CA2239983C - A polymeric composition in pellet form - Google Patents
A polymeric composition in pellet form Download PDFInfo
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- CA2239983C CA2239983C CA002239983A CA2239983A CA2239983C CA 2239983 C CA2239983 C CA 2239983C CA 002239983 A CA002239983 A CA 002239983A CA 2239983 A CA2239983 A CA 2239983A CA 2239983 C CA2239983 C CA 2239983C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/124—Treatment for improving the free-flowing characteristics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
Abstract
A polymeric composition in pellet form comprising a tacky hot melt composition, comprising a) from about 5 % by weight to about 90 % by weight of a thermoplastic polymer, b) from about 10 % by weight to about 65 % by weight of a tackifying resin, c) up to about 50 % by weight of a plasticizer, d) up to about 2 % by weight of an antioxidant, and a pelletizing aid, wherein the tacky hot melt composition is a pressure sensitive adhesive having a storage modulus, G', at about 25 ~C, of less than about 5 x 106 dynes/cm2, and each pellet has a substantially tack-free surface. This invention further discloses a polymeric composition in pellet from suitable for molding articles. The composition comprises a tacky hot melt composition comprising at least one high molecular weight triblock copolymer of the general configuration A-B-A
and a plasticizer and a pelletizing aid. The pelletizing aid substantially surroudns the tacky composition such that the molded articles are substantially free from surface tack. A method of forming the pellets is also disclosed.
and a plasticizer and a pelletizing aid. The pelletizing aid substantially surroudns the tacky composition such that the molded articles are substantially free from surface tack. A method of forming the pellets is also disclosed.
Description
A POLYMERIC COMPOSITION IN PELLET FORM
Field of The Invention This invention relates to a polymeric composition in pellet form comprising a tacky hot melt composition which can be used either for hot melt pressure sensitive applications or for molded articles. Those compositions suitable for pressure sensitive applications are defined by having a storage modulus, G', at 25°f, of about 5 x 105 dynes/cmZ or less, and each pellet has a substantially tack-free surface prior to melting, and pressure sensitive characteristics after resolidification. The polymeric compositions suitable for use in injection molding preferably comprise a high molecular weight block copolymer and have a tack-free surface both prior to melting the pellets, and after melting and resolidification.
Background Of The Invention Tacky hot melt compositions have been used widely in the adhesive industry for a wide range of applications such as for pressures sensitive adhesives due to their ability to adhere to a wide variety of substrates. A primayr property of a hot melt pressure sensitive composition is that it remain tacky at room temperature so that it may be adhered to substrates when it has completely cooled from its molterb state. Examples of applications which require this property are tape and label applications. Paper, polyethylene, polypropylene or other such substrates 2f may be coated with the tacky hot melt composition, covered with release liner, and then shipped this way for later applications such as for labels used on various containers, books, magazines, or envelopes just to name a few.
The use of tacky hot melt compositions in other applications has been precluded by the 2~ fact that they remain tacky. Yct it may be desirable to use these soft and very flexible compositions for other applications. One such application French Pat. No. 2,601,616 published tJct 22,1988 discloses forming blocks of hot melt pressure sensitive adhesive by casting the adhesive into molds precoated by spraying with a 30 film of non self sticking hot melt rna~terial.
German Pat. Nos. DE 31 :38 222, DE 32 34 065, and DE 36 25 358 teach coating or wrapping a formed hot melt block with various types of film.
3_'~ U.S. Pat. No. 5,257,491 to Rouyer et al. teaches a method of packaging a hot melt adhesive composition wherein the adhesive composition is sufficiently solidified or when flowable.
U.S. Pat. No. 5,401,455 to Hatfield et al. issued March 28, 1995 teaches a method for packaging hot melt adhesive comp<:~sitions comprising the use of a mold being in contact with a refrigerant gas or liquid heat sink.. Hatfield teaches that when a hot melt adhesive is poured into a cavity lined with film in its molten state, the adhesive is fused to some extent with the film. According to Hatfield, this in turn allows some mixing and compatibilizing from the film, improving the opportunity for more complete mixing.
U.S. Pat. No. 5,057,571 to Malcolm et al. discloses at column 8 line 59 to column 9 line 14 a method for pelletizing a preblend of a radial block copolymer and a tackifying resin.
This preblend is then used to make hat melt adhesives for disposable article construction. The preblend is manufactured on an extruder. l: he pelletized preblend was then used to make an adhesive using conventional hot melt mixers. This is a tvvo step process of making hot melt pressure sensitive adhesives, and it was never intended to teach making a finished product in a free-flowing pellet form.
EP 0 410 914 A1 describes h~ourable particles of normally soft and tacky plastic materials formed by extruding molten plastic material into contact with a cooling fluid containing a non-sticky material that as compatible with the plastic material, cutting the plastic material into particles, separating these particles from the cooling fluid, and contacting these particles with a second comparable non-sticky material. The document mentions that "excluding the second contacting of the particles with the non-sticky material, the particles are not pourable and block after setting for a short period of time."
EP 0 115 307 A2 describes a process for producing non-blocking hot melt adhesive by contacting the adhesive at a temperature above its melting point with a dispersion of a parting agent. Tackiness is observed in the adhesive objects produced in accordance with this method with parting agent concentrations a,s high as 20°/~ by weight in the dispersions employed in this reference.
The current inventors have found novel polymeric compositions in a free-flowing pellet form that can be either a hot melt pressure sensitive adhesive or a polymeric composition that has a surface that remains tack-free after melting and resolidification Summary of The Invention The present invention discloses a polymeric composition in pellet form, comprising:
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 5°i~ to 90°io by weight of a thermoplastic polymer;
(b) from 10°/. ti> 6~5% of a tackifying resin; and (c) from 0°io to SCE°~o by weight of a plasticizer; and II. from 0.1% to 3°ro by weight of a pelletizing aid substantially surrounding the tacky hot melt composition, wherein the hot melt composition has a storage modulus G', at about 25°C of about 5 x 105 dynes,'cm' or less, and each pellet has a substantially tack-free surface.
The tacky hot melt composition is a pressure sensitive adhesive having a storage modulus, G', at 25°C, of about 5 x l0' dynes/cm' or less, suitably from 1 x 104 dynes/cm2 to about 5 x 105 dynes/cm', as measured using a Rheometrics Scientific Dynamic Mechanical Spectrometer Model #RDS7700.
The pelletizing aid is used to provide hot melt pressure sensitive adhesives in pellet form wherein the pellet has a tack-free surface. Once the pellets are melted and resolidified, these compositions once again return to their original tacky state. These pellets are free-flowing and the resultant pelletized composition ca.n be used in various tape and label applications, in non-woven applications where pressure sensitive adhesives are used such as for positioning of feminine napl~:ins, diaper fastenirug systems, and disposable article construction, in the automotive industry where hot melt pressure sensitive adhesives are used for assembly applications, and for medical applications.
2~
The present invention ftrrther discloses a polymeric composition in pellet form, comprising:
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 1% to 20°ro by weight of a high molecular weight block 3C~ copolymer having a general configuration A-B-A and a molecular weight greater than 200,000;
(b) fronu 20 to 98 percent by weight of a compatible plasticizer; and (c) fronu 0% to 30 percent by weight of a compatible polymer;
35 II. from 0.1% to 3 percent by weight of a pelletizing aid, wherein the resultant polymeric compositions have a tack-free surface both prior to melting the pellets, and after melting and resolidification, The resultant tacky hot melt compositions are characterized by a specific gravity of greater than about 0.8, Mettler Softening Points of greater than about 90°C and Bloom Gelometer readings of greater than about 20 grams.
The pellets thus formed are soft, non-blocking, substantially without surface tack and exhibit an elastic rebound, as characterized by G' (elastic or storage modulus) measurements.
These compositions are suitable for use in molding, especially injection molding. Any molded products produced therefrom also retain the substantially tack-free surface.
While the bulk composition determines the properties of pellets, the palletizing aid determine the surface properties of the pellets, and has no effect on the bulk properties.
These pellets are suitable for use in molding, a pecially injection molding.
The composition suitable for such processca comprises:
I. A tacky hot melt composition, comprising:
(a) at least one high molecular weight triblock copolymer of the general configuration A-B-A; and (b) a plasticizer; and II. A palletizing aid, wherein said palletizing aid substantially surrounds the tacky composition such that the molded articles are soft, norn-blocking and have a substantially tack-free surface. Optionally, other compatible block copolymers such as radial blocks and diblocks and other triblocks can be added. Preferably, the tacky hot melt be ellipsoidal and cylindrical. The preferred dimensions for these shapes can range from about 3 mm by about 10 mm to about 10 mm by 20 min.
Any molded articles produced therefrom also retain the substantially tack-free surface and rebound properties. Such articles can include drum pads useful as acoustical pads for vibration damping, disc players, ear phones, percussion surfaces on electronic drum kits and so on; soles, shoes insoles, in-line skate soles and so on; pads for use in athletic gear such as mouth pads, protective guards, encapsulants for other solid protective pads and so on; bicycle seats, gloves, bicycle shorts and so on; medical equipment such as pads for wheel chairs, donut-I O shaped pads for seats and so on; furniture pads such as mattress pads, chair pads and so on; special effects articles such as body parts, Santa Claus' bellies, synthetic skin, and others that are useful in movies; and bandages, especially for burn wounds. While the rest of the composition determines the overall bulk properties of the pellets and articles molded therefrom, the pelletizing aid determines the surface properties of not only the pellets, but the articles made from such pellets.
