CA1293074C - Hot melt sealant compositions - Google Patents

Abstract

A B S T R A C T

HOT MELT SEALANT COMPOSITIONS

A hot melt sealant composition which comprises:-a. 0-50 parts by weight of a multiblock copolymer having at least two endblocks A and at least one elastomeric midblock B;
b. 50-100 parts by weight of one or more diblock copolymers consisting of one block A' and one block B', wherein:
the blocks A and A' comprise monoalkenyl arene blocks and the blocks B and B' comprise hydrogenated conjugated diene polymer blocks, and the average molecular weight of the blocks A and A' is greater than the minimum molecular weight needed to obtain microphase separation and domain formation of the blocks A and A', and is less than the maximum molecular weight which would render the polymer incapable of being melt processed;
c. 50-400 parts by weight of a midblock compatible component wherein said midblock compatible component is preferentially compatible with block B and B', said component present in a content sufficient to maintain the resultant composition in a pliable condition at room temperature and to maintain Tg of the composition below 10 °C; and d. 0-100 parts by weight of an endblock compatible resin, with said resin being preferentially compatible with block A, being coumarone-indene resin, polystyrene, vinyltoluene-.alpha.-methyl-styrene copolymer or polyindene.

Description

:1~930 ;J~

HOT ~I.T SEALZ~NT CCMPOSITIONS

This invention relates to improved adhesives, sealants and caulking co~pounds. More particularly, it relates to solvent free, hot melt sealant compositions containing mixtures of hydrogenated styrenic block copolymers with tackifying resins and reinforcing resins which yield a sealant composition having improved adhesion without a primer, creep resistance at elevated temperatures and low moisture vapour transmission rates, rapid build up in viscosity with cooling and thixotropic application characteristics.
US patent specification 4,294,733 concerns a sealant system comprising an adhesive composition and a primer co~position. The use of a primer provides relatively good adhesion and cohesive failure in peel tests for adhesion. Both adhesive and primer composltions involve the use of Kraton G rubber, which has low moisture transmission rates compared to unsaturated Kraton D rubber products. "Kraton G" is a trade~rk for block copolymers having two polystyrene endblocks linked to a substantially saturated polyolefin rubber midblock. "Kraton D" is a trademark for block copolymers having two polystyrene endblocks linked to an unsaturated polyolefin rubber midblock. The adhesive composition has a moisture vapour transmission rate of not more than about 0.5 g per m~ per day, measured at 38 C and comprising per hundred parts by weight of the adhesive composition, from 5 to about 50 parts by weight of the adhesive copolymer having two polystyrene endblocks linked to a substantially saturated polyolefin rubber midblock, from about 5 to about 50 parts by weight of an aliphatic hydrocarbon resin having a melting point not less than 60 C, from about 2 to about 40 parts by weight of a curable epoxy resin and a finely divided inorganic filler, and the primer composition. A primer was needed when using the Kraton G rubber formulation in order to obtain a sufficiently strong bond for bonding panes of glass to a spacer assembly. In some instances, additional heat, pressure and ultraviolet radiation 1~93~

was required to assure a secure bond.
It is an object of the present invention to provlde a hot melt sealant composition prepared from a diblock copolymer, triblock~-diblock copolymer, a triblock copolymer, or mixtures thereof that is 100~ solids, one component, with a low moisture vapour transmission rate, high peel adhesion to glass and aluminium and does not require the use of a primer.
It is a further object of the invention to adjust the cohesive strength of the sealant by formulating the sealant to a specific A-B-A/A-B ratio thereby achieving cohesive failure in peel tests for adhesion while maximizing cohesive strength.
Accordingly, the invention provides a hot melt sealant composition which comprises-- ~
a. 0 to 50 parts by weight of a multiblock copolymer having at least two endblocks A and at least one elastomeric midblock B;
b. 50 to 100 parts by weight of one or more diblock copolymers consisting of one block A and one block B', wherein:
the blocks A and A' comprise monoalkenyl arene blocks and the blocks B and B' comprise substantially completely hydrogenated con~ugated diene polymer blocks, and the average molecular weight of the blocks A and A' is greater than the minimum molecular weight needed to obtain microphase separation and domain formation of the blocks A and A', and is less than the maximum molecular weight which would render the polymer incapable of being melt processed;

~293~74 -2a 63293-2769 c. 50 to 400 parts by weight of a midblock compatible component wherein said midblock compatible component is a resin, plasticizer or mixture thereof, that is compatible with block B and B', said component present in a content sufficient to maintain the resultant composition in a pliable condition at room temperature and to maintain the glass transition temperature of the resultant compositlon below 10C; and d. 0 to 100 parts by weight of an endblock compatible resin wherein said resin is preferentially compatible with blocks A

