CA1236610A - Adhesive thermoplastic compositions - Google Patents

Abstract

A B S T R A C T
Adhesive thermoplastic compositions. The invention relates to new adhesive thermoplastic compositions. The adhesive thermoplastic compositions according to the invention comprise at least one rubbery constituent and at least one resinous constituent and, if appropriate, other constituents, such as a plasticizer, filler and/or stabilizer, which are commonly incorporated into known adhesive thermoplastic compositions, generally called hot melts, but they also contain at least one special resin including regions of high cohesion incompatible with the rubbery constituent on the molecular scale, but miscible on the macroscopic scale. The compositions according to the invention are particularly useful for sealing double glazing units.

Description

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ADHESIVE THERMOPLASTIC COMPOSITIONS
The present invention relates to thermoplastic compositions exhibiting adhesive properties, that it to say compositions commonly called hot melts, and in particular thermoplastic sealing agents and compositions hereafter called hot melts.
Hot melt techniques axe extremely diversified and range from the weakest types of glue bonding, for example in the cardboard trade, to the most difficult types of sealing, such as joining metal to metal, metal to glass and glass to glass.
The question of durable and perfectly lactate metal to metal seals, for example for certain types of steel work, or metal to glass seals, for example for light bulbs, and glass to glass seals, for example for double glazing, will be dealt with below with specific reference to double glazing, for which the criteria imposed are the strictest.
Double glazing must satisfy two conditions of primary importance, namely the permanent existence of a sheet of dry air preventing internal condensation, and the cohesion of the whole unit.
The sheet of dry air can be obtained by means of a desiccant (silica gel, molecular sieve or the like) located between the two panes, and of moisture barriers set up around the edge of the double glazing The cohesion of the whole unit can be achieved by means of welding or glue bonding.
Welding the glass to itself or to an inserted metal frame provides perfect leak tightness and cohesion, but this technique has been abandoned because it is very difficult and expensive to carry out.
glue bonding by means of polysulfides and more rarely, with the aid of other cross linked elastomers polymers, which are applied cold as a mixture with a I

catalyst, does not provide perfect leak tightness, which can only be achieved by the additional application of a hydrocarbon polymer which is perfectly hydrophobic but of low cohesion. The cohesion of the whole unit is acquired by virtue of the second crosslinkable polymer, but at the expense of rather slow polymerization (up to 24 hours), which remains dependent on the dose and the activity of the catalyst. Briefly, crosslinkable elastomers are suitable for industrial manufacture with specialized means, but are hardly suitable for the work of the small craftsman in glazing.
A more recent technique, which is mentioned in French Patent application No. 73 140~6 (now French Patent No, 2,185,669), is to apply hot melts, which are not cross linked and permit immediate use. A new improvement in this field is the coating, on three faces, of the spacer bars forming the frame on either side of which the two panes are placed.
The limitations of the current technique are related to the character of sealing agents whereby they melt when heat is applied, the sealing agents being reversible thermoplastics; there it a certain amount of flow when cold Rand a fortiori when hot), and, consequently, if the units are stored under conditions where the two panes are not supported simultaneously by their lower edge, the unsupported pane can slide downwards and, in the worst cases, lose the leak tightness.
The object of the present invention is to improve the sag resistance of joints produced by means of hot melts, and in particular the creep resistance of double glazing, by the addition, to the conventional hot melt compositions, of a resin which gives these hot melts satisfactory properties in the areas of cohesion and impermeability to water vapor.

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For this purpose, the invention relates Jo a hot melt of otherwise conventional composition, comprising at least one rubbery constituent and at least one resinous constituent, whose composition includes a "special resin"
miscible with the rubbery constituent on the macroscopic scale, this special resin including regions of high cohesion incompatible with the rubbery constituent on the molecular scale, and regions of low cohesion compatible with the same rubbery constituent on the molecular scale.
This special resin imparts a better sag resistance, has certain synergic effects and increases the modulus of this rubbery constituent, even for small elongations.
Apart from these rubbery and resinous constituents and the said special resin, the adhesive thermoplastic composition according to the invention can comprise other constituents which usually form part of the composition of a hot melt, and in particular plasticizers, fillers and/or stabilizers.
The hot melts according to the invention will be described below by defining more precisely the various constituents which they comprise or may comprise, and the relative amounts of these constituents.
In the description given below of the Compositions according to the invention, unless indicated otherwise, the amounts are indicated in parts by weight per 100 part by weight of the rubber which is one of the constituents.
The hot melts according to top invention always comprise a number of constituents which are divided up I into the following categories:
- the rubbers - the resins - the "special rosins depending on the relative amounts and the particular type of the constituents falling into these I