The present invention. also discloses an under-water pelletizing process for making the tacky hot melt compositions in pellet form, utilizing a pelletizing aid to produce pellets that have a substantially tack-free surface making them non-blocking, and are soft. The process varies slightly for each product, dependent mainly on the plasticizer loading, and comprises the steps of:
a) blending the hot melt components to form a substantially homogeneous hot melt mixture;
b) forcing said substantially homogeneous hot melt mixture through a die for forming substantially homogeneous hot melt ribbons and forming resultant pellets therefrom;.
c) solidifying said pellets by use of a cooling medium; and d) applying said peiletizing aid at some point during the pelletizing process.
The pellets can be nxade into any convenient size. Preferably, the pellets are substantially spherical, with sizes ranging from about 1/8 to about 3/8 inch (about 3mrn to about l Omrn) in diameter for easy handling. The pellets can also be ellipsoidal and cylindrical. Th: preferred dimznsioas for these shapes can range tom about 3 nun by about IO mm to aboux 1Q aim by ZOmrn.
Description of the Figure Figure 1 is a plot of t:he storage modulus of the product of examples 1-4 as a function of temperature.
Detailed Descriptions of The Preferred Embodiments The pelletized polymeric compositions of the present invention can exhibit a spectrum of properties, ranging from compositions having hot melt pressure sensitive adhesive properties to compositions suitable for molding non-tacky articles. Those polymeric compositions for use in pressure sensitive applications have a storage modulus, G', at 2S°C of about 5 x 105 dynes/cmz or less, and preferably have a storage modulus, G', at about 25°C, from about 1 x 104 to about 5 x 105 d~-nes/cm'' while those useful for molding applications can have a storage modulus of greater than about 5 x 105 dynes/cm''. The storage modulus, G', is measured using a Rlreometrics Scientific Dynamic Mechanical Spectrometer Model #RDS7700.
The thermoplastic polymer may be a styrenic block copolymer having a styrene content from 10% by weight to 50'io b v weight, an isoprene:, butadiene, ethylene/butylene or ethylene/propylene midblock and a diblock content of less than about 90%.
The thermoplastic polymers useful for the present invention can include A-B-A
triblock copolymers, A-B diblock copolynuers, A-B-A-B-A-B multiblock copolymers, radial block copolymers and grafted versions thereof: homopolymers, copolynuers and terpolymers of ethylene; and homopolymers, copolymers and terpolymers of propylene; and mixtures thereof.
Radial block copolymers include Y-block and star polymers as well as other configurations.
The A-B-A block copolymers that are most useful herein are as described in U.S. Pat.
No. 4,136,699 to (Collins et al), which states: there are two basic types of heat-stable robbery or elastomeric block copolymers that are particularly well-suited for use in this invention, namely: (a) an A-B-A block copolymer having polystyrene end blocks and a nrbbery polyolefin center or mid-block, the polyolefin being a rubbery polyethylene-butylene) block, and (b) a teleblock copolymer comprising molecules having at least three branches radially branching out from a central hub, each said branch havin~; polystyrene terminal blocks and a butadiene segment in the center. It is believed that this type of block copolymer could also be described as having a branched polymerized butadiene mid-block with a polystyrene terminal block at the end of each branch.. l~xamples include those polymers available under the KratonTM G series from Shell Chemical C.o in Houston, T'X. There are various grades available including KratonTM G-1726, KratonT"' G-Iti50, KratonTM G-1651, KratonTM G-1652, KratonTM
G-1657, all saturated A-B diblock~'A-B-A triblock mixture°s with ethylene/butylene midblocks;
KratonTM D-1112 a high percent A-B diblock linear styrene-isoprene-styrene polymer;
KratonTM D-1107 and KratonTM D-111 l , primarily A-B-A triblock linear styrene-isoprene-styrene block copolymers; Kraton'~'"~ D4433X, a linear SIS block copolymer with an oil content of 30% by weight and KratonTM 1:)11$4, a high molecular weight SBS block copolymer both available from Shell Chemical Co; StereonTM 840A and StereonTM 841A, A-B-A.
B-A-B multiblock SBS block copolymers available from Firestone in Akron, Ohio; EuropreneTM Sol T-i93B, a linear SIS block copolymer available from Enichem Elastomers in.1'tew York, NY; EuropreneTM Sol. T-I90, a linear styrene-isoprene-styrene block copolymer and EuropreneTU Sol T-163, a radial SBS block copolymer both also available from Enichem 131astomers; VectorTM 4461-D, a linear SBS block copolymer available from Exxon Chemical Co. in Houston, Texas; VectorTM 4111, 4:? 11 and 4411, fully coupled linear SIS block copolymers containing different weight percentages of styrene endblock; and VectorTM
4113, a highly coupled linear SI~~ block capolymer also available from Exxon Chemical IO Co.; and DPX-550, DPX-551 and DPX-552 radial SIS block copolymers available from Dexco Polymers in Houston, Texas. This list in not exclusive and there are numerous grades of block copolymers available from various sources for hot melt pressure sensitive adhesives. These polymers may be used alone, or in any combinations. These polymers are useful from about 5°/~ to about 90% by weight in the polymeric composition.
The polymeric compositions suitable for molding applications may comprise any of the above mentioned polymez-s which have a high molecular weight and preferably have a weight average molecular weight greater than about 200,000 as measured by Gel Permeation Chromatography, with values reported relative to styrene standards. The polymer is preferably a substantially linear copolymer having the general co~guration A-B-A. wherein the A block can be polystyrene and the B block can be ethylene-butylene, ethylene-propylene, isoprene, butadiene or mixtures thereof, and preferably the B block is ethylene-butylene or ethylene-propylene. Polymers of this type, such as KratonTM G-1651, are twice the molecular weight of conventional styrene-ethylene/butylene-styrene (S-EB-S) block copolymers used in the hot melt adhesive industry. This copolymer is present izn 2unounts from about 2 to about 20 percent by weight and preferably from about :p to about 2U percent by weight in the polymeric composition.
Other lower molecular weight block copolymers may be utilized with these high molecular weight biiock copolymers. Sorne examples are A-B-A triblock copolymers, A-B diblcrch copolymers, A-B-A-B-A-B multiblock copolymers, radial block copolymers, and grafted versions of ouch copolymers including Shell Chemical's TKG-101 and RP-6912. Such A-B-A, block copolymers are disclosed in CoIlins et al., U.S. Pat. No. 4,136,699. Some of these block copolymers are commercially available from Shell Chemical Co. under the KratonTM G series which are S-EB-S block cofsolymers.
Other useful polymers include atactic polyalphaolefins such as those available from Rexene Products C:o. in Dallas, Texas under the tradename of RextacTM such as RT-228t:) and R'r-2315 and RT-2585 having various amounts of ethylene and homogeneous .linear or substantially linear interpolyrners of ethylene with at least one Ci to C2~, ailphaolefin, further characterized by each said interpolymer having a polydiispersity less than about 2.5 including such polymers as ExactTM 5008, an ethylene-butene copolymer, :Exxpol SLP-0394TM, and ethylene-propylene copolymer, ExactTM 3031, an ethylene-hexene copolymer, all available from Dow Chemical Co. in Midland, MI. These polymers may have to be used in small concentrations if utilized with such block copolymers as KratonTM G-1651 to maintain compatibility without phase separation or snotty, gel-like compositions. T'hes;e concentrations may be as low as 5% by weight in the composition.
Other compatible polymers may be useful in the polymeric compositions of the present invention including ethylene vinyl acetate copolymers such as EIvaxTM 410, a 14% vinyl ac;etate/400 melt index copolymer and ElvaxTM 210, a 28% vinyl acetate/400 rn~lt index copolymer, both available from DuPont Chemical Co. in Wilmington, DE; EscoreneTM UT 7505 an ethylene vinyl acetate copolymer available from Exxon Chemical Co.; Ultrathene''M UE 64904 available from Quantum Chemical Co., U.S~I. Division in Cincinnati, OH; and AT 1850M
available from AT Polymer:9 & Film Co, in Charlotte, North Carolina.
Copolymers of ethylene and. methyl acrylate (meihacryiates as well as acrylates) are also useful including OptemaTM T'C-140, XS-93.04 and 'fC-221 available from Exxon Chemical Co.; LotrylTM 28 MA 175 and 35 MA OS 1000 available from Elf Atochem North America i.n Philadelphia, PA. Ethylene methyl acrylate copolymers are also avail:xbie from Chevron under the tradename of EmacTM and from Quanturr~ Chemical a:c>. under the tradename of AcrytheneTM. Copolymers of ethylene and n-butyl ac:rylate are also useful in the adhesives of the invention.
They are available frorrc CZuanturn Chemical Co. under the tradename of EnatheneTM including EA80808, EA 89821 and EA89822; from Elf Atochem North America under t1e ttadename of Lotryh"~ including 35 BA 900 and 35 BA , 5 1000; from Exxon Chemical Co. under the tradename of EscoreneTM including XW-23.AH and XW-2~'.. These polymers may also have to be used in small concentrations with some of the block copolymers such as Kraton'''''~ G-1651.
The polymeric compositions may also comprise a tackifying resin. While they are preferable for use in hot melt pressure sensitive composirions, they may I O or may not be utilized in the molded article compositions.. The tackifying resins useful herein include aliphatic, cycloaliphatic and aromatic hydrocarbons and modified hydrocarbons arid hydrogenated derivatives; terpenes and modified terpenes and hydrogenated derivatives; rosins and modified rosins and hydrogenated derivatives; and mixtures thereof: These tackifying resins have a ring and ball softening point of between about '70°C and 150°C.
