CA1113637A - Film composite and packaged articles therewith - Google Patents
Film composite and packaged articles therewithInfo
- Publication number
- CA1113637A CA1113637A CA312,577A CA312577A CA1113637A CA 1113637 A CA1113637 A CA 1113637A CA 312577 A CA312577 A CA 312577A CA 1113637 A CA1113637 A CA 1113637A
- Authority
- CA
- Canada
- Prior art keywords
- styrene
- weight
- unvulcanized
- rubber
- package
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Packages (AREA)
- Wrappers (AREA)
Abstract
Abstract of the Disclosure The invention relates to a film composite comprised of an admixture of (1) an unvulcanized elastomeric block copolymer, (2) a thermoplastic resin and (3) a selected hydrocarbon paraffin wax. Invention further relates to a package of an article wrapped in said film composite where said article is selected from unvulcanized rubber, com-pounding ingredients for unvulcanized rubber, and compounding ingredients for thermoplastic polymers. Invention addi-tionally relates to compounded high unsaturation rubber or thermoplastic polymer prepared by utilizing a package of said film composite containing compounding material.
Description
3~
This invention rela-tes -to an elastomeric block polymer ~ilm having an anti~block proper-ty and par-ticularly to wrapped un~llc~nized rubber an~ to wrapped compounding ingredients -therefor wi-th such film. The inven-tion ~urther relates to cured or vulcanized rubber prepared -therewi-th.
Many films of unvulcanized block copolymers such as styrene-butadiene-styrene block copolymers -tend to block or ligh-tly s-tick toget,her when s-tacked or rolled against -themselves, This blocking or s-ticking phenomenon can resul-t in a tolerable nuisance or can amount to an intolerable problem. For example, such film wrapping of individual stacked bales o~ unvulcanized rubber has been observed to be separable only by rupture and tearing o~ the film. Pieces o~ the film remain stuck to the rubber.
Those having skill in the art are generally -~ continually seeking to enhance the storage capability o~
unvulcanized rubber. In this regard, it is desired to substantially reduce or eliminate blocking tendencies o~
~ilms and shee-ts o~ the various thermoplastic ~ilms, especially those such as the unvulcanized styrene-butadiene-styrene block polymers at production recov~ry temperatures such as 180F (82C.) or higher. Commonly used an-ti-blocking agents which may be compounded with such block polymers include various individual or combinations o~
waxes, soaps, silicones, pigments, vegetable leci-thins as well as selected mixtures o~ s-tearyl erucamide, oleyl palmitamide and behenamide. However, particularly for extrusion-prepared compounded films o~ unvulcanized styrene-butadiene-styrene, such anti-blocking agents are .
~ .
363~7 deficien-t when packaging ho-t productio~ rubber a-t 180F. (82C.) or higher to effec-tively prevent blocking or sticking -toge-ther of packaged unvulcanized rubber bales.
Therefore, i-t is an object of this inven-tion -to provide a compounded elastomeric block copolymer ~ilm having an antiblock propert;y and to provide packaged articles therewi-th.
In accordance with -this invention, i-t has been discovered that a ~ilm composi-tion having an antiblock property comprises an admixture of (1) 100 parts by weight of an unvulcanized elas-tomeric block copolymer having the general configuration A-B-A wherein each A is an independently selected nonelastomeric monovinyl aromatic hydrocarbon polymer block selected ~rom styrene, a-me-thyl styrene and vinyl toluene ha~ing an average molecular weight of about 7,000 to about 25,000 and a glass transi-tion temperature above about 25C., the -total block A
content being ~rom about 12to about 62 percent by weight of the copolymer~ and B is an elastomeric conjugated diene polymer bloc~ selected from 1,3-butadiene and isoprene having an average molecular weight from abou-t 30,000 to about 100,000 and a glass transition temperature below about 10C., said block copolymer being further charac-terized by having a melt viscosity in the range o~ about 0.1 to about 10 grams/10 minutes according to ASTM
#D-1238, (2) about 25 to about 120 parts by weight of a thermoplastic resin selected from at least one polymer of styrene, a-methyl styrene, styrene/a-methyl styrene, vinyl toluene, vinyl toluene/a-methyl styrene, indene ~3 ~ 3 ~
resins, alkyl phenolic resins, petroleum and coal -tar resins, and high impact po:lystyrene comprised of (a) abou-t 100 parts by weigh-t polystyrene having a molecular weight in the range of about 15,000 -to abou-t 50,000 and, dispersed therein, (b)about 3 -to abou-t 35, pre~erably about 3 to about lO, parts by weight of an elas-tomeric polymer selected from a-t leas-t one of polybutadiene, polyisoprene and bu-tadiene/styrene copolymers and (3) abou-t 0.5 to about lO par-ts by weight hydrocarbon paraffin ; 10 wax having a congealing point according to ASTM ~D-938-L~9 in the range of abou-t 190F. (88C.) to about 220~.