first three categories, and depending on the particular type of composition required, the hot melts according to the invention can also comprise one or more of the constituents which are divided up into the following categories:
- plasticizers - fillers - stabilizers and various other constituents.
The rubber present into the hot melts of the invention constitutes the elastomers base, the purpose of which is to absorb shocks at low temperature and to form the barrier to water vapor, in addition to keeping the so-called tackifiers in dispersion, the tackifiers being the agents which give a tacky character to the mixture into which they are incorporated.
The specific compositions according to the present invention contain 100 parts by weight of one or more rubbery constituents which consist, at least in part, of one or more "virgin" rubbery constituents chosen from amongst solid elastomeric polymers having a molecular weight of about 15,000 to 200,000 or 300,000 or more.
These polymers and the trade names by which they are sometimes known include in particular, the bottle rubbers such as isobutylene/isoprene copolymers, polyisobutylene ("Vistanex * L"), ~tyrene/butadiene polymers ("GAS" and "Keaton * SUBS"), styrene/isoprene polymers ("Keaton* SKIS"), hydrogenated styrene/butadiene and styrene/isoprene polymers ("Kraton*SEBS"), and the halogenated rubbers ("Parson*").
The bottle rubber used according to the invention can be any type of bottle rubber having a Mooney viscosity (ML 1 + 3 at 127C) of about 30 to 80, namely an isobutylene homopolymer or alternatively a copolymer of * trade mark I

isobutylene with a small amount, for example about 1 to 5 mow %, of a conjugated dine or pylon such as, inter alias butadiene, isoprene, piperylene or

2,3-dimethylbutadiene. This bottle rubber can be slightly cross linked and consist of one of the products conforming to U.S. Patent no. 3,674,735. Special preference is given to bottle rubbers having a Mooney viscosity, such as defined above, of about 50 to 60, corresponding to a molecular weight of approximately 450,000, which have a degree of unsaturation of about 1,5 mow % and, after vulcanization at 150C for 40 minutes of a standardized mixture, a modulus at 300% elongation of about 7 to 9 Ma, an ultimate tensile strength of about 16 Ma and an elongation at break of 450%. An example of a rubber of this kind is Pulsar* P301~
Apart from the "virgin" rubbery constituents as listed above by way of examples, the hot melts according to the invention can also comprise regenerated rubbers and/or prevulcanized rubbers.
An example of a regenerated rubber which can be used is a rubber having an ultimate tensile strength of 8.8 1.6 Ma and an elongation at break of 525 + 40%. A
prevulcanized rubber which can be used in particular is the rubber Killer.
As indicated above, the amount represented by all the rubbery constituents forming part of the composition of the hot melts according to the invention is considered as the reference amount namely 100 parts by weight.
It is generally advantageous for at least a major part, that is to say at least half (at least 50 parts), of this amount of rubbery constituents to be formed of one or more "virgin" rubbers, it being possible fox the remainder ( f rum 0 to 50 parts) to be represented by regenerated rubbers and/or prevulcanized rubbers.
* trade mark ,.~ ,.
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The resins form the second class of functionally _ important constituents of the hot melts of the invention.
They can be chosen, in particular, from amongst the following types:
(a) Aliphatic hydrocarbon resins and cou~arone/indene resins which have a softening point (ring and ball) of about 100C, of the kind described in U.S. Patent 4,294,733, for example the resin Escorez*(Esso) taken in amount of up to 500 parts and preferably of about 165 parts. Another suitable resin is Impresses).
It is generally advantageous for at least part of the amount of resinous constituents of the hot melts according to the invention to be represented by one or more aliphatic hydrocarbon resins and/or one or Gore coumarone/indene resins. It is the resins of this kind, in particular, which constitute the tackifiers of the composition.
(b) Aromatic resins (polymers of C8 cuts) or terpene-phenolic resins, having a softening point (ring and ball) of up to 200C, for example the resin Norris*
having a softening point (ring and ball) of 150C, taken in an amount of up to 300 part and preferably of about 100 parts. Another suitable resin is the resin Piccofyn*(Hercules).
(c) EVA resins, or ethylene/vinyl acetate copolymers, having a melt flow index, usually called MFI, of not more than 700 and preferably of about 25, for example an EVA resin containing 28% of vinyl acetate and having an MFI of 22 to 28, such as the resin Elvax*
(Dupont), taken in an amount of up to 200 parts and preferably of about 100 parts. It is the EVA resins, in particular, which are widely used in all adhesive compositions for ensuring a good spread and a good adhesion to metals.