They are also available with differing levels of hydrogenation, or saturation which is another commonly used term. Useful examples include EastotacTM H-100, H-115 and H-130 from Eastman Chemical Co. in Kingsport, TN which are partially hydrogenated cycloaliphatic petroleum hydroc~~rbon resins with different softening points. These acre available in the E _e;rade, the R grade, the L
grade and the W grade. These have differing levels of hydrogenation from least hydrogenated to most hydrogenated. The E grade has a bromine number of 15, the R grade a bromine number of 5, the L grade has a bromine number of 3 and the W grade a bromine number of 1. There is also an EastotacTM H-1428 resin available. Other useful tankifying resins include Escorez 1310 LC, an aliphatic hydrocarbon resin, EscorezTM 5300 and Escore::TM 5400, partially hydrogenated cycloaliphatic petroleurxi .hydrocarbon resins, and EscorezT"" 5600, a partially hydrogenated aromatic modified petroleum hyc(rocarbon resin all available from Exxon Chemical Co. in Houston, TX; WingtackTM Extra which is an aliphatic, aromatic petroleum hydrocarbon resin available from Goodyear Chemical C'o. in Akron, OH; Hercolite''T~ 2100 which is a partially hydrogenated cycloaliphatic petroleum hydrocarbon resin available from Hercules in Wilmington, DE; and W
ZonatacTM 105 Lite which is a styrenated terpene resin made from d-Iimonene and available from Arizona Che:mical Co, in Panama. City, FL. There are numerous types of rosins and modi3:ied rosins available with differing levels of hydrogenation including gum rosins, wood rosins, tall-oil rosins, distilled rosins, dimerized rosins and polyrr~erized rosins. Some specific modified rosins include glycerol and pentaerythritoli esters of wood rosins and tall-oil rosins.
Commercially available grades include, but are not limited to, SylvatacTM
1103, a pentaerythritol rosin ester available from Arizona Chemical Co., UnitacTM R-Lite a pentaerythritol rosin ester from Union Camp in Wayne, NJ, ZonesterTM
100, a glycerol ester of t<~11 oil rosin from Arizona Chemical Co., PermalynTM
305, a pentaerythritol modified wood rosin available from Hercules, Inc. in Wilmington, DE and ForalTM l OS, which is a highly hydrogenated pentaerythritol rosin ester available. SylvatacTM R-85 which is ara 85°C melt point rosin acid and SylvatacTM 295 which is a 95°C melt point rosin acid are both available from Arizona Chemical Co.. For,rITM AX is a 75°C melt point hydrogenated rosin acid available from Hercules lnc. NirezTM V-2040 is a phenolic modified terpene resin available from Arizona Chemical Co. There are many available types and grades of tackifying resins available from many companies, and one skilled in the art would recognize that this is not an exclusive List, and that the available tackifying resins are too numerous to list here. Various encl.block resins are also useful in the compositions of the present invention. These include Ende:YTM 160, an aromatic hydrocarbon manufactured by Hercules, Inc. in Wilmington, DE; KristalexTM
3100 and KristalexTM 5140, alphamethyl styrene hydrocarbons manufactured by Hercules, Inc.; and also coumarone indene resins. These tackifiers are useful from about 0% to about 65% by weight, and preferably from about 10% to about 65%.
The plasticizers uye:Eul in the present invention may include mineral based oils and petroleum based oils, liquid resins, liquid clastomers, polybutene, polyisobutylene, functionalized oils such as glycerol trihydroxyoIeate and other fatty oils and mixtures thcre:of. A plasticizes is broadly defined as a typically organic composition that can be added to the therznopiastics, rubbers and other resins to improve extrudability, t'~exibility, workabilit3~ and stretchability in the finished adhesive. Any material which flows at ambient temperatures and is compatible with the block copolymer may be useful.
The most comrnc.~nly used plasticizers are oils which are primarily hydrocarbon oils that are low in aromatic content and are paraffmic or naphthenic S in character. The oils .:ire; preferably low in volatility, transparent and have as little color and odor as possible. This invention also contemplates the use of olefin oligomers, low molecu.la:r weight polymers, vegetable oils and their derivatives and similar plasticizing oils.
Examples of useful plasticizers include CalsolTM .5120, a naphthenic petroleum based oil available from Calumet Lubricants Co. in Indianapolis, IN;
KaydolTM White Mineral Oil, a paraffinic mineral oil available from Witco Corp.
in New York, NY; ParapolTM 1300, a liquid butene homopolymer available from Exxon Chemical Co. ire Houston, T'X; IndopolTM H-300, a liquid butene homopolymer, available iTOm Amoco Coip, in Chicago, IL; EscorezTM 2520, a liquid aromatic petroley.un based hydrocarbon resin with a pour point of 20°C, available from Exxon Chemical Co.; Regalrei''M 1018, a liquid hydrogenated aromatic hydrocarbon resin with a pour point of 18°C, available from Hercules, Ire. in Chicago, IL; and SylvatacTM SN, a liquid resin of modified rosin ester with a pour point of 5°C, available from Arizona Chemical Co. in Panama City, FL.
One skilled in the art would recognize that any generic 500 second or 1200 second naphthenic process oil would also be useful. These plasticizers are useful in amounts from about 0% to about 50% by weight for the hot melt pressure sensitive compositions, acid up to about 98% by weight in the molded article compositions, and preferably up to about 90% by weight.
A pelletizing aid is used to change the surface characteristics of the pellets.
It would be generally undesirable for molded articles manufactured by such , methods as injection molding, to remain tacky. Surprisingly, a small amount of pelletizing aid can make the surface of the pellets substantially non-tacky.
The pelletizing aids do not change the end use properties of the tacky composition, as in the formulas used as hot melt pressure sensitive adhesives, or they do change the physical properties i>f the tacky composition, as in the case of the formulas used for the molding applucations.
The pelietizing aid is selected from the group consisting of polyethylene waxes, modified polyethylene waxes, polyamide waxes and stearamide waxes.
Many other waxes or pelletizing aids not on this list could also be useful provided the surface of the resultant pellet is tack-free_ Preferred waxes are Acrawax CTM
stearamide wax available .from Lonza, Inc. in Fair lawn, NJ; CastorTM hydroxy waxes and ParicinTM hydroxyamide waxes available form Caschem in Bayonne, NJ; NeptuneTM 968 available: from Shamrock Technologies in Newark, NJ;
ShamrockTM S-395 polyethylene wax available from Shamrock Technologies; and HoechstTM Wax PED 121, a modified polyethylene available from Hoechst Celanese in Somerville, N7. More preferably, these pelletizing aids are polyethylene waxes and come in powder form. The pelIetizing aid is present from about 0.1 percent to about 3 percent by weight and preferably from about 0.1 percent to about 1 percent: b:y weight. This amount is substantially less or comparable to the packaging film of prior art packaging methods. It is believed that the temperature of use~ c>f the tacky hot melt composition controls whether the surface of tacky hot melt ca:mposition returns to the substantially tack-free state after melting the pellets, and subsequent resolidification.
A stabilizer or antioa~idant can also be used in the polymeric compositions.
These compounds are added to protect the adhesive from degradation caused by reaction with oxygen induced by such things as heat, light or residual catalyst from the raw materials such as the tackifying resin. Such antioxidants are commercially available from Ciba-Geigy in Hawthorne, NY and include IrganoxTM 565, IrganoxTM 1010 and IrganoxTM 1076, all hindered phenolic antioxidants. These are primary antioxidants which act as free radical scavengers and may be used alone or in combination with other antioxidants such as phosphite antioxidants like IrgafosTM 168 available from Ciba-Geigy. Phosphite antioxidants are considered secondary antioxidants, are primarily used as peroxide decomposers and are generally not used alone, but are instead used in combination with other antioxidants. tether available antioxidants are CyanoxTM LTDP, a thioether antioxidant, available from Cytec Industries in 5tamford, CT
,EthanoxTM
330, a hindered phenolic antioxidant, available from Albemarle in Baton Rouge, LA. Many other antioxidants are available or use by themselves, or in combination with other antioxidants. These compounds are added to the hot melts in small amounts, up to about 2% by weight in the hot melt pressure sensitive adhesive, and have no effect on the physical properties of the adhesive.
Other compounds that also could be added that have no effect on the S physical properties are pi~;ments which add color, fluorescing agents, any compounds That mask odor and fillers to mention only a few. Additives such as these are known to one of'skill in the art.
Fillers come in zhe form of particulate rnatter, fibers and powders, or may be any material that does ;not interfere with the other components in the adhesive.
Some examples include c<~lcium carbonate, ceramics, glass, silica, quartz, mica, treated clay, titanium dioxide, boron nitrides, graphite, carbon black, metals, barium, sulfate, talc and mixtures thereof. Such additives are known to one of skill in the art.
As discussed above, the resultant pellets are soft, non-blocking, 1 S substantially free from surface tack a.nd exhibit an elastic rebound. This last.
characteristic can be measured by the elastic or storage modulus, G'. The higher the modulus, the more likely that the material will return to its original shape. At lower loadings of the high molecular weight triblock copolymer, the pellets formed resemble gels. ":f hey possess some elastic rebound, but tend to retain the same physical property ~:wer a wide-temperature range, or over a long period of time. These pellets are desirable for making articles such as Santa Claus' bellies.
At higher loadings of the copolymer, the pellet.5 formed have high elastic modulus and tend to return to their original shape faster. They are more suited for producing articles such ~:~s drum pads.
2S Compatible polymers or copolymers discussed above can also be added to modify the properties of the pellets. These are generally of low molecular weight, and pellets made with am amount of the high molecular weight triblock copolymer tend to have more rebound than those made with the same amount of a blend of this copolymer and the lovv molecular weight compatible polymer or copolymer.
These compatible polymers or copolymers are thus added for customizing the final applications or uses.
These pellets are suitable for use in molding, especially injection molding.
The composition suitable: for such processes comprises:
I. A tacky hot melt composition, comprising:
a) at lesst one high molecular weight triblock copolymer of 5 the general configuration A-B-A; and b) a pia;~ticizer; and II. A pelletizing aid;
wherein said pelletizing aid substantially surrounds the tacky composition such that the molded articles are soft, non-blocking and substantially without surface 10 tack. Optionally, other polymers such as diblock or other triblocks can be added.
