CA1278132C - Tackifiers and their use in pressure sensitive adhesives - Google Patents

Abstract

ABSTRACT

Resins having a softening point from 10°C to 120°C
especially 10°C to 80°C being a copolymer of a feed which is predominantly C5 olefines and diolefines and 10 to 60 wt.%
of one or more monovinyl aromatic compounds are used as a tackifier for acrylic polymers or copolymers particularly in aqueous based pressure sensitive adhesives.

Description

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1 Tackifiers and Their Use in Pressure Sensitive Adhesives The Present invention relates to pressure sensitive adhesives comprising a synthetic latex and a tackifier resin.

Pressure sensitive adhesives are, among other applications, used in the tape and label field. A pressure sensitive adhesive may be used in a number of applications such as masking tape, electrical tape and medicinal tapes for holdinq dressinqs and the like in place. The term label covers a broad ranqe of products and includes items such as price tags in the supermarket and labels on glass or plastic containers. In the case of "labels" two types of bonding are required namely permanent and removable. Permanent bondinq is required for items such as labels on glass or 1~ plastic containers when the life of the label will be relatively lonq. Removable bonding is desirable for items such as price taas and peelable tape.

Pressure sensitive adhesives should have a high initial tack so that the adhesive surface merely needs to be contacted and pressed to a substrate to achieve bonding. There should be little or no requirement to hold the adhesive and substrate in position for anv significant time while a bond develops. Dependinq upon the strength of adhesion required the bonding force of the adhesive may increase with time to provide a relatively permanent bond.

It is known to prepare at least three different types of adhesives usinq natural or synthetic tackifiers, natural or synthetic resins, or blends thereof, namely, hot melt adhesives, solution adhesives and aaueous based adhesives.
Hot melt adhesives are made from a blend of resins and are normally solid at room temperature. Hot melt adhesives ' ~

3Lr~7~3~32 1 require an elevated temperature for application to a substrate necessitatinq some type of hot melt gun.

Solution adhesives such as those described in United States Patents 4037016, 4048124 and 4248748 do not suffer from the same drawback since the adhesives comprise a solution of a tackifier resin or a blend of tackifier resins in a low boiling hydrocarbon solvent. When the adhesive is applied to a substrate the solvent evaporates. Due to environmental concerns and the risinq cost of hydrocarbon solvent there has been an increasing need to reduce or eliminate the hydrocarbon solvent in such adhesives. Accordingly, the adhesives industry is seekinq improved aqueous based adhesive compositions. Exist-nq aqueous based adhesive compositions usually comprise a natural or a synthetic latex in admixture with cellulose materials such as starch or natural or synthetic tackifier resins.

United States Patent 4,189,419 to Avery International discloses a pressure sensitive adhesive comprisinq from about 50 to 60~ by weiqht on a dry basis of a tackifier and from about 50 to 40% by weight on a dry basis of a carboxylated styrene butadiene polymer (SBR).

A paper entitled "Styrene Butadiene Latexes for Adhesive ~pplications" by Robert G. Kahn of Dow Chemical, published in Adhesives Age, December of 1977 discloses a similar pressure sensitive adhesive composition which also contains butyl benzyl phthalate, as a "plasticizer". While the amount o~ plasticizer is relatively small the plasticizer comprises a hydrocarbon phase in the adhesive and the composition is not entirely aqueous based.

~L~7~3~3;2 1 ~nited States Patent 4,179,415 issued December 18, 1979, to Johnson and Johnson discloses a substantially ac3ueous based adhesive composition COntaininCJ a latex havinq a high proportion of isoprene.

United Kingdom patent application 2097410A discloses novel pressure sensitive adhesives comprising a latex oE a polymer and a tackifier resin the polymer being obtained from particular amounts of vinyl or vinylidene aromatic monomers and C4-Cg conjugated diene monomers and an unsaturated carboxylic acid. Similarly European pa,tent appl,icatio~n ~ ~ 61~e~ 3 ~ e~er~q~,~
publication number 0062343 A2~'discloses a latex of a J
copolymer obtained from a hard monomer such as styrene, a sof-t monomer such as butadiene and an unsaturated acid which may be blended with a tackifying resin to produce a formulation useful as a pressure sensitive adhesive.

Various resinous materials have been suggested as tackifiers Eor these latices. Examples of materials suggested include emulsified rosin, partially decarboxylated rosin, glyceryl esters of polymerised rosin, partially dimerised rosin, ; 20 natural resins, hydroqenated wood rosin, plasticised hydroqenated rosin, aliphatic hydrocarbon resins from petroleum, aromatic petroleum resins, EVA, terpene/phenol resins, cumarone/indene resins, rosin esters~
pentaerythritol esters and polydicylopentadiene resins.