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and A' and is a coumarone-indene resin, a polystyrene resin, a vinyltoluene-alphamethylstyrene copolymer or a polyindene resin.
The average molecular weight of the A and A' blocks are between 3,000 and 40,000.
The monoalkenyl arene content of the multiblock and diblock copolymers is no re than the maximum weight per cent needed to retain a modulus suitable as a sealant in the resultant composition and no less than the minimum weight per cent needed to obtain the desired phase separation and the desired cohesive strength. The average monoalkenyl arene content is between 7% and 45% and preferably between 10% and 40% by weight. The most preferred weight per cent is between 10% and 30%, particularly between 15% and 30%. Very good results have been obtained with said contents being in the range of from 15~ to 18%.
The hot melt sealant formulations of the instant invention can also include fillers, pigments, ultraviolet inhibitors, antioxidants, adhesion promoters and thixotropic agents.
The midblock compatible component can be either a midblock compatible resin or a midblock ccmpatible plasticizer or mixtures thereof. When mixtures of midblock compatible components are used, each may be included in the formulation up to a total of 400 parts by weight.
The midblock ccmpatible resins may be any of a variety of hydrocarbon resins, such as hydrogenated rosins, synthetic poly-terpenes and the like. For optimum heat stability, weatherability and compatibility, the preferred tackifying resin is a saturated resin, e.g. a hydrogenated dicyclopentadiene resin or a hydrogenated polystyrene or polyalphamethylstyrene resin.
m e midblock compatible plasticizer may be rubber extending plasticizers, or compounding oils or liquid resins. These may be oils having a high content of saturated compounds or of aromatic compounds. Naphthenic or paraffinic processing oils having a low content of aromatic compounds are preferred.

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The endblock compatible component is used at a content which is less than the solubility limit of the component in the polymer with utility to maintain the cohesive qualities of the resultant co~position at elevated temperatures.
The present invention also includes sealant compositions comprising combinations of at least one of the group oonsisting of diblock copolymer, triblock/diblock co~olymer, triblock copolymer, and mixtures thereof.
Kraton G rubber in solvent based sealants have demonstrated thermal, oxidative and ultraviolet stability, excellent mechanical properties at ro~m temperature, high upper service temperature, good ozone resistance, and resistance to slump at elevated tempera-tures. Although adequately fulfilling the performance requirements for some sealants, solvent systems have the disadvantages of solvent release, long cure time, and shrinkage. A solventless system has the advantage of low energy consumption, high speed processing and little or no air pollution. In addition, saturated Kraton G r~bber is thermally stable during heat processing and exhibits excellent weatherability in outdoor applications. Kraton G
r~bber based hot melt sealants would have excellent mechanical properties rivaling silicone but with lower moisture vapour trans-mission (MVT) rates, the hot melt processing advantages of butyl hot melts but with better low temperature flexibility and creep resistance and adhesion comparable to polysulphides but with better ultraviolet resistance.
The most significant advantage of a hot melt sealant based on Kraton G r~b~er is hot melt processing. Some of the advantages of hot melt processing are: (l) simple application, requiring no mixing or proportioning of reactants, (2) rapid set to a solid state allowing rapid production rates. Units can be moved and packaged within minutes after fabrication (3) virtually no waste.
Trim or excess sealant can be reused. In contrast to the inherently high viscosity of partially crosslinked butyl based hot melt systems, physical crosslinking Kraton G rubber sealants can be formulated at lcwer viscosity than butyls. The advantages of high " 1293~

speed processing equipment dcvelopment, including melt-on-demand applicators which reduce the pot-life requirement, reduce the possibility of thermal degradation.
A one-part, single-seal hot melt sealant based on Kraton G
rubber will have a good balance of properties matching or exceeding the unique advantages of ccm~ercial sealants. By reinforcing the domain structure of Kraton G rubber in sealants, formulations can be developed with the proper balance of properties: high upper service te~perature without slump or creep, low temperature flexi-bility and good adhesion to a broad range of substrates and excellent weatherability inherent to saturated Kraton G rubber.
At elevated temperatures polystyrene damains soften and Kraton G rubber based campounds can be processed as thermoplastics. Upon cooling polystyrene domains reform to give outstanding properties without chemical crosslinking.
Block copolymers with polyisoprene and polybutadiene ~idblock segments have found a wide variety of applications. Saturated S-I-S
and S-B-S block copolymers, designated S-EP-S and S-EB-S, have better ultraviolet and therma] stability than their unsaturated counterparts. Diblock S-EB and S-EP polymers that are weaker than triblock polymers are also available. By blending d;hlock and triblock polymers in specific ratios, sealants can bc formulated with optimum cohesive strength such that the sealant demonstrates good peel adheslon and fails cohesively in peel.
This composition uses Kraton G rubber of three types: A-B
diblock copolymer, A-B-A/A-B copolymer, and A-B-A triblock copolymer.
The blocks A and A' have average molecular weights ranging from 4,000 to 150,000. The elastameric hydrogenated polyconjugated diene block B has average molecular weights ranging fram 18,000 to 250,000 and even 500,000. The poly(conjugated diene) block contains at least 20% of the monomer units polymerized in the 1,2 confi-guration. Hydrogenation of those blocks is carried out to a point where at least 95% of the aliphatic double bonds is saturated, and less than lO per cent of the aromatic double bonds of the poly(alpha-m~noalkenyl arene) block are hydrogenated.