Preferably, the tacky hot melt composition comprises .from about 97 to about 99.9 percent by weight of the artiicle, more preferably from about 99 to about 99.9 percent by weight.
Any molded articles produced therefrom also retain the substantially tack-15 free surface and rebound properties. Such articles can include drum pads useful as acoustical pads for vibration damping, disc players, ear phones, percussion surfaces on electronic drum kits and so on; soles shoes insoles, in-line skate soles and so on; pads for use in athletic gear such as mouth pads, protective guards, encapsulants for other solid protective pads and so on; bicycle seats, gloves, bicycle shorts and so on; medical eguipment such as pads for wheel chairs, donut-shaped pads for seats and so on; furniture pads such as mattress pads, chair pads and so on; special effects articles such as body parts, Santa Claus' bellies, and other that are useful in movies. Unlike the prior art, the palletizing aid used herein blooms to the surface during the molding process, such that it substantially completely surrounds the tacky composition below and produces articles substantially free of surface tack when cooled. This is surprising because the amount of palletizing aid used in the formulation is small, and according to prior art teachings, should not substantially interfere with the properties of the bulk composition, nor should it: change the surface properties.
The present invention further discloses a method for making such pellets for all the formulations of the invention. The manufacturing process can vary slightly for each product depending on the plasticizer loading. The current WO 97/19582 PC'IYUS96/18507 process requires multiple passes through a co-rotating twin screw extruder with the product being pelIetized at the end of each pass, and then refed into the extruder for the further arildition of plasticizer. The compositions with 90 percent plasticizer or more need tJhree passes, while lower plasticizer loadings may require only two. It is important to note that the materials are pelletized with the pelletizing aid after both passes. The concentration of the pelletizing aid in the water can range from about 0.1 percent to about 3 percent by weight, preferably about O.I to about 1 percent by weight based on anticipated production rate for each pass. A specific preferred manufacturing process comprises:
a) blending W a hot melt components to form a substantially homogeneous hot melt mixture;
b) forcing said substantially homo~;eneous hot melt mixture through a die having a series of~ voids in a circular pattern to form a series of substantially homogeneous hot melt ribbons;
c) further forcing said homogeneous hot melt ribbons past rotating blades in. substantially parallel position to said die, cutting said substantial:fy homogeneous hot melt ribbons to form resultant pellets;
d) substantially solidifying said pellets by use of a liquid cooling medium said liquid cooling medium containing a pelletizing aid, being circulated past said die and rotating blades on the side where said substantially homogeneous hot melt ribbons emerge;
e) transport:in;~ said hat melt pellets to a drying area;
f) substantially removing liquid from said hot melt pellets by blowing.
As depicted above, the pelletizing aid is present in the cooling medium. It can also be added to the hot melt composition prior to blending or during the pelletizing steps by cofeeding a solution of pelletizing aid with the hot melt composition.
As noted above, it is well known in the art that stabilizers or antioxidants can also be added to the compositions in small amounts and have no effect on the other physical properties csf the compositions. I~ther compounds that could be added that also do not effect physical properties are pigments for color, fluorescing agents, and an;y compounds that mask odor. Additives such as these are known to one of skill r.n the art.
This invention is fur~rher illustrated by the following non-limiting examples.
EXAMPLES
Test Methods 1. Melt Vi~,cosities The melt viscosities of the hot melt adhesives were determined on a Brookfield Thermosel Viscosmeter Model DV-Il+. using either a number 21 ar 27 spindle.
I S 2. Specific Gravity The specific gravity was determined using test method ASTM D792 with isopropyl alcohol as the liquid.
3. Mettler Softenine Point The Mettler softening points are determined using test method ASTM
D3461.
Field of The Invention This invention relates to a polymeric composition in pellet form comprising a tacky hot melt composition which can be used either for hot melt pressure sensitive applications or for molded articles. Those compositions suitable for pressure sensitive applications are defined by having a storage modulus, G', at 25°f, of about 5 x 105 dynes/cmZ or less, and each pellet has a substantially tack-free surface prior to melting, and pressure sensitive characteristics after resolidification. The polymeric compositions suitable for use in injection molding preferably comprise a high molecular weight block copolymer and have a tack-free surface both prior to melting the pellets, and after melting and resolidification.
Background Of The Invention Tacky hot melt compositions have been used widely in the adhesive industry for a wide range of applications such as for pressures sensitive adhesives due to their ability to adhere to a wide variety of substrates. A primayr property of a hot melt pressure sensitive composition is that it remain tacky at room temperature so that it may be adhered to substrates when it has completely cooled from its molterb state. Examples of applications which require this property are tape and label applications. Paper, polyethylene, polypropylene or other such substrates 2f may be coated with the tacky hot melt composition, covered with release liner, and then shipped this way for later applications such as for labels used on various containers, books, magazines, or envelopes just to name a few.
The use of tacky hot melt compositions in other applications has been precluded by the 2~ fact that they remain tacky. Yct it may be desirable to use these soft and very flexible compositions for other applications. One such application French Pat. No. 2,601,616 published tJct 22,1988 discloses forming blocks of hot melt pressure sensitive adhesive by casting the adhesive into molds precoated by spraying with a 30 film of non self sticking hot melt rna~terial.
German Pat. Nos. DE 31 :38 222, DE 32 34 065, and DE 36 25 358 teach coating or wrapping a formed hot melt block with various types of film.
3_'~ U.S. Pat. No. 5,257,491 to Rouyer et al. teaches a method of packaging a hot melt adhesive composition wherein the adhesive composition is sufficiently solidified or when flowable.
U.S. Pat. No. 5,401,455 to Hatfield et al. issued March 28, 1995 teaches a method for packaging hot melt adhesive comp<:~sitions comprising the use of a mold being in contact with a refrigerant gas or liquid heat sink.. Hatfield teaches that when a hot melt adhesive is poured into a cavity lined with film in its molten state, the adhesive is fused to some extent with the film. According to Hatfield, this in turn allows some mixing and compatibilizing from the film, improving the opportunity for more complete mixing.
U.S. Pat. No. 5,057,571 to Malcolm et al. discloses at column 8 line 59 to column 9 line 14 a method for pelletizing a preblend of a radial block copolymer and a tackifying resin.
This preblend is then used to make hat melt adhesives for disposable article construction. The preblend is manufactured on an extruder. l: he pelletized preblend was then used to make an adhesive using conventional hot melt mixers. This is a tvvo step process of making hot melt pressure sensitive adhesives, and it was never intended to teach making a finished product in a free-flowing pellet form.
EP 0 410 914 A1 describes h~ourable particles of normally soft and tacky plastic materials formed by extruding molten plastic material into contact with a cooling fluid containing a non-sticky material that as compatible with the plastic material, cutting the plastic material into particles, separating these particles from the cooling fluid, and contacting these particles with a second comparable non-sticky material. The document mentions that "excluding the second contacting of the particles with the non-sticky material, the particles are not pourable and block after setting for a short period of time."
EP 0 115 307 A2 describes a process for producing non-blocking hot melt adhesive by contacting the adhesive at a temperature above its melting point with a dispersion of a parting agent. Tackiness is observed in the adhesive objects produced in accordance with this method with parting agent concentrations a,s high as 20°/~ by weight in the dispersions employed in this reference.
The current inventors have found novel polymeric compositions in a free-flowing pellet form that can be either a hot melt pressure sensitive adhesive or a polymeric composition that has a surface that remains tack-free after melting and resolidification Summary of The Invention The present invention discloses a polymeric composition in pellet form, comprising:
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 5°i~ to 90°io by weight of a thermoplastic polymer;
(b) from 10°/. ti> 6~5% of a tackifying resin; and (c) from 0°io to SCE°~o by weight of a plasticizer; and II. from 0.1% to 3°ro by weight of a pelletizing aid substantially surrounding the tacky hot melt composition, wherein the hot melt composition has a storage modulus G', at about 25°C of about 5 x 105 dynes,'cm' or less, and each pellet has a substantially tack-free surface.
The tacky hot melt composition is a pressure sensitive adhesive having a storage modulus, G', at 25°C, of about 5 x l0' dynes/cm' or less, suitably from 1 x 104 dynes/cm2 to about 5 x 105 dynes/cm', as measured using a Rheometrics Scientific Dynamic Mechanical Spectrometer Model #RDS7700.
The pelletizing aid is used to provide hot melt pressure sensitive adhesives in pellet form wherein the pellet has a tack-free surface. Once the pellets are melted and resolidified, these compositions once again return to their original tacky state. These pellets are free-flowing and the resultant pelletized composition ca.n be used in various tape and label applications, in non-woven applications where pressure sensitive adhesives are used such as for positioning of feminine napl~:ins, diaper fastenirug systems, and disposable article construction, in the automotive industry where hot melt pressure sensitive adhesives are used for assembly applications, and for medical applications.
2~
The present invention ftrrther discloses a polymeric composition in pellet form, comprising:
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 1% to 20°ro by weight of a high molecular weight block 3C~ copolymer having a general configuration A-B-A and a molecular weight greater than 200,000;
(b) fronu 20 to 98 percent by weight of a compatible plasticizer; and (c) fronu 0% to 30 percent by weight of a compatible polymer;
35 II. from 0.1% to 3 percent by weight of a pelletizing aid, wherein the resultant polymeric compositions have a tack-free surface both prior to melting the pellets, and after melting and resolidification, The resultant tacky hot melt compositions are characterized by a specific gravity of greater than about 0.8, Mettler Softening Points of greater than about 90°C and Bloom Gelometer readings of greater than about 20 grams.
The pellets thus formed are soft, non-blocking, substantially without surface tack and exhibit an elastic rebound, as characterized by G' (elastic or storage modulus) measurements.