In developing adhesive formulations one seeks the optimum combination of several adhesive properties ancl since it is not generally possible to achieve the optimum for every property it is necessary to obtain the best balance of properties for the particular use in mind. For pressure sensitive adhesives for use in the label industry one tries to optimise the loop tack and ball tack and at the same time provide an adhesive whose component will not migrate during .
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1 storage leading to unsightly colouring and lowering of adhesive properties. Althou~h the improved loop tack and ball tack can be provided by the tackif ier resins of the type descrihed above we have found that those tackifiers which provide such tack for example hydrogenated rosins such as Staybelite ester 10 and modified rosins such as Snowtack 52CF tend to mi~rate.

It has been generally suggested in United Kingdom patent application 2097410A (published 3 November 1982) and European Patent application 00623~3 (published 13 October 1982) that petroleum hydrocarbon resins such as those manufactured from a ~g cut of an aromatic hydrocarbon stream or a Cs cut of an aliphatic of cycloalipha~ic hydrocarbon stream are useful as tackifiers.
There is however no suggestion of the particular type of resin th~t should be used and indeed many of the r~sins falling within such broad descriptions are unsuitable for tackification of lattices.

Our European published Patent Application 85302057.6 describes lattices of resins having a softening point from 10C to B0C which are copolymers of a feed which is predominantly Cs olefines and diolefines and one or more monovinyl aromatic compounds which contain from 10 to 3~
wt.% of the monovinyl aromatic compound and their use as tackifiers for for carboxylated styrene butadiene copolymer rubbers. We have now found that this type of copolymer is useful to tackify the polyacrylate emulsions frequently used in aqueous based adhesives.

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1 The present invention therefore provides the use as a tackifier for an acrylic polymer or copolymer of a resin havinq a softening point from 1~C to 120C preferably 10 to 80C being a copolymer of a feed which is predominantly Cs olefines and diolefines and one or more monovinyl aromatic compounds containing from 10 to 50 wto% preEerably lO to 30 wt.% of the monovinyl aromatic compounds.

The invention further provides a pressure sensitive adhesive comprisinq from 30% to 85% by weight of an acrylic polymer or copolymer and from 15% to 70% by weight of a resin having a softeninq point from 10C to 120C pereferably 10C to 80C beinq a coPolymer of a feed which is predominantly Cs olefines and diolefines and one or more monovinyl aromatic compounds containing from 10 to 60 wt.% preferably 10 to 30 wt.% of the monovinyl aromatic compounds.

The resins used-as tackifier according to the present invention are prepared by the polymerisation of a mixture of a petroleum cracked distillate qenerally boiling in the ranqe 25C to 80C and a monovinyl aromatic monomer in the proportions to yield a resin containinq from 10 to 60 wt.%
preferably 10 to 40 wt.% more preferably 10 to 30 wt.%
of the monovinyl aromatic compound as determined by Nuclear Magnetic Resonance analysis. The petroleum cracked distillate comprises a mixture of saturated and unsaturated monomers the unsaturated monomers being mono-olefines and diolefines and although the unsaturated materials are predominantly Cs some higher and lower materials such as C6 olefines and diolefines may be present. The distillate may also contain saturated hydrocarbons includinq aromatics which can act as polymerisation solvent.

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1 The preferred monovinyl aromatic monomer is styrene which may be substituted in the aromatic group. Alternatively ,methyl styrene or vinyl toluene may be used. It is preferred to use the pure monomer rather than the commercially available mixtures of vinyl aromatic monomers.

The resins are conveniently prepared by Friedel-Crafts catalysed polymerisation in which the mixture of cracked distillate and monovinyl aromatic monomer are treated with 0.25-2.5 wt.~ of a catalyst such as a]uminium chloride, aluminium bromide, or solutions, slurries or complexes thereof or borontrifluori~e. These reactions are qenerally carried out at temperatures in the ranqe 0 to 120C, preferably 0 to 70C more preferably 20 to 55C the conditions being controlled to yield a resin of the reauired softeninq point. Residual catalyst is quenched by suitable methods such as addition of methyl alcohol and subsequent filtration followed by water and/or caustic washing. The final solution may then be stripped o~ unreacted hydrocarbons and low molecular weiqht oils by vacuum or steam distillation.