lZ~3~74 Blocks A comprise predominantly polymer blocks of at least one monoalkenyl arene while blocks B comprise predominantly hydrogenated polymer blocks of at least one conjugated diene.
Blocks A are prepared by block polymerization of such monomers as styrene and vinyltoluene. Blocks B are prepared by block poly-merizing conjugated dienes such as butadiene or isoprene and thereafter hydrogenating the polymer block.
Each block A or A' for a triblock or a diblock copolymer preferably has a true average molecular weight in the range of from 4,000 to 50,000, more preferably from 7,000 to 40,000 and most preferably frcm 10,000 to 25,000.
Each B block of the ABA block copolymer is suitably twice the size of the B' block of the A'B' block copolymer.
For the block B, the true molecular weights are preferably in the range of 18,000 to 300,000, more preferably in the range of 70,000 to 225,000 and most preferably in the range of 150,000 to 200,000.
For the block B', the true molecular weights are in the range of 9,000 to 150,000, preferably in the range of from 35,000 to 115,000, and more preferably in the range of 75,000 to 100,000.
These molecular weights are true molecular weights corrected from styrene equivalent molecular weights from gel permeation chromotography.
Tackifying resins are blended with the block copolymer to provide tack. Examples of tackifying resins which may be used in the compositions accord~ng to the present invention are terpene resins (Piccohesive 125); polyterpene resins (Wing Tack 95 and Foral 105~; phenolic resins (SP559 and Super Beckocite 2000);
hydrogenated rosin (Stab lite ester 10); and hydrocarbon resins (Nevillac 10 and ERJ 683~. Typical plasticizers are polybutylenes having a m~lecular weight not to exceed about lO,OOO; (Vistanex LMMS~; phosphate esters (Santicizer 148~; dibutyl phthalate; low temperature plasticizers such as straight chain aliphatic acid esters (TP9OB, TP95, TP680); paraffin oils (Sun Par 2100); coal tars, asphalts; and m iokol~TP95 and T9OB. Chlorinated polyphenyl ~ral~

