymer, produced by Asahi Chemical Co. and containing 40% by weight of styrene. The diblock content is not specified by the manufacturer.

- ESCOREZ CR 368 is a hydrogenated modified hydrocarbon resin produced by Exxon with a softening point of 100 ° C.

- CATENEX P941 is a paraffinic mineral oil produced by Shell which is supposed to have an aromatics content of less than 5% by weight.

- KRISTALEX F100 is an aromatic resin based on À-methyl styrene and styrene, produced by Hercules and with a softening point of 100 ° C.

This formulation is prepared according to the teachings of EP-A-0424295 (Example V). The formulation of Comparative Example B has the following differences compared to Example V of EP-A-0424295:

0.2 parts of the antioxidant IRGA-NOX 1010 are added, per 100 parts by weight of the composition, as indicated in Example V of EP-A-0424295. As is obvious to those skilled in the art, the attempt to prepare and process the composition exactly as described in EP-A-0424295, i.e. without an antioxidant, would certainly have led to thermal degradation of the system. To follow the teachings of EP-A-0424295 as exactly as possible, the antioxidant used in Comparative Example A of this document is used. However, the antioxidant is added in the normal amount of 0.2% (since this is also the amount used in the previous examples according to the invention), rather than the unusual (and even unnecessary) high amounts used in Comparative Example A by EP-A-0424295.

The main properties can be summarized as follows:

- total block styrene = 12% by weight

- viscosity at 180 ° C at 80 sec '<1> = 5.620 cps

- modulus at 500% elongation = 0.204 MPa (low modulus)

- elongation at break> 1300%

- rheological solidification temperature (crossing point between G 'and G' ') = 106 ° C.

- loop tack on PE = 0.7 N / cm

- 90 ° peel on PE = 0.8 N / cm

- retention of tensile strength after 50 cycles between 800 and 920% = 21.3%

- retention of elastic energy after 3 hysteresis cycles between 0 and 800% = 25.0%

- Newtonian index (N.I.) = 1.16.

It has been found that processability, as indicated by viscosity and NI, is acceptable, although NI is high for an SBS-based composition. However, the formulation has modest pressure adhesive characteristics and the values of 0.7 N / cm for the loop tack and 0.8 N / cm for the 90 ° peel, demonstrate that it is practically unusable as a low elastic adhesive. form, if you intend to apply it in the ironed state in the preparation of absorbent sanitary articles. The elastic properties are unsatisfactory, as indicated by the loss of approximately 80% of the tensile strength of the composition after 50 successive stretching cycles and 75% of its elastic energy after 3 cycles of hysteresis.

The unsatisfactory properties of the composition can be related to the diblock content of TUFPRENE A. This is not indicated by the manufacturer and measuring it directly is difficult. However, the manufacturer's value for permanent plastic deformation measured by the ASTM D412 method is 47%. This is to be compared to the much lower values, around 10% or less, indicated for SBS copolymers with a diblock content lower than 20% by weight. On the other hand, the technical literature of SHELL reports the following values for the permanent plastic deformation for copolymers with a high diblock content

- KRATON D-1112 (SIS containing 40% by weight of diblock) = 20%

- KRATON D-1118X (SBS containing 80% diblock by weight) = 40%.

From this it can be deduced that TUFPRENE A probably has a diblock content well above 40%.

It should be noted that the above results seem discordant with the results reported in EP-A-0424295 at least in some respects. Thus, the aforementioned 90 ° peel of 0.8 N / cm must be compared with the 3.7 N / cm for the 180 ° peel reported by EP-A-0424295. This can be explained at least in part by both the different peel angle and the compression used in the test (400g versus 2kg), since the composition is stiff and the bond is greatly affected by compression. It should also be noted that the applied adhesive weight per square meter is not specified in EP-A-0424295, and this is extremely important in determining the bond strength. The test methods used according to the present invention lead to a realistic measurement of the compliance of the compositions for use in post applications. The modest properties of the composition of EP-A-0424295 can also be related to the combination of a rigid SBS (40% styrene) with an aromatic resin and with low quantities of plasticizer (10%).