These compositions are suitable for use in molding, especially injection molding. Any molded products produced therefrom also retain the substantially tack-free surface.
While the bulk composition determines the properties of pellets, the palletizing aid determine the surface properties of the pellets, and has no effect on the bulk properties.
These pellets are suitable for use in molding, a pecially injection molding.
The composition suitable for such processca comprises:
I. A tacky hot melt composition, comprising:
(a) at least one high molecular weight triblock copolymer of the general configuration A-B-A; and (b) a plasticizer; and II. A palletizing aid, wherein said palletizing aid substantially surrounds the tacky composition such that the molded articles are soft, norn-blocking and have a substantially tack-free surface. Optionally, other compatible block copolymers such as radial blocks and diblocks and other triblocks can be added. Preferably, the tacky hot melt be ellipsoidal and cylindrical. The preferred dimensions for these shapes can range from about 3 mm by about 10 mm to about 10 mm by 20 min.
Any molded articles produced therefrom also retain the substantially tack-free surface and rebound properties. Such articles can include drum pads useful as acoustical pads for vibration damping, disc players, ear phones, percussion surfaces on electronic drum kits and so on; soles, shoes insoles, in-line skate soles and so on; pads for use in athletic gear such as mouth pads, protective guards, encapsulants for other solid protective pads and so on; bicycle seats, gloves, bicycle shorts and so on; medical equipment such as pads for wheel chairs, donut-I O shaped pads for seats and so on; furniture pads such as mattress pads, chair pads and so on; special effects articles such as body parts, Santa Claus' bellies, synthetic skin, and others that are useful in movies; and bandages, especially for burn wounds. While the rest of the composition determines the overall bulk properties of the pellets and articles molded therefrom, the pelletizing aid determines the surface properties of not only the pellets, but the articles made from such pellets.
The present invention. also discloses an under-water pelletizing process for making the tacky hot melt compositions in pellet form, utilizing a pelletizing aid to produce pellets that have a substantially tack-free surface making them non-blocking, and are soft. The process varies slightly for each product, dependent mainly on the plasticizer loading, and comprises the steps of:
a) blending the hot melt components to form a substantially homogeneous hot melt mixture;
b) forcing said substantially homogeneous hot melt mixture through a die for forming substantially homogeneous hot melt ribbons and forming resultant pellets therefrom;.
c) solidifying said pellets by use of a cooling medium; and d) applying said peiletizing aid at some point during the pelletizing process.
The pellets can be nxade into any convenient size. Preferably, the pellets are substantially spherical, with sizes ranging from about 1/8 to about 3/8 inch (about 3mrn to about l Omrn) in diameter for easy handling. The pellets can also be ellipsoidal and cylindrical. Th: preferred dimznsioas for these shapes can range tom about 3 nun by about IO mm to aboux 1Q aim by ZOmrn.
Description of the Figure Figure 1 is a plot of t:he storage modulus of the product of examples 1-4 as a function of temperature.
Detailed Descriptions of The Preferred Embodiments The pelletized polymeric compositions of the present invention can exhibit a spectrum of properties, ranging from compositions having hot melt pressure sensitive adhesive properties to compositions suitable for molding non-tacky articles. Those polymeric compositions for use in pressure sensitive applications have a storage modulus, G', at 2S°C of about 5 x 105 dynes/cmz or less, and preferably have a storage modulus, G', at about 25°C, from about 1 x 104 to about 5 x 105 d~-nes/cm'' while those useful for molding applications can have a storage modulus of greater than about 5 x 105 dynes/cm''. The storage modulus, G', is measured using a Rlreometrics Scientific Dynamic Mechanical Spectrometer Model #RDS7700.
The thermoplastic polymer may be a styrenic block copolymer having a styrene content from 10% by weight to 50'io b v weight, an isoprene:, butadiene, ethylene/butylene or ethylene/propylene midblock and a diblock content of less than about 90%.
The thermoplastic polymers useful for the present invention can include A-B-A
triblock copolymers, A-B diblock copolynuers, A-B-A-B-A-B multiblock copolymers, radial block copolymers and grafted versions thereof: homopolymers, copolynuers and terpolymers of ethylene; and homopolymers, copolymers and terpolymers of propylene; and mixtures thereof.
Radial block copolymers include Y-block and star polymers as well as other configurations.
The A-B-A block copolymers that are most useful herein are as described in U.S. Pat.
No. 4,136,699 to (Collins et al), which states: there are two basic types of heat-stable robbery or elastomeric block copolymers that are particularly well-suited for use in this invention, namely: (a) an A-B-A block copolymer having polystyrene end blocks and a nrbbery polyolefin center or mid-block, the polyolefin being a rubbery polyethylene-butylene) block, and (b) a teleblock copolymer comprising molecules having at least three branches radially branching out from a central hub, each said branch havin~; polystyrene terminal blocks and a butadiene segment in the center. It is believed that this type of block copolymer could also be described as having a branched polymerized butadiene mid-block with a polystyrene terminal block at the end of each branch.. l~xamples include those polymers available under the KratonTM G series from Shell Chemical C.o in Houston, T'X. There are various grades available including KratonTM G-1726, KratonT"' G-Iti50, KratonTM G-1651, KratonTM G-1652, KratonTM
G-1657, all saturated A-B diblock~'A-B-A triblock mixture°s with ethylene/butylene midblocks;
KratonTM D-1112 a high percent A-B diblock linear styrene-isoprene-styrene polymer;
KratonTM D-1107 and KratonTM D-111 l , primarily A-B-A triblock linear styrene-isoprene-styrene block copolymers; Kraton'~'"~ D4433X, a linear SIS block copolymer with an oil content of 30% by weight and KratonTM 1:)11$4, a high molecular weight SBS block copolymer both available from Shell Chemical Co; StereonTM 840A and StereonTM 841A, A-B-A.
B-A-B multiblock SBS block copolymers available from Firestone in Akron, Ohio; EuropreneTM Sol T-i93B, a linear SIS block copolymer available from Enichem Elastomers in.1'tew York, NY; EuropreneTM Sol. T-I90, a linear styrene-isoprene-styrene block copolymer and EuropreneTU Sol T-163, a radial SBS block copolymer both also available from Enichem 131astomers; VectorTM 4461-D, a linear SBS block copolymer available from Exxon Chemical Co. in Houston, Texas; VectorTM 4111, 4:? 11 and 4411, fully coupled linear SIS block copolymers containing different weight percentages of styrene endblock; and VectorTM
4113, a highly coupled linear SI~~ block capolymer also available from Exxon Chemical IO Co.; and DPX-550, DPX-551 and DPX-552 radial SIS block copolymers available from Dexco Polymers in Houston, Texas. This list in not exclusive and there are numerous grades of block copolymers available from various sources for hot melt pressure sensitive adhesives. These polymers may be used alone, or in any combinations. These polymers are useful from about 5°/~ to about 90% by weight in the polymeric composition.
The polymeric compositions suitable for molding applications may comprise any of the above mentioned polymez-s which have a high molecular weight and preferably have a weight average molecular weight greater than about 200,000 as measured by Gel Permeation Chromatography, with values reported relative to styrene standards. The polymer is preferably a substantially linear copolymer having the general co~guration A-B-A. wherein the A block can be polystyrene and the B block can be ethylene-butylene, ethylene-propylene, isoprene, butadiene or mixtures thereof, and preferably the B block is ethylene-butylene or ethylene-propylene. Polymers of this type, such as KratonTM G-1651, are twice the molecular weight of conventional styrene-ethylene/butylene-styrene (S-EB-S) block copolymers used in the hot melt adhesive industry. This copolymer is present izn 2unounts from about 2 to about 20 percent by weight and preferably from about :p to about 2U percent by weight in the polymeric composition.
Other lower molecular weight block copolymers may be utilized with these high molecular weight biiock copolymers. Sorne examples are A-B-A triblock copolymers, A-B diblcrch copolymers, A-B-A-B-A-B multiblock copolymers, radial block copolymers, and grafted versions of ouch copolymers including Shell Chemical's TKG-101 and RP-6912. Such A-B-A, block copolymers are disclosed in CoIlins et al., U.S. Pat. No. 4,136,699. Some of these block copolymers are commercially available from Shell Chemical Co. under the KratonTM G series which are S-EB-S block cofsolymers.
Other useful polymers include atactic polyalphaolefins such as those available from Rexene Products C:o. in Dallas, Texas under the tradename of RextacTM such as RT-228t:) and R'r-2315 and RT-2585 having various amounts of ethylene and homogeneous .linear or substantially linear interpolyrners of ethylene with at least one Ci to C2~, ailphaolefin, further characterized by each said interpolymer having a polydiispersity less than about 2.5 including such polymers as ExactTM 5008, an ethylene-butene copolymer, :Exxpol SLP-0394TM, and ethylene-propylene copolymer, ExactTM 3031, an ethylene-hexene copolymer, all available from Dow Chemical Co. in Midland, MI. These polymers may have to be used in small concentrations if utilized with such block copolymers as KratonTM G-1651 to maintain compatibility without phase separation or snotty, gel-like compositions. T'hes;e concentrations may be as low as 5% by weight in the composition.
Other compatible polymers may be useful in the polymeric compositions of the present invention including ethylene vinyl acetate copolymers such as EIvaxTM 410, a 14% vinyl ac;etate/400 melt index copolymer and ElvaxTM 210, a 28% vinyl acetate/400 rn~lt index copolymer, both available from DuPont Chemical Co. in Wilmington, DE; EscoreneTM UT 7505 an ethylene vinyl acetate copolymer available from Exxon Chemical Co.; Ultrathene''M UE 64904 available from Quantum Chemical Co., U.S~I. Division in Cincinnati, OH; and AT 1850M
available from AT Polymer:9 & Film Co, in Charlotte, North Carolina.