12~3~74 ;~ (Aroclor 5460~ and chlorinated biphenyl (Aroclor 1254~ may be used for both their tackifying and plasticizing properties.
More particularly, Regalrez 1018 (Hercules) and ECR 327 (Exxon) are preferably present in the hot melt sealant compositions.
The polymers and tackifying resins are intimately mixed and blended with plasticizers to lcwer the mcdulus of the sealant and in some cases, lower the overall cost in making the hot melt sealant compositions according to the present invention.
Like plasticizers, adhesion promoters, such as organo silanes or organotitanates can be added to the mixture.
Like plasticizers, adhesion promoters are incorporated in most compositions in am~unts ranging from 0.5 to 50 parts by weight for each 100 parts by weight of the elastomer and are preferably epoxy resins, organo silanes, organotitanates, and mixtures thereof.
Typical adhesion promoters are epoxy resins having an epoxide equivalent of from 150 to 3000 such as the resins sold by Shell Chemical Ccmpany under the trade names Epon 1002 and Epon 828~f Among the organic silanes employed are those sold by Union Carbide Corporation which are vinyl, cyclic epo ~ , aliphatic e~oxy and methacryloxy silanes identified as A-186, A-187, A-153 and A-151.
Various kinds of inert fillers can be added to the mixture.
These fillers can include clay, calcium carbonate, talc and the like. Pigments such as titanium dioxide and carbon blacks may also be included.
A new type of block copolymer, hereinafter referred to as Block copolymer 3 having a 30% coupled version of a triblock blended with uncoupled triblock in a hot melt sealant formulation has been found to be extremely effective in achieving the objects of the invention set forth hereinbefore. m e polystyrene domains are reinforced with an endblock resin, as described hereinbefore, and the sealant resists slump at elevated t2mperatures. A midblock tackifying resin provides tack. m e plasticizer which may be optionally added lowers the m~dulus, and provides a lower cost overall. The addition of the fillers lowers cost and reduces slump ~<Jcr~Je ~,k " lZ~3(~74 in the adhesive. I~le antioxidants and ultraviolet inhibitors/
stabilizers enhance the weatherability and the processing stability of the novel composition. A crystalline polymer with high melt flow and lcw molecular weight that forms a third phase but improves processability and upper service temperature may be included in the final formulation.
Polymeric compositions described above can provide sealant compositions which are capable of extrusions as a hot melt and harden to yield a non-tacky cohesive elastic mass having a desirable moisture vapour transmission. Moisture vapour transmission rates (MVTR) as used here, are determined by ASIM method E-96.
A desirable MNrR for the compositions according to the invention is less than 0.2 g cm per m2 per day, measured at 25 C or less than 1.0 g cm per m2 per day measured at 38 C.
To produce any of the compositions according to the invention and to determine the advantages and characteristics of the formu-lations, the following methods can be followed:
Mix approximately 450 g of test formulation at 177 C for 30 minutes in a Perkin/Elmer hot oil mixer equipped with a sigma blade mixing head and nitrogen purge. High shear sigma blade mixers or twin-screw extruders are particularly suited for Kraton G rubber based sealants which exhibit a non-Newtonian variation of viscosity with shear rate. The order of addition of ingredients aims for good mixing in a short amount of time. Preferably if the midblock resin is added first, agglomeration of polymer to mixer blades can be avoided. To increase the shearing action solid ingredients can be added to the mixer at one time.
Tests which can be conducted on the resultant sealant formula-tion, include Shore A Hardness, Tensile Strength, Elongation at Break, Tensile Stress MDdulus (ASTM D412), 180 Degree Peel to glass, aluminium and steel, Slump in a Vertical Channel, Shear Adhesion Failure Temperature Flexibility. These tests were chosen to determine mechanical properties of the formulated sealant, the range of service temperatures and adhesion capability.

`` lZ93~
g Other tests relevant to field performance include Moisture Vapour Transmission rate (ASTM E96), Seal Durability of Sealed Insulating Glass Units (ASTM E773), Frost Point of Sealed Insulating Glass Units (ASTM E546) and CGSB 12-GP on Insulating Glass Units, a Canadian Standard.
Samples for testing can be prepared using a "Little Squirt"
(Slautterback Corp. model LS-10) hot melt applicator. Separate heaters and thermostats for the tank and hose allow the delivery temperature to be closely controlled at 177 C.
The results of peel adhesion tests for the different for~u-lations were prepared by heat compression in platens at 130 C and prepared fram a hot melt gun applicator (Hardman "P" Shooter, Model 240) and set forth in the tables. Application of hot sealants formulations to cold substrates by the hot melt gun applicator shawed significantly worse adhesion than sealant formulations applied by compression under heat. To determine the effect of substate temperature, tests were conducted on both roam temperature substrates and substrates heated to 130 C. Hot applied test formulations onto cold substrates without further heat processing approximates actual field application and gives good indications of performance in the field.
The novel sealant formulations contained Kraton rubbers selected on the basis of low melt viscosity and intermediate styrene endblock size. Law melt viscosity provided formulating latitude and good wetting of the substrate. An intermediate size endblock provided a domain structure large enough to "build-up" the endblock with endblock reinforcing resins while maintaining moderate hardness. One Kraton rubber formulation having a 30/70 blend of an S-EB-S bloc copolymer and an S-EB bloc copolymer was used and is denoted as block copolymer 2 in the tables hereinafter. Another Kraton rubber formulation is an S-EB block copolymer, which is half the molecular weight of the S-EB-S block copolymer and is referred to as block copolymer 3.
The midblock resin was chosen to keep the rubber midblock glass transition tem~erature (Tg) as law as possible while lZ93~