The resins contain from 10 to 60, preferably 1 n to ~0 more preferably 10 to 30 wt.~ of the monovinyl aromatic monomer, most preferably from 15 to 25 wt.~ and have a softening point from 10C to 120C, preferably 10C to 80C. The optimum softening point depends on the nature of the acrylic polymer or copolymer latex with which it is to be used but we prefer it be in the ranqe 30C to 95C since at hiqher softeninq points the adhesive properties can deteriorate whilst use of lower softeninq point materials can result in miqration of the tackifier. The resins are conveniently suppliecl as aqueous emulsions and the eml~lsions maY reaclily 7B~2 1 be produced by mixing with water and an anionic or nonionic emulsifer or a mixture of both and obtaining the emulsion by inversion. We prefer that the emulsion contain about 50 wt.% of the resin. The emulsions may conveniently be obtained by the process described in our European Patent Application 83300001.1, ~ublication Number 0085471.

The acrylic polymer qenerally in the form of a latex and the tackifier may be blended using conventional blenders to provide a homoqenous mixture. The tackifier resin may be added to the latex in an amount of from about 20 to about 100 parts by weiqht per hundred parts of polymer in the latex, more, preferably the tackifier resin is added to the latex in an amount from about 50 to about 150 parts by weight per 100 parts of polymer in the latex. It is preferred that the tackifier be added to the latex as an aqueous emulsion to provide the amounts of tackifier resin per amount of polymer ~iven above. The acrylic polymer may be any of those traditionally used in the adhesives industry such as the "Acronal" (Re~istered Trade Mark) products marketted by BASF.

The adhesive compositions of the present invention may be applied to a substrate and then dried using conventional substrates and procedures The substrate used depends upon the use envisaqed but it is usually relatively thin material, usually no qreater than about 3.2 mm in thickness and in the manufacture of tapes and labels the substrate is qenerally in sheet form. The sheet may be a polymeric material which is flexible at room temperature and may be a homo-polymer of an ethylenically unsaturated monomer such as ethylene, propylene or vinyl chloride, or be polyester or polyamide provided it has sufficient flexibility for the 78g~3~

1 desired end use. Alternativel~ the substrate may be made from cellulosic or reconstituted cellulosic material such as rayon. The substrate need not be a sheet material but may be co~posed of fibers which mav be woven, or non woven as in paperO Woven substrates may be made from cellulosic material, such as cotton or from fibers of any of the above mentioned polymers.
The composition is applied to the substrate usin~
conventional coatinq techniques such as roller coaters, blade coaters, meyer rods or air coaters. The coated substrate is then dried usually by passing it through a heatinq tunnel or oven throuqh which may be circulatinq hot air or the tunnel or oven may contain infrared lamps to dry the coated substrate. The drying time will be a function of a number of factors such as the heat capacity of the substrate, the type of heating, the oven temperature, air velocities (if circulating air is used) and the rate of passaqe of the substrate throuqh the heater.

The substrate should be coated with suf f icient composition to provide a dry coat weiqht from about 16 to about 57 q/cm2 Generally in the manufacture of tapes usinq a continuous sheet polymeric substrate a dry coat weiqht of about 15-30 g/m2 is used. In the manufacture of labels a dry coat weight from about 15 to 30 q/cm2 is usually used.
In the manufacture of masking tape a dry coat weight from about 35 to about 65 q/cm2 is usually used.

After ~lryinq the coated substrate is cut to the required dimension. In the manufacture of tape the substrate is cut into strips and rolled to provide a Einished product. The substrate may also be cut into shaped items to provide labels or medicinal tapes.

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1 The invention is ill~strated by the followin~ Examples in which the feed used to produce the resin tackifier had the followina composition.

Component (Wt.~) Cs Paraffin Cs olefins 28.9 C6 paraffins 3 C6 olefins 5 10 Isoprene 17 Pentadienes 14.1 CPD 2.2 Aromatics 30 This feed was copolymerised with varying amounts of a C5 olefin stream and styrene usinq 0.85 wt.% of an aluminium trichloride catalyst at a temperature of 40~C.
The feed and catalyst were added to the reactor over 45 minutes and left for a further 15 minutes, after polymerisation the materials were hydrolysed, then neutralised with ammonium hydroxide, and stripped to remove volatiles.

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--1 o--1 The Cs olefin stream used had the followinq compositions 3-Me-butene-1 0.3 Pentadiene 1.4 0.1 i-Pentane 0.7 Penténe-1 1.6 2-Me-butene-1 3.7 Isoprene 0.3 -pentane 4.7 Pentene-2 trans 15.4 10 Pentene-2 cis 5.4 2-Me-butene-2 15.7 Pentadiene-1.3 tris & trans 0.3 CPD 1.0 Cyclopentene 12.2 Cyclopentane 11.9 Aromatics 4.0 The properties of the feeds used and the properties of the resins obtained are shown in the followinq Table.