Copolymers of ethylene and. methyl acrylate (meihacryiates as well as acrylates) are also useful including OptemaTM T'C-140, XS-93.04 and 'fC-221 available from Exxon Chemical Co.; LotrylTM 28 MA 175 and 35 MA OS 1000 available from Elf Atochem North America i.n Philadelphia, PA. Ethylene methyl acrylate copolymers are also avail:xbie from Chevron under the tradename of EmacTM and from Quanturr~ Chemical a:c>. under the tradename of AcrytheneTM. Copolymers of ethylene and n-butyl ac:rylate are also useful in the adhesives of the invention.
They are available frorrc CZuanturn Chemical Co. under the tradename of EnatheneTM including EA80808, EA 89821 and EA89822; from Elf Atochem North America under t1e ttadename of Lotryh"~ including 35 BA 900 and 35 BA , 5 1000; from Exxon Chemical Co. under the tradename of EscoreneTM including XW-23.AH and XW-2~'.. These polymers may also have to be used in small concentrations with some of the block copolymers such as Kraton'''''~ G-1651.
The polymeric compositions may also comprise a tackifying resin. While they are preferable for use in hot melt pressure sensitive composirions, they may I O or may not be utilized in the molded article compositions.. The tackifying resins useful herein include aliphatic, cycloaliphatic and aromatic hydrocarbons and modified hydrocarbons arid hydrogenated derivatives; terpenes and modified terpenes and hydrogenated derivatives; rosins and modified rosins and hydrogenated derivatives; and mixtures thereof: These tackifying resins have a ring and ball softening point of between about '70°C and 150°C.
They are also available with differing levels of hydrogenation, or saturation which is another commonly used term. Useful examples include EastotacTM H-100, H-115 and H-130 from Eastman Chemical Co. in Kingsport, TN which are partially hydrogenated cycloaliphatic petroleum hydroc~~rbon resins with different softening points. These acre available in the E _e;rade, the R grade, the L
grade and the W grade. These have differing levels of hydrogenation from least hydrogenated to most hydrogenated. The E grade has a bromine number of 15, the R grade a bromine number of 5, the L grade has a bromine number of 3 and the W grade a bromine number of 1. There is also an EastotacTM H-1428 resin available. Other useful tankifying resins include Escorez 1310 LC, an aliphatic hydrocarbon resin, EscorezTM 5300 and Escore::TM 5400, partially hydrogenated cycloaliphatic petroleurxi .hydrocarbon resins, and EscorezT"" 5600, a partially hydrogenated aromatic modified petroleum hyc(rocarbon resin all available from Exxon Chemical Co. in Houston, TX; WingtackTM Extra which is an aliphatic, aromatic petroleum hydrocarbon resin available from Goodyear Chemical C'o. in Akron, OH; Hercolite''T~ 2100 which is a partially hydrogenated cycloaliphatic petroleum hydrocarbon resin available from Hercules in Wilmington, DE; and W
ZonatacTM 105 Lite which is a styrenated terpene resin made from d-Iimonene and available from Arizona Che:mical Co, in Panama. City, FL. There are numerous types of rosins and modi3:ied rosins available with differing levels of hydrogenation including gum rosins, wood rosins, tall-oil rosins, distilled rosins, dimerized rosins and polyrr~erized rosins. Some specific modified rosins include glycerol and pentaerythritoli esters of wood rosins and tall-oil rosins.
Commercially available grades include, but are not limited to, SylvatacTM
1103, a pentaerythritol rosin ester available from Arizona Chemical Co., UnitacTM R-Lite a pentaerythritol rosin ester from Union Camp in Wayne, NJ, ZonesterTM
100, a glycerol ester of t<~11 oil rosin from Arizona Chemical Co., PermalynTM
305, a pentaerythritol modified wood rosin available from Hercules, Inc. in Wilmington, DE and ForalTM l OS, which is a highly hydrogenated pentaerythritol rosin ester available. SylvatacTM R-85 which is ara 85°C melt point rosin acid and SylvatacTM 295 which is a 95°C melt point rosin acid are both available from Arizona Chemical Co.. For,rITM AX is a 75°C melt point hydrogenated rosin acid available from Hercules lnc. NirezTM V-2040 is a phenolic modified terpene resin available from Arizona Chemical Co. There are many available types and grades of tackifying resins available from many companies, and one skilled in the art would recognize that this is not an exclusive List, and that the available tackifying resins are too numerous to list here. Various encl.block resins are also useful in the compositions of the present invention. These include Ende:YTM 160, an aromatic hydrocarbon manufactured by Hercules, Inc. in Wilmington, DE; KristalexTM
3100 and KristalexTM 5140, alphamethyl styrene hydrocarbons manufactured by Hercules, Inc.; and also coumarone indene resins. These tackifiers are useful from about 0% to about 65% by weight, and preferably from about 10% to about 65%.
The plasticizers uye:Eul in the present invention may include mineral based oils and petroleum based oils, liquid resins, liquid clastomers, polybutene, polyisobutylene, functionalized oils such as glycerol trihydroxyoIeate and other fatty oils and mixtures thcre:of. A plasticizes is broadly defined as a typically organic composition that can be added to the therznopiastics, rubbers and other resins to improve extrudability, t'~exibility, workabilit3~ and stretchability in the finished adhesive. Any material which flows at ambient temperatures and is compatible with the block copolymer may be useful.
The most comrnc.~nly used plasticizers are oils which are primarily hydrocarbon oils that are low in aromatic content and are paraffmic or naphthenic S in character. The oils .:ire; preferably low in volatility, transparent and have as little color and odor as possible. This invention also contemplates the use of olefin oligomers, low molecu.la:r weight polymers, vegetable oils and their derivatives and similar plasticizing oils.
Examples of useful plasticizers include CalsolTM .5120, a naphthenic petroleum based oil available from Calumet Lubricants Co. in Indianapolis, IN;
KaydolTM White Mineral Oil, a paraffinic mineral oil available from Witco Corp.
in New York, NY; ParapolTM 1300, a liquid butene homopolymer available from Exxon Chemical Co. ire Houston, T'X; IndopolTM H-300, a liquid butene homopolymer, available iTOm Amoco Coip, in Chicago, IL; EscorezTM 2520, a liquid aromatic petroley.un based hydrocarbon resin with a pour point of 20°C, available from Exxon Chemical Co.; Regalrei''M 1018, a liquid hydrogenated aromatic hydrocarbon resin with a pour point of 18°C, available from Hercules, Ire. in Chicago, IL; and SylvatacTM SN, a liquid resin of modified rosin ester with a pour point of 5°C, available from Arizona Chemical Co. in Panama City, FL.
One skilled in the art would recognize that any generic 500 second or 1200 second naphthenic process oil would also be useful. These plasticizers are useful in amounts from about 0% to about 50% by weight for the hot melt pressure sensitive compositions, acid up to about 98% by weight in the molded article compositions, and preferably up to about 90% by weight.
A pelletizing aid is used to change the surface characteristics of the pellets.
It would be generally undesirable for molded articles manufactured by such , methods as injection molding, to remain tacky. Surprisingly, a small amount of pelletizing aid can make the surface of the pellets substantially non-tacky.
The pelletizing aids do not change the end use properties of the tacky composition, as in the formulas used as hot melt pressure sensitive adhesives, or they do change the physical properties i>f the tacky composition, as in the case of the formulas used for the molding applucations.
The pelietizing aid is selected from the group consisting of polyethylene waxes, modified polyethylene waxes, polyamide waxes and stearamide waxes.
Many other waxes or pelletizing aids not on this list could also be useful provided the surface of the resultant pellet is tack-free_ Preferred waxes are Acrawax CTM
stearamide wax available .from Lonza, Inc. in Fair lawn, NJ; CastorTM hydroxy waxes and ParicinTM hydroxyamide waxes available form Caschem in Bayonne, NJ; NeptuneTM 968 available: from Shamrock Technologies in Newark, NJ;
ShamrockTM S-395 polyethylene wax available from Shamrock Technologies; and HoechstTM Wax PED 121, a modified polyethylene available from Hoechst Celanese in Somerville, N7. More preferably, these pelletizing aids are polyethylene waxes and come in powder form. The pelIetizing aid is present from about 0.1 percent to about 3 percent by weight and preferably from about 0.1 percent to about 1 percent: b:y weight. This amount is substantially less or comparable to the packaging film of prior art packaging methods. It is believed that the temperature of use~ c>f the tacky hot melt composition controls whether the surface of tacky hot melt ca:mposition returns to the substantially tack-free state after melting the pellets, and subsequent resolidification.
A stabilizer or antioa~idant can also be used in the polymeric compositions.
These compounds are added to protect the adhesive from degradation caused by reaction with oxygen induced by such things as heat, light or residual catalyst from the raw materials such as the tackifying resin. Such antioxidants are commercially available from Ciba-Geigy in Hawthorne, NY and include IrganoxTM 565, IrganoxTM 1010 and IrganoxTM 1076, all hindered phenolic antioxidants. These are primary antioxidants which act as free radical scavengers and may be used alone or in combination with other antioxidants such as phosphite antioxidants like IrgafosTM 168 available from Ciba-Geigy. Phosphite antioxidants are considered secondary antioxidants, are primarily used as peroxide decomposers and are generally not used alone, but are instead used in combination with other antioxidants. tether available antioxidants are CyanoxTM LTDP, a thioether antioxidant, available from Cytec Industries in 5tamford, CT
,EthanoxTM
330, a hindered phenolic antioxidant, available from Albemarle in Baton Rouge, LA. Many other antioxidants are available or use by themselves, or in combination with other antioxidants. These compounds are added to the hot melts in small amounts, up to about 2% by weight in the hot melt pressure sensitive adhesive, and have no effect on the physical properties of the adhesive.