providing tack. Low temperature flexibility at -30 C to -40 C is required to prevent cracking or crazing failure of the sealant during low temperature exposure. Since the polymer midblock Tg is -58 C, the use of a tackifying resin in large quantities results in an increase in midblock Tg, leading to embrittlement at lcw temperatures. The addition of large amounts of Hercules resin Regalrez 1018 which has a Tg of -24.5 C will not increase Tg to the extent other resins with higher Tg would. Recently, Exxon resin ECR 327 has beccme available with a Tg of -35 C. This resin is claimed to have equivalent stability to Hercules Regalrez resins but has not been tested.
The endblock resin was chosen on the basis of high Tg and stability. Hercules resins Kristalex 5140 and Endex 160 have glass transition temperatures of 86 C and 113 C, respectively. Roth are crystal clear with excellent thermal and ultraviolet stability.
Both resins were studied for their effect on the upper service temperature, i.e. resistance to slump and shear at elevated temper-atures. Studies on clear solvent-based sealants suggest that a small quantity of endblock resin in a sealant with a sufficiently large polystyrene endblock size will produce a clear sealant.
Studies for clarity were not conducted.
A high melt flow polypropylene (PP) was included in the formulation studies to raise the upper service temperature. Isotactic polypropylene has a melting point temperature of 165 C. In Kraton rubber compounds, PP can form an interpenetrating network (IPN) under the proper processing conditions. At service te~peratures below its melting temperature the PP IPN gives higher upper service temperatures in the sealant as measured by slump and SAFT.
To improve resistance to thermal, oxidative and ultraviolet degradation a combination of hindered phenolic antioxidant (Irganox 1010~, benzotriazole ultraviolet inhibitor (Tinuvin P ~and a hindered amine ultraviolet inhibitor (Tinuvin 770~ are used to stabilize the formulation against degradation. Tinuvin P and Irganox 1010 are known to have a synergistic effect in polymer stabilization.

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lZS3(~ 4 - 11 ~
m e effects of endblock resin as compared to PP in upper service improvement are lower viscosity and modulus, greater elongation, peel, lap shear and 5AFT than for the same parts per hundred (phr) of PP. This demonstrates the improvement in properties that are possible through reinforcement of polystyrene domains structure in contrast to reinforcement through a third phase.
The use of Endex 160 at 50 phr gives dramatic improvements in properties. The effect on upper service temperatures is equivalent to 100 phr of Kristalex 5140 in tensile strength, SAFT, lap shear and slump. Peel to glass and elongation exceeds that of 100 phr Kristalex 5140 while hardness and viscosity increase to a lesser extent. Based on these results Endex 160 is chosen over Kristalex 5140 as the endblock resin.
A high performance insulating glass edge sealant must satisfy many requirements as discussed in the introduction. Of these requirements, peel adhesion to cold substrates may be considered a primary requirement since it affects many critical properties of the sealant. Once good adhesion to cold substrates is achieved the proper adjustments in the formulation will lead to a sealant with a good balance of properties.
The following Examples further illustrate the invention.
The polymers used in the Examples are shown in Tables 1 and 2.

Polystyrene Polymer Type Content (%wt) A-B-A/A-B Ratio Block copol~ner 1 A-B-A Triblock 30 100/0 Block copolymer 2 A-B Diblock 24 0/100 Block copolymer 3 A-B-A/A-B 30 30/70 Block copolymer 4 A-B Diblock 17 0/100 Block copolymer 5 A-B-A/A-B 17 70/30 Block copolymer 6 A-B Diblock 15 0/100 Block copolymer 7 A-B-A/A-B 15 60/40 Block copolymer 8 A-B Diblock 30 0/100 1~93(~'74 Polymer Type Molecular Wt.
Block copolymer 1 A-B-A Triblock 7,000-35,000-7,000 Block copolymer 2 A-B Diblock 40,000-105,000 Block copolymer 3 A-B-A/A-B 7,000-35,000-7,000/7,000-17,000 Block copolymer 4 A-B Diblock 11,000-57,000 Block copolymer 5 A-B-A/A-B 11,000-114,000-11,000/11,000-57,000 Block copolymer 6 A-B Diblock 15,000-85,000 Block copolymer 7 A-B-A/A-B 15,000-170,000-15,000/15,000-85,000 Block copolymer 8 A-B Diblock 7,000-17,000 m ese polymPrs noted hereinbefore are one of three types:
A-B-A triblock, A-B diblock or A-B-A/A-B triblock/diblock copolymers where A is polystyrene and B is hydrogenated polybutadiene or polyisoprene. m ese polymers may be used in hot melt sealant formulations alone or in various combinations to yield a final hot meit sealant formulation containing a specific A-B-A/A-B ratio.
When A-B, A-B-A/A-B, and A-B-A type block copolymers are used alone or in co~bination for the purpose of achieving low cohesive strength in the hot melt sealant, there are six difference classes that provide a low A-B-A/A-B ratio and increase the possibility of cohesive failure in peel tests for adhesion; these classes include:-Class l: A-B diblock copolymer Class 2: A-B-A/A-B block copolymer Class 3: A-B diblock copolymer and A-B-A triblock copolymer Class 4: A-B-A/A-B block copolymer and A-B diblock copolymer Class 5: A-B-A/A-B block copolymer and A-B-A triblock copolymer Class 6: A-B-AJA-B block copolymer, A-B diblock copolymer and A-B-A triblock copolymer.
Block copolymer 1, an A-B-A triblock copolymer, is included to demonstrate conventional prior art technology. Block copolymers 2 throu~h 8 are high molecular weight polymers that pr w ide a balance of properties such as improved high temperature creep resistance, good adhesion, and thixotropic application characteristics.