EXAMPLE 6

This example refers to the stress / strain diagrams of the compositions of Examples 1 to 5 and Comparative Examples A and B. The hot melt elastic compositions according to the invention should desirably have a much flatter stress / strain diagram than rubber bands. that is, even if already under tension further stretching (for example due to the movements of the wearer of the absorbent article) causes only a very small increase in modulus and tensile strength perceived by the wearer. This is especially true for low modulus compositions and can be highlighted by measuring the mean modulus increase for a given range. Low modulus compositions, which are typically applied in an already stretched state, are evaluated as the mean modulus increase for every 100% increase in elongation between 0 and 800% (9 times the initial length), i.e. the total increase of the module divided by 8.

Referring to the low modulus compositions mentioned in the previous Examples, the results are as follows:

EXAMPLE N. AVERAGE INCREASE OF THE MODULE FOR A 100% ELONGATION 1 0.044 MPa / 100% elongation 2 0.045 MPa / 100% elongation 3 0.063 MPa / 100% elongation Comparative example A 0.099 MPa / 100% elongation Comparative example B 0.079 MPa / 100 % elongation The high modulus compositions of Examples 4 and 5, which are generally used in the unstretched state or in any case with a lower elongation, are evaluated as an average modulus increase for a 100% increase in elongation between 0 and 300 % of final elongation:

EXAMPLE N AVERAGE INCREASE OF THE MODULE FOR A 100% ELONGATION 4 0.169 MPa / 100% elongation 5 0.284 MPa / 100% elongation As a comparison, an elastic in vulcanized natural rubber, used for the elasticization around the legs of cloth if applied with a much lower elongation (typically 220%) it shows, between 0 and 220%, an average increase in the modulus of 0.89 MPa for an elongation of 100%.

It is possible to compare the behavior of a natural rubber elastic and of a low modulus composition according to the invention.

In the case of the rubber elastic, even limited movements of the wearer that cause, for example, a stretching of the elastic parts with a further elongation of only 10%, will cause an average increase in the modulus of about 0.09 MPa . Using a low modulus composition, the increase in modulus will be approximately 20 times less and several times less even with the strongest high modulus compositions, so that the movements of the wearer of an absorbent stretch article with the compositions described in the present invention , they are much freer. Consequently, in these applications the low modulus and small changes in modulus with elongation are clearly an advantage.

Claims (71)