Other compounds that also could be added that have no effect on the S physical properties are pi~;ments which add color, fluorescing agents, any compounds That mask odor and fillers to mention only a few. Additives such as these are known to one of'skill in the art.
Fillers come in zhe form of particulate rnatter, fibers and powders, or may be any material that does ;not interfere with the other components in the adhesive.
Some examples include c<~lcium carbonate, ceramics, glass, silica, quartz, mica, treated clay, titanium dioxide, boron nitrides, graphite, carbon black, metals, barium, sulfate, talc and mixtures thereof. Such additives are known to one of skill in the art.
As discussed above, the resultant pellets are soft, non-blocking, 1 S substantially free from surface tack a.nd exhibit an elastic rebound. This last.
characteristic can be measured by the elastic or storage modulus, G'. The higher the modulus, the more likely that the material will return to its original shape. At lower loadings of the high molecular weight triblock copolymer, the pellets formed resemble gels. ":f hey possess some elastic rebound, but tend to retain the same physical property ~:wer a wide-temperature range, or over a long period of time. These pellets are desirable for making articles such as Santa Claus' bellies.
At higher loadings of the copolymer, the pellet.5 formed have high elastic modulus and tend to return to their original shape faster. They are more suited for producing articles such ~:~s drum pads.
2S Compatible polymers or copolymers discussed above can also be added to modify the properties of the pellets. These are generally of low molecular weight, and pellets made with am amount of the high molecular weight triblock copolymer tend to have more rebound than those made with the same amount of a blend of this copolymer and the lovv molecular weight compatible polymer or copolymer.
These compatible polymers or copolymers are thus added for customizing the final applications or uses.
These pellets are suitable for use in molding, especially injection molding.
The composition suitable: for such processes comprises:
I. A tacky hot melt composition, comprising:
a) at lesst one high molecular weight triblock copolymer of 5 the general configuration A-B-A; and b) a pia;~ticizer; and II. A pelletizing aid;
wherein said pelletizing aid substantially surrounds the tacky composition such that the molded articles are soft, non-blocking and substantially without surface 10 tack. Optionally, other polymers such as diblock or other triblocks can be added.
Preferably, the tacky hot melt composition comprises .from about 97 to about 99.9 percent by weight of the artiicle, more preferably from about 99 to about 99.9 percent by weight.
Any molded articles produced therefrom also retain the substantially tack-15 free surface and rebound properties. Such articles can include drum pads useful as acoustical pads for vibration damping, disc players, ear phones, percussion surfaces on electronic drum kits and so on; soles shoes insoles, in-line skate soles and so on; pads for use in athletic gear such as mouth pads, protective guards, encapsulants for other solid protective pads and so on; bicycle seats, gloves, bicycle shorts and so on; medical eguipment such as pads for wheel chairs, donut-shaped pads for seats and so on; furniture pads such as mattress pads, chair pads and so on; special effects articles such as body parts, Santa Claus' bellies, and other that are useful in movies. Unlike the prior art, the palletizing aid used herein blooms to the surface during the molding process, such that it substantially completely surrounds the tacky composition below and produces articles substantially free of surface tack when cooled. This is surprising because the amount of palletizing aid used in the formulation is small, and according to prior art teachings, should not substantially interfere with the properties of the bulk composition, nor should it: change the surface properties.
The present invention further discloses a method for making such pellets for all the formulations of the invention. The manufacturing process can vary slightly for each product depending on the plasticizer loading. The current WO 97/19582 PC'IYUS96/18507 process requires multiple passes through a co-rotating twin screw extruder with the product being pelIetized at the end of each pass, and then refed into the extruder for the further arildition of plasticizer. The compositions with 90 percent plasticizer or more need tJhree passes, while lower plasticizer loadings may require only two. It is important to note that the materials are pelletized with the pelletizing aid after both passes. The concentration of the pelletizing aid in the water can range from about 0.1 percent to about 3 percent by weight, preferably about O.I to about 1 percent by weight based on anticipated production rate for each pass. A specific preferred manufacturing process comprises:
a) blending W a hot melt components to form a substantially homogeneous hot melt mixture;
b) forcing said substantially homo~;eneous hot melt mixture through a die having a series of~ voids in a circular pattern to form a series of substantially homogeneous hot melt ribbons;
c) further forcing said homogeneous hot melt ribbons past rotating blades in. substantially parallel position to said die, cutting said substantial:fy homogeneous hot melt ribbons to form resultant pellets;
d) substantially solidifying said pellets by use of a liquid cooling medium said liquid cooling medium containing a pelletizing aid, being circulated past said die and rotating blades on the side where said substantially homogeneous hot melt ribbons emerge;
e) transport:in;~ said hat melt pellets to a drying area;
f) substantially removing liquid from said hot melt pellets by blowing.
As depicted above, the pelletizing aid is present in the cooling medium. It can also be added to the hot melt composition prior to blending or during the pelletizing steps by cofeeding a solution of pelletizing aid with the hot melt composition.
As noted above, it is well known in the art that stabilizers or antioxidants can also be added to the compositions in small amounts and have no effect on the other physical properties csf the compositions. I~ther compounds that could be added that also do not effect physical properties are pigments for color, fluorescing agents, and an;y compounds that mask odor. Additives such as these are known to one of skill r.n the art.
This invention is fur~rher illustrated by the following non-limiting examples.
EXAMPLES
Test Methods 1. Melt Vi~,cosities The melt viscosities of the hot melt adhesives were determined on a Brookfield Thermosel Viscosmeter Model DV-Il+. using either a number 21 ar 27 spindle.
I S 2. Specific Gravity The specific gravity was determined using test method ASTM D792 with isopropyl alcohol as the liquid.
3. Mettler Softenine Point The Mettler softening points are determined using test method ASTM
D3461.
4. Dvnamic Temperature St:ccgs Storage modulus, G"., at 25°C and Tg were: determined using a Rheometrics Scientific Dynamic Mechanical Spectrometer Model # RDS7700. The parallel plates used had a 25 mm diameter and a 1.502 mm gap. The instrument was set to a frequency of 10 rads/sec. and temperature sweep was performed from 180°C to -, 50°C.
,5. Bloom Gelomeier Rigidity of the samples was determined using a Precision Bloom Gelometer Catalog No. 687~)5.
Examples 1-4 The following compositions are provided for illustrative purposes only.
Formulations useful as tacky hot melt compositions in accordance with the invention were prepared from the components listed in Cable 1. Physical characteristics of these formulations are given in Table 2..
These examples illustrate the physical properties achieved with these types of hot melt compositions but there are many m<;~re compositions with differing physical characteristics.
Examples 1 and 2 illustrate the invention using only a high molecular weight block substantially linear A-B-A block copolymer. Examples 3 and 4 illustrate the use of a blend of a high molecular weight block cape>lymer and another block copolymer. These examples illustrate compositions that are uselrl for molded articles. The dynamic temperature steps are especially illustrative of this. See Figure 1.
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,5. Bloom Gelomeier Rigidity of the samples was determined using a Precision Bloom Gelometer Catalog No. 687~)5.
Examples 1-4 The following compositions are provided for illustrative purposes only.
Formulations useful as tacky hot melt compositions in accordance with the invention were prepared from the components listed in Cable 1. Physical characteristics of these formulations are given in Table 2..
These examples illustrate the physical properties achieved with these types of hot melt compositions but there are many m<;~re compositions with differing physical characteristics.
Examples 1 and 2 illustrate the invention using only a high molecular weight block substantially linear A-B-A block copolymer. Examples 3 and 4 illustrate the use of a blend of a high molecular weight block cape>lymer and another block copolymer. These examples illustrate compositions that are uselrl for molded articles. The dynamic temperature steps are especially illustrative of this. See Figure 1.
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Claims (17)
1. A polymeric composition in pellet form comprising:
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 5% to 90% by weight of a thermoplastic polymer;
(b) from 10% to 65% by weight of a tackifying resin; and (c) from 0% to 50% by weight of a plasticizer; and II. from 0.1% to 3% by weight of a pelletizing aid substantially surrounding the hot melt composition, wherein the hot melt composition has a storage modulus G', at about 25°C of about 5 x 10 5 dynes/cm2 or less, and a specific gravity greater than about 0.8, a Mettler Softening Point greater than about 90°C', and each pellet has a substantially tack-free surface.
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 5% to 90% by weight of a thermoplastic polymer;
(b) from 10% to 65% by weight of a tackifying resin; and (c) from 0% to 50% by weight of a plasticizer; and II. from 0.1% to 3% by weight of a pelletizing aid substantially surrounding the hot melt composition, wherein the hot melt composition has a storage modulus G', at about 25°C of about 5 x 10 5 dynes/cm2 or less, and a specific gravity greater than about 0.8, a Mettler Softening Point greater than about 90°C', and each pellet has a substantially tack-free surface.
2. A polymeric composition in pellet form comprising:
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 2% to 20% by weight of a high molecular weight block copolymer having the general configuration A-B-A and a molecular weight greater than 200,000;
(b) from 20 to 98 percent by weight of a compatible plasticizer; and (c) from 0% to 30 percent by weight of a compatible polymer, II. from 0.1% to 3 percent by weight of a pelletizing aid, wherein the resultant polymeric compositions have a tack-free surface both prior to melting the pellets, and after melting and resolidification.
I. from 97 to 99.9 percent by weight of a tacky hot melt composition, comprising:
(a) from 2% to 20% by weight of a high molecular weight block copolymer having the general configuration A-B-A and a molecular weight greater than 200,000;
(b) from 20 to 98 percent by weight of a compatible plasticizer; and (c) from 0% to 30 percent by weight of a compatible polymer, II. from 0.1% to 3 percent by weight of a pelletizing aid, wherein the resultant polymeric compositions have a tack-free surface both prior to melting the pellets, and after melting and resolidification.