12~3~4 Example 1 Table 3 compares the water vapour transmission rate of unsat-urated S-B-S or S-I-S polymers such as Kraton D formulations to block copolymer 1 being an S-EB-S polymer in which the EB block is substantially completely hydrogenated. ~ested under standard testing condition of 37.8 C and 90% relative humidity, hydrogenated S-EB-S block copolymer 1 allows less water vapour to permeate than unsaturated S-I-S or S-B-S polymers. In the novel sealant appli-cations where the sealant must provide a barrier function to moisture penetration, these hydrogenated block copolymers are preferred over Kraton D block copolymers.

Water Vapour Transmissions Rates of Block Copolymers g cm per m2 per day Block copolymer SBS 1.07 Block copolymer SIS 0.871 Block copolymer l 0.35 Example 2 The effect of an A-B diblock copolymer in an A-B-A/A-B polymer such as block copolymer 3 is illustrated in Table 4. The tensile strength of block copolymer 3 is 2.41 MPa at break where as the tensile strength at break of block copolymer 1 is 31.0 MPa. Hot melt sealants formulated with Kraton Formulation A are high in cohesive strength and will not fail cohesively in peel tests for adhesion without a primer.

`` lZ93~4 TABT~ 4 Com~arative Properties of Thenmoplastic Rubkers Block Copolymer 1 Block Copolymer 3 Tensile strength at 31.0 2.41 break, (MPa) 300~ Modulus, (MPa) 4.83 __ Elongation at Break (~) 500 200 Example 3 me effect of adjusting the A-B-A/A-B ratio is illustrated in Table 5. By blending block copolymer 1 with block copolymer 3, the A-B-A/A-B ratio in the sealant formulation is increased from 30/70, 50/50, to 70/30 in formulations A, B, and C respectively. The effect of a higher A-B-A/A-B ratio is to increase tensile strength, elongation, modulus and hardness. Additionally, a higher ratio of A-B-A/A-B so~iwhat improves the upper service temperature properties such as slump and SAFT. At high A-B-A/A-B ratios, however, the mcde of adhesion failure to glass becomes adhesive failure to the glass substrate resulting from the high cohesive strength of the sealant.
Test results in Table 5 show the effect of coupling efficiency on performance. A monotonic increase in m~duli, tensile strength and elongation i5 observed. Melt viscosity, hardness, lap shear and degree of slump at elevated temperatures also correlate directly with coupling efficiency showing an increase with higher coupling efficiency. These results are expected from the stronger network for higher triblock content Kraton rubber.
Peel results show greater variability with substrate. Maximum adhesion to glass is at 50% coupling efficiency while maxim~m adhesion to aluminium and steel is at 70% coupling efficiency. The mechanism of failure in peel tests is critical in determining the significance of the peel value. Cohesive failure with a high kN per m value is the most desirable while adhesive failure to substrate indicates poor adhesion and high cohesive strength of the polymer.

1293(~74 Coupling efficiency of the polymer in the range of 50-70% will give high peel values to glass and the mode of failure was oohesive for both glass and aluminium.
Similar results are found in Table 6, where the addition of an A-B diblock copolymer, block co~olymer 8 in a 50/50, A-B-A/A-B
weight ratio with block copolymer 1 provides improved adhesion in sealant D compared to sealant E consisting of 100 parts by weight A-B-A triblock, block copolymer 1.

~29313'74 Formulation A B C
-Block eopolymer 1 0 30 57 Block eopolymer 3 100 70 43 Midblock Resin tRegalrez 1018)a 270 270 270 Endbloek Resin (Endex 160)a 54 54 54 Polypropylene (Shell DX 5088)b 18 18 18 Stabilizer (Irganox 1010) Stabilizer (Tinuvin 770)c Stabilizer (Tinuvin p)c 1.5 1.5 1.5 Class 2 5 5 Properties Tensile strength (MPa) 0.41 0.69 0.72 Elongation (~) 425 550 675 lO0~ Modulus (MPa) 0.23 0.24 0.30 Hardness ~Shore A) 26 27 37 Melt Viscosity (Pa.s)d 1.040 1.780 3.055 180 Peel to Glass (kN per m)e 3.3C 6.8C 3.0AS
SAFT (C) 54 54 64 Slump (C) 65 65 70 a) Produet from Hereules Ine.
b) Produet from Shell Chemieal Co.
e) Product from Ciba Geigy d) At 177 C
e) C: cohesive failure AS: adhesive failure f) Shear adhesion failure temperature .