* trade mark The list of resins indicated above is not exhaustive and other resinous constituents, especially those used in known hot melt compositions, can also form part of the composition of the hot melts according to the invention.
The relative amount of the resinous constituent or constituents of the composition can vary within fairly wide limits according to the resins used and the particular properties which it is desired to impart to the hot melt.
As a general rule, all the resinous constituents incorporated into the composition will represent from 50 to 1,000 parts and advantageously from 100 to 500 parts The third class of essential constituent of the hot melts according to the invention is formed by the "special resins", which will be defined below.
In the same way as the resins which Norm part of the second class of constituents as described above, the "special resins" obviously form part ox a very large number of substances called "resins".
For the purpose of describing the object of the present invention, however, it is useful to consider these "special resins" as forming a separate class of constituents because it is essentially the incorporation of these "special resins" into the composition which constitutes the naivete and the originality of the hot melts according to the invention, compared with thy known hot melt 5 .
It is by virtue of the incorporation of these

3 "special resins" that the hot melts according to the invention have advantageous properties in comparison with analogous hot melt compositions which do not comprise these "special rosins The "special resins" which form part of the third class of the essential constituents of the hot melts according to the invention are resins which incorporate . , ~23~
g regions of high cohesion incompatible with the rubbery constituent on the molecular scale, but which are miscible on the macroscopic scale.
In general, the resins which are called "special resins" in the present specification form part of the class of the block or multi block copolymers consisting of elastomeric segments and rigid segments of high cohesion.
More particularly, the said elastomeric segments consist of polyols, polyethers or polyesters and the rigid segments of high cohesion consist of poly(tetramethylene terephthalate), polyurethane, polyamides or copolyamides.
Examples of these block or multi block copolymers which are commercially available are as follows (designated by their trade name): Paybacks (AUTO) and Pellethane (Upjohn).
It is these block copolymers which give the hot melts of the invention their superiority over analogous products by improving, in particular, the flow resistance when cold and even when hot.
According to an advantageous embodiment of the invention, these block copolymers consist of copolyetheresteramides which are formed of the product resulting from the copolycondensation of an , dicarboxylic polyamide or copolyamide having a molecular 25 weight of 300 to 15,000 and preferably of 400 to 5,000, employed in an amount of 90 to 5% by weight, and of an aliphatic dihydroxylated polyoxyalkylene having a molecular weight of 100 to 6,000 and preferably of 200 to 5,000, employed in an amount of 10 to 95% by weight, the said product having a softening point (ring and ball) of between 80 and 210C and preferably of 100 to 200C, and a viscosity in the molten state of 10 to 2,000 Pays at 200C.
According to one embodiment, the said condensation product comprises 60 to 20% of the said polyamide or copolyamide and 40 to 80% of the said Jo -dihydroxylated polyoxyalkylene.

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Preferably, the said "special resin" is a block polyetheresteramide formed of Cop 6.11/PPG/PTMG, PA 12/PTMG or Cop 6.12/PPG. The abbreviations have the following meanings:
PUG : polyoxypropylene glycol PTMG : polyoxytetramethylene glycol PA : polyamide Cop : copolyamide 6, 11 or 12 : respectively, polyamide-6, 11 or 12.
More particularly, the said special resin can consist of a block copolyetheresteramide which has a softening point (ring and ball) of 120 to 190C and a viscosity in the molten state of 100 to 800 Pads at 200C, and which corresponds to the formula:

Ho - C - PA - C 0 PI - 0 - - H
_ n o in which:
Pi represents a rigid polyamide segment having a 25 molecular weight of approximately 500 to 2,000, and PI represents a flexible polyether segment having a molecular weight of approximately 1,000 to 3,000.
The amount of special resin in the composition of the hot melts according to the invention can vary within fairly wide limits. In general, the compositions will comprise from 1 to 300 parts of one or more special resins and more particularly from 10 to 150 parts. An example of a special resin of this type is Pebax*(ATO), which is used in an amount of up to 250 parts, preferably of 10 to 150 parts and especially of 30 to 80 parts.