Resin 1 2 3 4 5 6 7 . . . _ _ _ 20 Feed Composition Styrene: (wt.%) 8.6 8.6 14.3 20 27.3 18.2 33 ~-Me-styrene (wt.~) - - - - 9.1 Feed 30.4 30.4 28.6 26.7 24.2 24.2 22.2 Cs stream (wt.~)61 61 57.1 53.3 48.5 48.5 44.8 Resin yield (%) 38 30 39 45 55 54 62 Softening point (~C) 33 50 31 38 40 30 40 Styrene in resin (~ wt.) 20 20 30 40 43 45 50 Example 2 was stripped using steam ~7~32 1 The resins were emuls~fbi/e~ ~ an equal weiaht of water by r the process of European~Patent Application 83300001.1 using 5.5 parts of the commercially available emulsifier Atlox 3404FB and their properties as tackifiers for polyacrylate emulsions commercially available for water based pressure sensitive adhesives were determined by mixinq the resin emulsion and the latices commercially available from BASF as ACRONAL 80 D and ACRONAL 85D and ACRONAL V205 to give a mixture combining eaual amounts of resins and polyacrylates on a dry basis. The mixture was coated onto Mylar film to aive a coverinq of 25 grams/sauare metre and the 180 peel strenath, loop tack on metal and ~lass and the ball tack were meas~red as well as the shear on metal and the results compared with systems containin~ the commercially availahle tackifier the modified resin known as Snowtack 52 CF.

The results obtained with Acronal 80D were as follows:

Snow RESIN 1 2 3 4 5 6 7 Tack Peel Strenath Newtons/in 9.9 10.910.7 11.6 8.9 10.1 9.5 12.5 Loop tack Newtons/in 8.2 8.8 8.8 10.3 7.56.5 8 9.3 Shear (Hours) 10.5 10 7.5 9.7 18.7 6 8.7 7.5 lX7BL32 1 The peel strength, Loop Tack and Shear of Adhesives obtained from equal parts of an Snowtack 52 CF and emulsions of Acronal 85D and V205 D were measured at varying resin concentrations and the values obtained are set out in the ~raphs which are Figures 1 to 6 hereto in which the wt.~
resin is on a dry basis in relation to the total weiqht of polvmer and resin.

The followinq further resins were prePared using the feeds previously described.

10 RESIN ~ER 8 9 10 Feed composition wt.%

Styrene 17.7 8.9 11.7 ~eed 42.1 53.7 52.1 C5 stream 40~2 37.4 36.2 Resin yield % 46 26.1 47.3 Softeninq Point C 77 26 75 Styrene in Resin (~ wt.) 35 9 22 All the resins were steam stripped.

The resins were evaluated as tackifiers for acrylic emulsion in mixtures containinq 100 parts by weiqht acrylic and 20 parts by weiqht resin on a dry weiqht basis.

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1 The results were as follows:

Acrylic Emulsion ACRONAL V205 ACRONAL 85D

Emulsion of Resin 8 9 10 8 9 10 Peel (N/Inch) 20 17 20 9~9 8.8 8.8 Loop Tack (N/Inch) 1.5 12 11 1.5 6.5 7.8 Ball Tack (cm) 4.511 4.5 10 1814 Shear (Hrs) 1 0.8 0.5 >300 83200

Claims (4)

1 A pressure sensitive adhesive comprising from 30%
to 85% by weight on a dry basis of an acrylic polymer or copolymer and from 15% to 70% by weight on a dry basis of a resin having a softening point from 10°C to 120°C being a copolymer of a feed which is predominantly C5 olefines and diolefines and one or more monovinyl aromatic compounds said resin containing from 10 to 60 wt.% of the monovinyl aromatic compound.

2 A pressure sensitive adhesive according to Claim 1 in which the acrylic polymer or copolymer has a softening point from 10°C to 80°C and contains from 10 to 60 wt.% of the monovinyl aromatic compound.

3 A pressure sensitive adhesive according to Claim 1 or Claim 2 in which the resin contains from 10 to 25 wt.% of the monovinyl aromatic compound.

4 A pressure sensitive adhesive according to Claim 1 in which the monovinyl aromatic compound is styrene.

A pressure sensitive adhesive according to Claim 1 in which the resin and the acrylic polymer or copolymer are present in aqueous carriers.