CLAIMS 1. Hot melt elastomeric adhesive composition comprising at least one thermoplastic elastomer and at least one "tackifier" type resin, the thermoplastic elastomer (s) being a styrene / butadiene / styrene (SBS) copolymer or a styrene / butadiene / styrene with styrene / isoprene / styrene (SIS), in which SIS is present in an amount equal to or less than 50% by weight of the total block copolymer, the composition being characterized in that: a) is able to bind, when applied in the molten state, to plastic and / or cellulosic materials, with a peel force at 90 ° of not less than 0.5 N / cm (as defined here); b) has a retention of tensile strength after 50 cycles (as defined here) of at least 40%; c) has a viscosity of 120,000 cps or less at 180 ° C and under an applied shear stress of 80 sec'1. 2. Composition according to claim 1, which is a low modulus composition, having a modulus of 0.5 MPa or less at an elongation of 500% at 23 ° C, with an elongation rate of 500 mm / minute. 3. Composition according to claim 2, which has a modulus of between 0.05 and 0.3 MPa. 4. A composition according to claim 2 or 3, which has a viscosity of 60,000 cps or less. 5. A composition according to claim 4, which has a viscosity of 30,000 cps or less. 6. A composition according to claim 1, which is a high modulus composition, having a modulus greater than 0.5 MPa at an elongation of 500% measured at 23 ° C, with an elongation rate of 500 mm / minute. 7. Composition according to claim 6, which has a modulus of between 1 and 10 MPa. 8. A composition according to claim 6 or 7, which has a viscosity of 80,000 cps or less. 9. A composition according to claim 8 which has a viscosity of 35,000 cps or less. Composition according to any one of claims 1 to 9, which has a loop tack greater than 2.5 N / cm and a 90 ° peel greater than 3 N / cm (separation speed 300 mm / min) (both values were measured as defined here). 11. A composition according to claim 10, which has a loop tack greater than .5 N / cm and a 90 ° peel greater than 7 N / cm (both values were measured as defined herein). Composition according to any one of claims 1 to 11, which has a retention of the tensile strength after 50 cycles of at least 50%. 13. Composition according to claim 12, which has a retention of the tensile strength after 50 cycles of at least 60%. A composition according to any one of claims 1 to 13, which has an actual rheological solidification temperature (as defined herein) of 80 ° C or more. 15. A composition according to claim 14, which has an actual rheological solidification temperature of 100 ° C or more. A composition according to any one of claims 1 to 15, which has a Newtonian index (as defined herein) of 1.5 or less. 17. A composition according to claim 16, which has a Newtonian index of 1.05 or less. Composition according to any one of claims 1 to 17, wherein the tackifier-type resin (or resins) are essentially compatible only with the soft blocks of the styrene block copolymer. 19. Composition according to any one of claims 1 to 18, wherein the "tackifier" type resin (or resins) are selected from: hydrocarbon resins; aliphatic resins; polyiterpene resins; phenol-terpene resins; synthetic resins C5; synthetic resins C5 / C9; rosin and rosin esters; and their totally or partially hydrogenated derivatives. Composition according to any one of claims 1 to 19, wherein the tackifier-type resin (or resins) have a softening point between 85 and 150 ° C (R & B). 21. Composition according to any one of claims 1 to 20, which contains up to 40% by weight of plasticizer (or plasticizers). 22. Composition according to claim 21, wherein the plasticizer is selected from: - "tackifier" type resins with a softening point between 50 and 85 ° C; - liquid hydrocarbon resins, rosin esters and polyiterpene resins, with softening points not exceeding 30 ° C; - paraffinic or naphthenic mineral oils, with an aromatic content lower than 10% by weight; - liquid polyisoprene, depolymerized natural gums, polyisobutylene oils, polybutetic or polypropylene oils and their liquid copolymers. 23. Hot melt adhesive elastomeric composition comprising: 1) between 10 and 80% by weight of at least one styrene block copolymer, comprising at least two styrene end blocks and at least one rubbery intermediate block per molecule, the styrene block copolymer being a styrene / butadiene / styrene copolymer (SBS ) or a mixture of styrene / butadiene / styrene with styrene / isoprene / styrene (SIS), in which SIS is present in an amount equal to or less than 50% by weight of the total block copolymer, and containing less than 40% by weight of the total block copolymer of a block copolymer containing only one styrene block and one rubber block per molecule (diblock); 2) between 20 and 90% of at least one "tackifier" type resin essentially compatible only with the intermediate rubber blocks; 3) between 0 and 40% of plasticizer or plasticizers, -4) between 0 and 20% of an aromatic resin; the composition being further characterized by the fact that: a) is capable of binding when applied in the molten state to plastic and / or cellulosic materials, with a 90 ° peel of not less than 0.5 N / cm (as defined here); b) has a retention of tensile strength after 50 cycles (as defined here) of at least 40%; c) has a viscosity of 120,000 cps or less at 180 ° C under an applied shear stress of 80 sec <-1>. 