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Formulation D E

Block Copolymer 1 50 100 Block Copolymer 8 50 0 Midblock Resin (Regalrez 1018) 250 250 Endblock Resin (Kristalex 5140) 50 50 Stabilizer (Irganox lO10) Stabilizer (Tinuvin 770) Stabilizer (Tinuvin P) 1.5 1.5 A-B-A/A-B Ratio 50/50100/0 Class 3 __ Properties Hardness (Shore A) 22 32 180 Peel to Steel (kN per m) 3O3 1.6 Melt Viscosity (Pa.s) 0.8002.200 Example 4 Table 7 compares the prcperties of three hot melt sealants formulated by combining polymers to achieve an A-B-A/A-B ratio of 50/50. me other sealant ingredients are identical in all three ~onmulations. In successive formulations from F to H, the sealants possess improved strength and more importantly better high tempera-ture characteristics. me Experimental Kraton G polymers also provide the desired application viscosity for a hot melt insulated glass edge sealant.

~Z~3~'74 Formulation _ G H_ Block copolymer 1 30 0 0 Block copolymer 3 70 0 0 Block copolymer 4 0 28 0 Block copolymer 5 0 72 0 Block copolymer 6 0 0 21 Block copolymer 7 0 0 79 Regalrez 1018 270 270 270 Endex 160 71 71 71 Tinuvin P 1.5 1.5 1.5 Tinuvin 770 Irganox 1010 S-EB/S-EB-S Ratio 50/50 50/50 50/50 Class 5 4 4 Properties Tensile Strength (MPa) 0.94 2.65 3.15 Elongation (%) 590 1280 1300 Modulus, 100~ (MPa) 0.28 0.15 0.19 Hardness, Shore A 32 16 15 Melt Viscositya, (Pa.s) 1.090 71.467 --Peel to Glass (kN per m)b5.6PC 7.4 9.6 Peel to Glass/Soak (kN per m)3.7 1.2 --Peel to Aluminium (kN per m)2.1 3.3 4.2 SAFT (C) 59 72 84 Slump (C) 65 110 150 a) measured at 177 C
b) PC = partial cohesive failure 1~3C~'74 E~ample 5 Sealants in Table 8 are formulated to low A-B-A/A-B ratios that give cohesive failure in peel tests for adhesion while maximizing tensile strength. This table illustrates the use of various ingre-dients that promote the final properties of the sealant such ascoupling agents, fillers, carbon black and terpene phenolic resin.
m e formulation can be compared to the properties of a cammercially available hot melt butyl sealant (formulation Q).

1293(i'74 Formulation _ J K L M N O P Q_ Block copolymer 1 Block copolymer 2 33 33 33 0 Block copolymer 3 5 5 5 5 5 Block copolymer 4 72 35 35 Block copolymer 5 28 27 27 Block copolymer 6 100 68 33 66 66 Block copolymer 7 32 29 29 Midblock Resin 270 270 270 250250 250 250 250 (Regalrez 1018) Endblock Resin 71 71 71 50 50 50 50 50 (Endex 160) Polar Resin 50 (Super Nirez 6040) Stabilizer (Irganox 1010) Stabilizer (Tinuvin 770) Stabilizer 1.5 1.5 1.5 1.51.5 1.5 1.5 1.5 (Tinuvin P) Filler (Calcium 100 Carbonate) Coupling agent 1 4.5 (A-1120) Coupling agent 2 2 (LICA-09) Pigment (carbon 5 5 black) A-B-A/A-B Ratio 0/10020/80 20/80 20/80 20/80 20/80 20/80 20/80 Class 1 4 4 6 6 6 6 6 ` 1;~93(:17~