* trade mark I

The fourth class of constituents which the hot melts of the invention can comprise includes plasticizers, which are divided into:
(a) Polyisobutylenes of low molecular weight, namely of at most 50,000, which impart the adhesion to glass, for example Vistanex*LM taken in an amount of up to 500 parts and preferably of 100 parts. Similar suitable polymers are the polybutene Hyvis*(BP) and Indopol*
(Amoco).
(b) Tactic polypropylene, which are the hydrocarbon-soluble residue from the polymerization of propylene by the Ziegler-Natta process. A polymer of this type makes the flow rate uniform when the hot melts are applied. An example of these polymers is Vispol*
(Interchimica) taken in an amount of up to 250 parts and preferably of about 40 parts. Another useful agent of this type is Afax*(Hercules).
(c) ~aphthenic oils, the addition of which is optional and whose purpose is to adapt the viscosity to the characteristics of the extrusion machines. Examples of these oils are En~rthene*(BP) and Coors). The amount of naphthenic oil could be up to 300 parts.
The fifth class of constituents which the hot melts of the invention can comprise includes fillers. The purpose of these is to reinforce, to protect against ultraviolet radiation and to absorb infrared radiation.
; The fillers can be ox organic type, such as carbon black, for example FEZ Sterling, taken in an amount of up to 300 parts and preferably of 50 to 100 parts, or alternatively of inorganic type, such as chalk, talc, titanium dioxide, asbestos, fibers, clay or silica, inter alias the addition of which is optional and can amount to ~00 parts.
The sixth class of constituents which the hot * trade mark ;

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melts can comprise includes stabilizers and additives making it possible Jo optimize the properties of the product according to requirements.
The stabilizer used can be any stabilizer commonly used for rubbers, plastics and resins, for example Irganox*1010 (Ciba-Geigy), in an amount of up to 20 parts and preferably of 3 to 5 parts.
The glass/hot melt bond can be improved by means of an organosilane, which may or may not be coupled with an epoxy resin. Amongst the sullenness used there may be mentioned those sold under the names A-172, A-186, A-187, A-153 and A-151 (Union Carbide Corporation). These organosilanes are used at concentrations ranging, for example, from 0,5 to 30 parts and preferably of about 15 parts The invention is illustrated by the specific examples below, with reference Jo the attached drawings;
in these drawings:
Figure 1 is a simplified side view showing the assembly of a test piece for a flow test;
Figure 2 is simplified side view showing the assembly of a test piece for a peel strength test at 180;
Figure 3 is a simplified side view showing a test piece for a dynamic shear test; and foggier 4 is a simplified side view of the arrangement for measuring the movement in a double glazing unit.
In the examples, the useful properties of the hot melts are measured and compared by means of the tests described below.

1. As indicated in Figure 1, the following are placed successively on a plane surface: galvanized steel plate 1 (75 mm x 150 mm x 1 mm), a glass plate 2 (75 mm x * trade mark Jo ,.
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150 mm x 6 mm) protected by silic~ne-coated paper Jo serve as a spacer and offset by 35 mm, and a second glass plate 3 having the same dimensions, offset by 10 mm relative to the steel plate 20 The hot melt 4 is extruded between the steel and glass plates. A 10 kg weight is placed on the whole structure, which is left to cool for 30 minutes. The surplus hot melt 4 is removed by means of heated knife so as to give a joint of 25 mm x 75 mm x 6 mm.
3. One hour after assembly, the glass spacer is removed, the position of the steel plate relative Jo the glass is marked and the test piece is suspended, by means of a hole made in the steel plate in an oven at 85 + 2C
for 1 hour, with the glass facing downwards.