3. The polymeric composition of claim 1 or claim 2 wherein the thermoplastic polymer is a styrenic block copolymer having a styrene content from 10% by weight to 50% by weight, an isoprene, butadiene, ethylene/butylene or ethylene/propylene midblock and a diblock content of less than about 90%.
4. The polymeric composition of claim 1 wherein the thermoplastic polymer is selected from the group consisting of A-B-A triblock copolymer, A-B diblock copolymers, A-B-A-B-A-B multiblock copolymers, radial block copolymers, and grated versions thereof, homopolymers, copolymers and terpolymers of ethylene;
homopolymers, copolymers, and terpolymers of propylene; and mixtures thereof;
homopolymers, copolymers, and terpolymers of propylene; and mixtures thereof;
5. The polymeric composition of claim 1 wherein said thermoplastic polymer is a homogeneous, substantially linear ethylene alpha olefin.
6. The polymeric composition of Claim 1 wherein the tackifying resin has a softening point of at least 70°C and is selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons and modified hydrocarbons and hydrogenated derivatives; terpenes and modified terpenes and hydrogenated derivatives; and rosins and modified rosins and hydrogenated derivatives; and mixtures thereof.
7. The polymeric composition of claim 1 or claim 2 wherein the plasticizer is a material which flows at ambient temperature and is selected from the group consisting of mineral based hydrocarbon oils, petroleum based hydrocarbon oils, polybutene, polyisobutylene, liquid tackifying resin, liquid elastomers, functionalized oils, fatty oils, and mixtures thereof.
8. The polymeric composition of claim 1 or claim 2 wherein said pelletizing aid is selected from the group consisting of polyethylene waxes, modified polyethylene waxes, polyamide waxes and stearamide waxes, and mixtures thereof.
9. The polymeric composition of claim 1 or claim 2 wherein said pelletizing aid is a polyethylene wax.
10. The polymeric composition of claim 9 wherein said pelletizing aid is in powder form.
11. The polymeric composition of claim 1 wherein the tacky hot melt composition further comprises an antioxidant in an amount of up to 2% by weight.
12. The polymeric composition of claim 1 wherein the storage modulus G', of the hot melt composition is in the range of from about 1 x 10 4 dynes/cm2 to about 5 x dynes/cm2.
13. A method for preparing a polymeric composition as in any of claims 1-10 comprising the steps of:
(a) blending the components of the tacky hot melt composition to form a substantially homogeneous mixture;
(b) forcing said substantially homogeneous mixture through a die for forming substantially homogeneous ribbons and forming pellets from said ribbons;
(c) solidifying said pellets by use of a cooling medium containing therein a pelletizing aid at a concentration of from 0.3 to 3% by weight of the cooling medium;
(d) separating the pellets from the cooling medium; and (e) substantially removing the liquid from the pellets.
(a) blending the components of the tacky hot melt composition to form a substantially homogeneous mixture;
(b) forcing said substantially homogeneous mixture through a die for forming substantially homogeneous ribbons and forming pellets from said ribbons;
(c) solidifying said pellets by use of a cooling medium containing therein a pelletizing aid at a concentration of from 0.3 to 3% by weight of the cooling medium;
(d) separating the pellets from the cooling medium; and (e) substantially removing the liquid from the pellets.
14. The method of Claim 13 wherein the blending step is carried out by means of a twin screw extruder.
15. The method of Claim 13 wherein said liquid is removed from said pellets by blowing.
16. An article molded from a polymeric composition in pellet form wherein said polymeric composition in pellet form comprises:
I. a tacky hot melt composition, comprising:
(a) at least one high molecular weight triblock copolymer of the general configuration A-B-A; and (b) a plasticizer; and II. a pelletizing aid, wherein said pelletizing aid substantially surrounds the tacky hot melt composition such that the molded articles are soft, non-blocking and have a substantially tack-free surface.
I. a tacky hot melt composition, comprising:
(a) at least one high molecular weight triblock copolymer of the general configuration A-B-A; and (b) a plasticizer; and II. a pelletizing aid, wherein said pelletizing aid substantially surrounds the tacky hot melt composition such that the molded articles are soft, non-blocking and have a substantially tack-free surface.
17. Molded article of claim 16 wherein said article is selected from the group consisting of drum pads, shoe soles, therapeutic hand exercising grips, shock absorbers, acoustical insulators, pads for athletic gear, pads for medical equipment, furniture pads, bandages, burn victim bandages, synthetic skin and special effects articles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55900695A | 1995-11-16 | 1995-11-16 | |
| US08/559,006 | 1995-11-16 | ||
| PCT/US1996/018507 WO1997019582A2 (en) | 1995-11-16 | 1996-11-18 | A polymeric composition in pellet form |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2239983A1 CA2239983A1 (en) | 1997-06-05 |
| CA2239983C true CA2239983C (en) | 2002-07-30 |
Family
ID=24231901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002239983A Expired - Fee Related CA2239983C (en) | 1995-11-16 | 1996-11-18 | A polymeric composition in pellet form |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US5869555A (en) |
| EP (1) | EP0861285B1 (en) |
| JP (1) | JP3792724B2 (en) |
| CN (1) | CN1193068C (en) |
| AU (1) | AU719936B2 (en) |
| BR (1) | BR9611968A (en) |
| CA (1) | CA2239983C (en) |
| DE (1) | DE69635829D1 (en) |
| WO (1) | WO1997019582A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6169138B1 (en) * | 1994-12-15 | 2001-01-02 | Saint-Gobain Performance Plastics Corporation | Foamed pressure sensitive tapes |
| WO1996035741A1 (en) * | 1995-05-08 | 1996-11-14 | Eastman Chemical Company | Process for coextruding a tacky amorphous propylene copolymer composition with a low viscosity polyolefin and article prepared thereby |
| US5863440A (en) | 1996-05-24 | 1999-01-26 | Abtech Industries, Inc. | Methods for ameliorating oil spills in marine and inland waters |
| US6120899A (en) * | 1997-10-08 | 2000-09-19 | H. B. Fuller Licensing & Financing Inc. | Hot melt adhesive pellet comprising continuous coating of pelletizing aid |
| DE69827937T2 (en) * | 1997-01-10 | 2005-12-22 | Abtech Industries, Inc., Scottsdale | SYSTEMS FOR IMPROVED TREATMENT OF HYDROCARBONS IN AQUEOUS MILIEU |
| US6541569B1 (en) | 1997-01-10 | 2003-04-01 | Abtech Industries, Inc. | Polymer alloys, morphology and materials for environmental remediation |
| US6099723A (en) | 1997-06-06 | 2000-08-08 | Abtech Industries, Inc. | Catchbasin systems for filtering hydrocarbon spills |
| EP1073610B1 (en) | 1998-02-18 | 2009-04-01 | Abtech Industries, Inc. | Curb-inlet storm drain systems for filtering trash and hydrocarbons |
| US6200509B1 (en) * | 1998-06-26 | 2001-03-13 | Union Carbide Chemicals & Plastics Technology Corporation | Form of synthetic rubber |
| US6797377B1 (en) * | 1998-06-30 | 2004-09-28 | Kimberly-Clark Worldwide, Inc. | Cloth-like nonwoven webs made from thermoplastic polymers |
| US6124391A (en) * | 1998-08-18 | 2000-09-26 | Stockhausen Gmbh & Co. Kg | Superabsorbent polymers having anti-caking characteristics |
| US6080307A (en) | 1998-09-29 | 2000-06-27 | Abtech Industries, Inc. | Storm drain systems for filtering trash and hydrocarbons |
| AU2347700A (en) * | 1998-12-10 | 2000-06-26 | Henkel Kommanditgesellschaft Auf Aktien | A process for packaging pressure-sensitive hotmelt adhesive |
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-
1996
- 1996-11-18 JP JP52053997A patent/JP3792724B2/en not_active Expired - Fee Related
- 1996-11-18 DE DE69635829T patent/DE69635829D1/en not_active Expired - Lifetime
- 1996-11-18 CA CA002239983A patent/CA2239983C/en not_active Expired - Fee Related
- 1996-11-18 AU AU10546/97A patent/AU719936B2/en not_active Ceased
- 1996-11-18 BR BR9611968A patent/BR9611968A/en not_active IP Right Cessation
- 1996-11-18 US US08/751,828 patent/US5869555A/en not_active Expired - Lifetime
- 1996-11-18 EP EP96941387A patent/EP0861285B1/en not_active Expired - Lifetime
- 1996-11-18 WO PCT/US1996/018507 patent/WO1997019582A2/en active IP Right Grant
-
1998
- 1998-08-31 US US09/143,757 patent/US5942569A/en not_active Expired - Lifetime
-
2001
- 2001-01-22 CN CNB011015225A patent/CN1193068C/en not_active Expired - Fee Related
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|---|---|
| CA2239983A1 (en) | 1997-06-05 |
| WO1997019582A3 (en) | 1997-07-03 |
| AU1054697A (en) | 1997-06-19 |
| AU719936B2 (en) | 2000-05-18 |
| US5942569A (en) | 1999-08-24 |
| JP2000502120A (en) | 2000-02-22 |
| EP0861285A2 (en) | 1998-09-02 |
| EP0861285B1 (en) | 2006-02-15 |
| BR9611968A (en) | 1999-07-13 |
| CN1193068C (en) | 2005-03-16 |
| WO1997019582A2 (en) | 1997-06-05 |
| DE69635829D1 (en) | 2006-04-20 |
| CN1314433A (en) | 2001-09-26 |
| JP3792724B2 (en) | 2006-07-05 |
| US5869555A (en) | 1999-02-09 |
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| EEER | Examination request | ||
| MKLA | Lapsed |
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