24. Composition according to claim 23, wherein the block styrene copolymer (or copolymers) contains between 10 and 50% by weight of block styrene. 25. Composition according to claim 23 or 24, wherein the "tackifier" type resin (or resins) are selected from: hydrocarbon resins; aliphatic resins; polyiterpene resins; phenol-terpene resins; synthetic resins C5; synthetic resins C5 / C9; rosin and rosin esters; and their totally or partially hydrogenated derivatives. Composition according to any one of claims 23 to 25, wherein the tackifier-type resin (or resins) have a softening point between 85 and 150 ° C (R & B). 27. Composition according to any one of claims 23 to 26, which has a loop tack greater than 2.5 N / cm and a 90 ° peel greater than 3 N / cm (separation speed 300 mm / min) (both measured values as defined here). 28. A composition according to claim 27, which has a loop tack greater than 5 N / cm and a 90 ° peel greater than 7 N / cm (both values measured as defined herein). 29. A composition according to any one of claims 23 to 28, which has an actual rheological solidification temperature (as defined herein) of 80 ° C or more. 30. A composition according to claim 29, which has an actual rheological solidification temperature of 100 ° C or more. 31. A composition according to any one of claims 23 to 30, having a Newtonian index (as defined herein) of 1.5 or less. 32. A composition according to claim 31, having a Newtonian index of 1.05 or less. 33. Composition according to any one of claims 23 to 32, which is a low modulus composition, having a modulus at 23 ° C and an elongation of 500% and under an elongation rate of 500 mm / minute, ranging from 0 , 05 and 0.5 MPa. 34. A composition according to claim 33 which has a viscosity of 60,000 cps or less. 35. A composition according to claim 34 which has a viscosity of 30,000 cps or less. Composition according to any one of claims 33 to 35, containing between 15 and 50% by weight of a styrene block copolymer (or copolymers). A composition according to any one of claims 33 to 36, wherein the styrene block copolymer (s) is styrene / butadiene / styrene. 38. Composition according to any one of claims 33 to 37, wherein the block styrene content of the block styrene copolymer is between 20 and 50% by weight. 39. Composition according to claim 38, wherein the content of block styrene is comprised between 20 and 50% by weight. Composition according to any one of claims 33 to 39, wherein the final block styrene content of the composition is between 3 and 17% by weight. 41. Composition according to claim 40, wherein the final block styrene content of the composition is between 6 and 15% by weight. 42. Composition according to any one of claims 33 to 41, wherein the tackifier-type resin (or resins) has an R & B softening point of between 100 and 140 ° C. 43. Composition according to claim 42, wherein the content of resin (or resins) of the "tackifier" type is comprised between 20 and 90% by weight. 44. Composition according to claim 43, wherein the content of resin (or resins) of the "tackifier" type is comprised between 30 and 55% by weight. 45. Composition according to any one of claims 33 to 44, wherein the composition comprises up to 15% by weight of a high molecular weight rubber, having a Mooney viscosity ML (1 + 4) at 100 ° C ranging from 30 to 70. 46. A composition according to claim 45, wherein the high molecular weight rubber is a polyisoprene, a polybutadiene, a polyisobutylene, a natural rubber, a butyl rubber, a styrene / butadiene rubber, a styrene / isoprene rubber or a mixture of two or more of these. 47. Composition according to claim 45 or 4 6, wherein the high molecular weight rubber is a styrene / butadiene rubber, wherein the styrene is partially distributed in blocks. 48. Composition according to any one of claims 33 to 47, wherein the composition comprises at least one of the following plasticizers: - up to 40% by weight of a tackifier resin with a softening point between 50 and 85 ° C, - up to 20% by weight, and preferably up to 15% by weight, of a liquid hydrocarbon resin, rosin ester or polytherpene resin, with a softening point not exceeding 30 ° C, - between 3 and 30% by weight, and preferably between 5 and 15% by weight, of a paraffinic or naphthenic mineral oil, having an aromatics content lower than 10% by weight, - up to 15% by weight of a liquid polyisoprene or a depolymerized natural rubber or polyisobutylene, polybutylene or polypropylene oils and their liquid copolymers. 