4. The test piece is removed from the oven and the slip of the glass away from the initial mark is measured. The value is rounded off to the nearest millimeter.
b. Peel strength at 180 on a test piece 1. us indicated in figure 2, the test pieces are prepared by extruding the hot melt 5 into the gap made by a silicone-treated glass plate 6 (25 mm x 150 mm x 4 mm) between a clean virgin glass plate 7 (25 mm x 150 mm x 4 mm) and a new aluminum foil 8 (25 mm x 150 my x 0,1 mm) placed on a supporting glass plate 9 (25 mm x 150 mm x 4 mm). After extrusion, pressure is applied with the hand and the surplus it removed to give a sealing area of 25 mm x 50 mm. The whole structure is left to cool for about 10 minutes and the silicone-treated glass plate is removed.
I The test pieces are conditioned for 4 hours at ambient temperature (23 + 2C) before being subjected to aging, if appropriate.
3. After aging, the test pieces are allowed to return to ambient temperature (60 minutes).
4. The test pieces are placed in the tensile testing machine operating at a spend of 50 mm/minute.

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5. All the peel strength values must be measured at ambient temperature (23 + 2C).
I The peel strength test consists in pulling the aluminum foil off the glass plate, forming an angle of 180 by folding back the free end of the aluminum foil.
JO The value of the peel strength is equal to the average of 3 values measured for each conditioning operation.
8. If breaking occurs, it must be stated whether this is cohesive or adhesive. It is cohesive if it occurs within the hot melt. It is adhesive if it occurs at the junction between the hot melt and the substrate and, according to the particular case, is referred to as glass-adhesive or aluminum-adhesive.
9 The accuracy is estimated to be + 15~.
c Dynamic shear test _ 1. Using the same general conditions as for the flow test and peel strength test, with an adapted arrangement, test pieces such as shown in Figure 3 are prepared, which comprise a 4 mm thick glass plate 10, a seal 11 of 25 mm x 25 mm over a thickness of 4 mm, and a galvanized steel plate 12.
2. After conditioning for 24 hour at ambient 25 temperature ~23 + 2C), a tensile force of 10 mm/minute is exerted at 25C using a tensile testing machine.
; 3. The tabulated value is the average of 3 measurements.
d. Creep Test 1. Double glazing units 13 of 350 mm x 500 mm are constructed as illustrated in Figure 4; their 4 mm thick paps 14, 15 are separated by 12 mm wide aluminum spacers 16 filled with a OR molecular sieve, the whole structure being assembled by the conventional process for extrusion of the hot melt 17.
2. The creep test is carried out in accordance with the technique recommended by the Dutch COMMA Institute under the designation K24, the lower pane 15 being held against an abutment 18 while the upper pane 14 is pulled, along the 350 mm side, by means of a hook 19 on which a 10 kg weight 20 pulls via a wire 21 passing over a pulley 22. A comparator having a precision of 0,01 mm, which is mounted at 23 and whose pointer on the glass plate under tension, makes it possible to measure the movements as a function of time.
The invention is illustrated further, without being limited, by the examples which follow.
To carry out the examples, a number of hot melts, whose compositions are given in Table I, are prepared.

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T A B L E
-jot melts 1 2 3 4 - 5 6 7 8 _ Bottle rubber 74 74 74 74 7474 74 74 7 Regenerated bottle Vredestein POOR 26 26 26 26 26 26 2$ 26 26 Hydrocarbon resin Esquires 1304 122 122 122 122 122 122 122 122 122 Terpene-phenolic Norris 2150 74 74 74 7474 74 74 _ 74 Block c~poly-etheresteramide _ 20 4488 44 44 ~44 44 44 Paybacks Hal 15 ~thylene/vinyl .
acetate copolymer I 74 74 74 74 _ 37 _ 74 74 Ethylene/vinyl acetate copolymer _ _ _ _ 74 37 _ _ _ I Low molecular weight polyisobutylene 74 74 7474 74 74 74 74 74 Vistanex IT
Tactic polypropylene 41 41 4141 41 41 41 41 Vispol 3000 Carbon black 74 74 74 7474 '74 74 74 74 Antioxidant 4 4 4 4 4 4 4 4 4 Organosilane A-172*** _ _ _ _ _ _ _ 11 _ _ _ _ _ _ * Elvax~ MFI = 25 I* Elvax, MFI - Owe *** A-172 : vinyltrimethoxyethoxysilane ~236~