Formulation I J K L M N O P Q

Properties Tensile strength 0.300.41 0.91 0.39 0.620.64 0.85 1.03 0.01 (MPa) Elongation (%)1050 10801000 863 600 10501400 1467 1300 100% Modulus IMPa) 0.130.11 0.26 0.12 0.300.25 0.12 0.23 0.21 Hardness (Shore A) 16 15 15 17 24 15 13 28 45 Melt Index 1152 -- 549 319 209 254 391 1116 207 (g/10 m m) 180 Peel to Glassa 5.6C 6.3C 14.0PC 9.6C 9.6 10.5PC13.1C 10.7C 3.0C
(kN per m) 180 Peel to Glass/ 07.9C 0 0 4.6 0.5 0.7 -- 2.6C
soak (kN per m) 180 Peel to Alumi- 6.1C3.7 6.6 8.2C 7.0 5.8 6.7 13.1C 3.5C
nium (kN per m) SAFT (C) 64 61 76 69 77 77 73 67 60 Slump (C) 130 75 145 185 195 145 150 105 210 a) PC = partial cohesive failure Example 6 The moisture vapour transmission rate of the Kraton G polymer is affected by the selection of ingredients. Table 9 illustrates the effect of a midblock compatible resin, an endblock compatible resin and polyisobutylene (Vistanex I~S, Exxon), a low moisture vapour transmission rate polymer. When properly formulated, Kraton G block copolymer based hot melt sealants (formulations B and M) are as effective as a commercial hot melt butyl sealant (formula-tion Q) in providing a barrier to moisture vapour transmission.

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Moisture Vapour Transmission Rates Condition 23 C, 50% R.H. 37.7 C, 90% R.H.
g cm per m2 ~er dayl g cm per m2 per day Block copolymer 1 0.42 (1.4) 1.97 (1.4) Block copolymer 2 0.19 (1.6) 1.67 (1.6) Regalrez 1018 200 PHR

Block copolymer 2 0.37 (1.4) 2.46 (1.4) Endex 160 50 PHR

Block copolymer 2 Vistanex LM-MS 50 PHR 0.23 (1.4) 1.04 (1.4) Formulation B 0.93 (0.51) Formulation M 0.25 (1.5) Formulation Q 0.22 (1.4) 1.03 (1.4) 1) the thickness in mm of the test piece is stated between brackets 2) R.H. means relative humidity PHR means parts per hundred

Claims (14)

1. A hot melt sealant composition which comprises:
a) 0 to 50 parts by weight of a multiblock copolymer having at least two endblocks A and at least one elastomeric midblock B;
b) 50 to 100 parts by weight of one or more diblock copolymers consisting of one block A' and one block B', wherein:
the blocks A and A' comprise monoalkenyl arene blocks and the blocks B and B' comprise substantially completely hydrogenated conjugated diene polymer blocks, and the average molecular weight of the blocks A and A' is greater than the minimum molecular weight needed to obtain microphase separation and domain formation of the blocks A and A', and is less than the maximum molecular weight which would render the polymer incapable of being melt processed;
c) 50 to 400 parts by weight of a midblock compatible component wherein said midblock compatible component is a resin, plasticizer or mixture thereof, that is compatible with block B
and B', said component present in a content sufficient to maintain the resultant composition in a pliable condition at room temperature and to maintain the glass transition temperature of the resultant composition below 10°C; and d) 0 to 100 parts by weight of an endblock compatible resin wherein said resin is a coumarone-indene resin, a polystyrene resin a vinyltoluene-alphamethylstyrene copolymer or a polyindene resin.

2. The composition as claimed in claim 1, wherein the endblock compatible resin is compatible with blocks A and A'.

3. The composition of claim 1 wherein the blocks A and A' are polystyrene blocks.

4. The composition of claim 1 wherein the blocks A and A' are polyvinyltoluene blocks.

5. The composition as claimed in claim 1, 2, 3 or 4 wherein the B and B' blocks are hydrogenated polybutadiene blocks.

6. The composition as claimed in claim 1, 2, 3 or 4 wherein the B and B' blocks are hydrogenated polyisoprene blocks.

7. The composition as claimed in claim 1, 2, 3 or 4 wherein the block copolymers contain 10% to 40% by weight of monoalkenyl arene.

8. The composition as claimed in claim 1, 2, 3 or 4 wherein said blocks A and A' have a true molecular weight in the range of from 4,000 to 50,000.

9. The composition as claimed in claim 1, 2, 3 or 4 wherein said block A and A' in said multiblock copolymer and said diblock copolymer have different molecular weights.

10. The composition as claimed in claim 1, 2, 3 or 4 wherein said block B has a true molecular weight in the range of from 18,000 to 300,000.

11. The composition as claimed in claim 1, 2, 3 or 4 wherein said block B' has a true molecular weight in the range of from 9,000 to 150,000.

12. The composition as claimed in claim 1, 2, 3 or 4 wherein said endblock compatible resin has a true molecular weight in the range of from 3,000 to 9,000.

13. The composition as claimed in claim 1, 2, 3 or 4 which further contains a filler, a pigment, an ultraviolet stabilizer and/or an antioxidant.

14. Articles provided with a hot melt sealant composition as claimed in claim 1, 2, 3 or 4.