49. Composition according to claim 48, wherein the total plasticizer content is not less than 10% by weight. Composition according to any one of claims 33 to 49, wherein the amount of aromatic resin is less than 20%. 51. Composition according to claim 50, wherein the amount of aromatic resin is less than 10%. 52. Composition according to claim 51, wherein the amount of aromatic resin is zero. 53. Composition according to any one of claims 33 to 52, which comprises up to 20% by weight of antioxidants, U.V. inhibitors, pigments, coloring products and mineral fillers. 54. Composition according to any one of claims 23 to 32, which is a high modulus composition, having a modulus greater than 0.5 MPa at 23 ° C and at an elongation of 500% and below a velomine of 10% by weight , - up to 15% by weight of a liquid polyisoprene or a depolymerized natural rubber or polyisobutylene, polybutene or polypropylene oils and their liquid co-polymers. 72. Composition according to claim 71, wherein the total plasticizer content is not more than 25% by weight. 73. Composition according to any one of claims 54 to 72, wherein the amount of aromatic resin is zero. 74. Composition according to any one of claims 54 to 73, which comprises up to 20% by weight of antioxidants, U.V. inhibitors, pigments, coloring products and mineral fillers. 75. Composition according to any one of claims 54 to 74, wherein the non-adhesive / non-elastomeric part of the composition (as defined herein) does not exceed 50% by weight of the total composition. elongation rate of 500 mm / minute. 55. Composition according to claim 54, having a modulus of between 1 and 10 MPa. 56. A composition according to claim 54 or 55, wherein the composition has a viscosity of 80,000 cps or less at 180 ° C. 57. A composition according to claim 56, wherein the composition has a viscosity of 50,000 cps or less at 180 ° C. 58. Composition according to any one of claims 54 to 57, containing between 35 and 75% by weight of block styrene copolymer (or copolymers). 59. Composition according to any one of claims 54 to 58, wherein the final block styrene content of the composition is between 15 and 30% by weight. 60. Composition according to claim 59, wherein the final block styrene content of the composition is between 15 and 25% by weight. 61. Composition according to any one of claims 54 to 60, wherein the styrene block copolymer (s) is styrene / butadiene / styrene. 62. Composition according to any one of claims 54 to 61, wherein the block styrene copolymer has a diblock content not exceeding 25% by weight. 63. A composition according to claim 62, wherein the block styrene copolymer has a diblock content which does not exceed 10% by weight. 64. A composition according to claim 63, wherein the block styrene copolymer has a diblock content of zero. 65. Composition according to any one of claims 54 to 64, wherein the block styrene copolymer contains between 20 and 50% by weight of styrene. 66. Composition according to any one of claims 54 to 65, wherein the tackifier resin content is between 20 and 40% by weight. 67. Composition according to any one of claims 54 to 66, wherein the composition comprises up to 10% by weight of a high molecular weight rubber, having a Mooney viscosity ML (1 + 4) at 100 ° C ranging from 30 to 70. 68. Composition according to claim 67, wherein the composition comprises up to 5% by weight of a high molecular weight rubber, having a Mooney ML viscosity (1 + 4) at 100 ° C comprised between 30 and 70. 69. Composition according to claim 67 or 68, wherein the high molecular weight rubber is a polyisoprene, a polybutadiene, a polyisobutylene, a natural rubber, a butyl rubber, a styrene / butadiene rubber, a styrene / isoprene rubber, or a mixture of two or more of these. 70. Composition according to any one of claims 67 to 69, wherein the high molecular weight rubber is a styrene / butadiene rubber, wherein 10 styrene is partially distributed in blocks. 71. Composition according to any one of claims 54 to 70, wherein the composition comprises at least one of the following plasticizers: - up to 25% by weight of a tackifier resin with a softening point between 50 and 85 ° C, - up to 20% by weight, and preferably up to 15% by weight, of a liquid hydrocarbon resin, rosin ester or polytherpene resin, with a softening point not exceeding 30 ° C, - between 3 and 25% by weight, and preferably between 11 5 and 15% by weight, of a paraffinine or naphthenic mineral oil, having an aromatic content