EXAMPLE 1.-Influence of the proportion of block copolyetheresteramide The sag test on a test piece (or static shear), the peel strength test at 180 and the hardness test (Shore A are carried out on hot melts 1, 2, 3 and 4.
The results collated in table II demonstrate that the copolyetheresteramide Paybacks (hot melts 2, 3 and 4) is essential and has an effective action even at low concentration, the best results being obtained with the hot melts comprising at least 44 parts of Paybacks.
TABLE II
-_._ ._ Hot melt Sag at 85C Peel strength Hardness over 1 Hart 180 (Shore A) (mm) (N/cm) , . _ . .. .__ _ _ 88 __ EXAMPLE 2.-Influence of the e-thylene/vin acetate copolymers.
The same tests as in Example 1 are carried out on hot melts in which the proportion of ethylene/vinyl acetate copolymer varies.
The results collated in Table III show that these copolymers are necessary (hot melts 5, 6 and 3) for a good sag resistance, the best adhesion being imparted by an EVA
copolymer having a medium MFI (hot melt 3).

TABLE III

. Hot melt Sag (mm) at 85C Peel strength over 1 hour at 180 (N/cm) . . I.. _ EXAMPLE 3.-Influence of the terpene-phenolic resin In addition to the flow test and the peel strength test at 180, the viscosity in the molten state is estimated by extrusion using a Monsanto Capillary Remoter at 1.75C under 40 spa, with a 15:1 capillary.
The results given in Table IV show that the terpene-phenolic resin, although lowering the sag resistance, imparts a better viscosity in the molten state (which is important for pumps) and a better adhesion.
TABLE IV

ought melt sag (m=) at Pee; strength Viscosity 85C over 1 at 180 ( Pot sues) hour cam 30 3 4 go 520 8 2 _ 750 EXAMPLE 4.-Resistance to awing Test pieces for the peel strength test and for the dynamic shear test, constructed using hot melts 1 and 3~3~

3, are subjected to various aging conditions for a period of 2 weeks.
The aging conditions are:
(1) In an oven at high humidity (65C, relative humidity ox 95%) (2) In a water bath at 60C
(3) In a water bath at 25C under US irradiation (conditions described in testing technique P10 of the "Sealed Insulating Glass Manufacturers Association"
(SIGMA), United States of America) (4) In dry heat at 60C
(5) Under alternating 6-hour climatic cycles comprising sty hour: from 25C to 60C, with spraying to simulate rain during the first 30 minutes end hour: holding at 60C
3rd hour from 60C to 25C
Thea hour: from 25C to -30C
Thea hour: holding at -30C
Thea hour: from -30C to ~25C
and including intense US irradiation for the first 3 hours (in accordance with ASTM Standard Specification EG-PI).
For conditions 3 and 5, the transparent face is exposed to the US radiation.
The results are collated in Table V.

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TABLE V
Accelerated aging _ _.

aging conditions reel strength Dynamic shear (N/cm) (N/cm ) Hot melt Hot melt 10 Initial 80 MU 2 3 High humidity 55 81 20.0 22.4 Hot Water 65 84 21.2 23.3 Water + US I 107 14.7 15.4 15 Heat 69 76 20.6 22.0 Climatic cycles 57 . .. .. 13.2 15.1 It may be concluded that the block copolyetheresteramide has a beneficial action on preserving the adhesion properties under various aging conditions.
EXAMPLE 5.-, Effect of the block co~olyetheresteramide in heavy glazed units O
A creep test, as described in paragraph d on page 14, it carried out on double glazing units assembled using hot melts 1 and 3, applied in the conventional manner;
this test makes it possible to simulate to a certain extent the loads which exist in double glazing units of very large dimensions while at the same time working on a convenient scale The result given in Table VI show the creep resistance of the glazed units under a very strong pull is considerably improved by the bloc copolyetheresteramide.

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EXAMPLE 6.-Effect of the block copolyetheresteramide in hoe_ razed units mounted on coated spacer bars.
The same experiments as in Example 5 are carried out on double glazing units assembled using spacer bars coated on 3 sides beforehand The results given in Table VI demonstrate the same usefulness of the block copolyetheresteramide.
TABLE VI
10 Creep of Zen unit under a 10 kg load (Comma K24 test) . . _ , I. .. _ _ _ Load Conventional unit Coating on 3 sides application Hot melt Hot melt time _ 1 3 1 3 10 minutes 0.37 0.04 0.06 0.03 24 hours 1.48 0.26 0.23 0.08 207 days 2.00 0~40 0.64 0.14 Moreover, comparison of the results achieved by the conventional technique extrusion) and those achieved with coating on 3 sides shows that the improvement factor provided by a hot melt of the invention is approximately the same in both cases.
EXAMPLE 7.-Effect of vinyltrimethoxxethoxysilane on the resistance to a combination of W with water Double glazing units assembled using hot melts 3 and 9, applied in the conventional manner, are immersed in a water bath to a depth of approximately 5 cm below the surface.
The whole structure is exposed to ultraviolet rays by means of 2 W lamps. Amongst these lamps, there may be mentioned those sold under the reference "PHILLIPS

MU 300 W B22 3 US". The penetration of water into the double glazing unit is checked visually by the separation which takes place between the glass and the hot melt, caused by W bombardment. The minimum number of days of exposure necessary, over a number of samples subjected to this test, for the water to penetrate into the double glazing unit is thus recorded. The results are collated in table VII.
TABLE VII
Minimum number of days before the penetration of water into the double razing unit.
_. _ __ Jo Hot melt Minimum number of days _ . ,,_._ . . ...
This shows the considerable increase in the life of a double glazing unit subjected to the conditions described above, when this double glazing unit is constructed with hot melt 9 which contains an agent for coupling with glass, in this case vinyltrimethoxyethoxysilane, as in the example mentioned.
To summarize, the invention provides new hot melts which have a better sag resistance, which are suitable for application by conventional techniques (follower-plate pump and gun) or techniques of coating on ; 3 sides, which have a lower hardness and a better impact strength Pease of transportation and handling), which have a better aging resistance, which have a better resistance to the expansion of the unit under the effect of temperature differences and which have a better resistance .

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to asymmetrical overloads than hot melts which do not contain the special resin used in tune compositions of the invention.
Of course, the invention is not limited to the embodiments which have been described and shown by way of non-limiting examples, and it can form the subject of numerous modifications without exceeding the scope of the invention.

Claims (9)

C L A I M S

1.- An adhesive thermoplastic composition comprising at least one rubbery constituent and at least one resinous constituent, wherein the rubbery constituent has a molecular weight of at least 15000 and the resinous constituent contains a special resin and at least one other resinous constituent, the said special resin being a block copolyetheresteramide consisting of a product resulting from the copolycon-densation of an ?,.omega.-dicarboxylic polyamide or copo-lyamide having a molecular weight of 300 to 15000, employed in an amount of 90 to 5% by weight, and of an aliphatic ?,.omega.-dihydroxylated polyoxyalkylene having a molecular weight of 100 to 6000, employed in an amount of 10 to 95% by weight, the said polycondensation product having a softening point (ball and ring) of between 80 and 210°C and a viscosity in the molten state of 10 to 2000 Pa.s at 200°C, and the said other resinous constituent being at least one resin chosen from amongst :
a) an aliphatic hydrocarbon resin and/or a coumarone/indene resin;
b) a terpene-phenolic resin, and c) an ethylene/vinylacetate copolymer.

2.- A composition as claimed in claim 1, wherein the said block copolyetheresteramide has a softening point (ball and ring) of between 100 and 200°C and consists of a product resulting from the polycondensation of a polyamide or copolyamide having a molecular weight of 400 to 5000, employed in an amount of 60 to 20% by weight, and of an aliphatic ?,.omega.-dihy-droxylated polyoxyalkylene having a molecular weight of 200 to 5000, employed in an amount of 40 to 80% by weight.

3.- A composition as claimed in claim 1, which contains 1 to 300 parts by weight of said special resin per 100 parts by weight of the rubbery constituent.

4.- A composition as claimed in claim 2, which contains 1 to 300 parts by weight of said special resin per 100 parts by weight of the rubbery constituent.

5.- A composition as claimed in anyone of claims 3 and 4, which contains 10 to 150 parts by weight of said special resin per 100 parts by weight of the rubbery constituent.

6.- A composition as claimed in anyone of claims 1 to 3, which also comprises at least one plasticizing constituent.

7.- A composition as claimed in anyone of claims 1 to 3, which also comprises at least one filler.

8.- A composition as claimed in anyone of claims 1 to 3, which also comprises at least one stabilizer.

9.- A double glazing unit sealed with a combo-session as claimed in any one of claims 1 to 3.