(105C.).
Preferably, -the film composi-tion has a thickness in the range of about 0.5 to about 20, and more preferably in the range of about l to about 10, mils.
It is understood that such film composite can desirably contain various typical lubricants, fillers, pigments, extenders and stabilizers.
The elastomeric block copolymers useful in the practice of this invention for the packaging of rubber or various compounding ingredients can be of the radial- -type or of the linear type. Generally, the linear styrene-butadiene-styrene block copolymer is desired.
The thermoplastic composition of this inven-tion is typically in the form of a film having a thickness of about 0.5 to abou-t 10 mils and characterized by having an antiblock property according -to an-tiblock test No. 2, hereinaf-ter described, of about 0 to about 10 grams.
.
~ ~3 ~'7 In general, -the radial-type block copolymers are prepared by coupling ~B block polymers with poly~unctional agents as described in U. ~. Pa-ten-t 3,2~1,382.
In general, the li~ear block copolymer type is prepared by any o~ -the me-thods commonly used for block copolymers o~ styrene and bu-tadiene, ~or example, (1) by ~irs-t preparing "living" polystyryl li-thium ~rom s-tyrene and an alkyl lithium and adding this to a mix-ture o~
styrene-butadiene, (2) by mixing either lit~ium me-tal or a dilithium alkyl (e.g., -tetrame-thylene dilithium), both o~ which are repor-ted to grow at both ends, (3) by pre-paring polystyryl li-thium and sequentially polymerizing butadiene and then styrene, or (L~) polymerizing butadiene with polystyryl li-thium and coupling with coupling agents known to those skilled in this art.
The thermoplastic aromatic resins useful in the preparat1on o~ -the ~ilms o~ this invention are aromatic resins desirably selec-ted ~rom a-t leas-t one of s-tyrene, ; a-methyl styrene, a-methyl styrene/vinyl toluene, a-methyl styrene/styrene, vinyl toluene, indenes, modified phenolics and~resins from petroleum and coal-derived monomers, characterized by having an intrinsic viscosity in toluene at 30C. of about 0.02 to about 0.50. High impact polystyrene has been ~ound to be particularly use~ul for extrusion-prepared compounded ~ilms.
In generali the arom~tic resins are prepared by conventional polymerization techniques, well known to those skilled in the art.
~-ligh impact po~Lys-tyrene is prepared by conven--tional -techniques and is -t~Jpically comprised o~ about lO0 parts by ~eigh-t polystyrene having a molecular weight in the range of abou-t 15,000 to about 50,000 and having dispersed -therein about 5 -to abou-t 20 parts by weight of an elastomer selec-ted from a-t leas-t one o~ polybutadiene, polyisoprene and butadiene/styrene copolymers.
In the practice of -this inven-tion, the styrene-butadiene-styrene block polymer/resin blend composition can be prepared by extrusion or by solution cast tech-niques. Extrusion is generally pre~erred because of more ~avorable processing economics, versatili-ty of produc-tion (flat film or collapsed tube method) and less health and hazard problems due to absence of solvent in the extru-sion process. However, extrusion typically presents production problems for producing an effective film not found in solution cast methods.
In the solution cast method o~ preparation, a blend of the block polymer, thermoplastic resin can conveniently be dissolved in an organic solvent at a -tem-perature in -the range of about 40C. to about 80C.
~ollowed by mixing therewith the selected wax. The mixture is desirably cast as a ~ilm onto a substrate, dried by evaporating the organic solvent to yield -the - 25 required composition in the form of a film which is then stripped from the casting substrate. Typically, the mixture can be dried a-t a temperature of about 40~C. to about 150C., depending primarily upon the organic solvent used. It should be readily understood that if the '' ' ' ' ' ' 31F~3'7 composi-tion is to be drled as a film, substantially reduced temperatures and times can be used such as temperature in -the range of abou-t 70C. -to about 90C. for a period of about 15 to about 60 minutes.
In the extrusion method of preparation, the following -techni~ue can con~eniently be used. The compo-sition is melted in a conventional ex-truder, preferably with a 24/1 length/diame-ter ratio. The melt passes upward through a circular die, forming a "bubble" which is -then collapsed in a cooling tower. The collapsed "bubble" is either slit -to form a single web or no-t slit to remain as a coll~psed tube. The film or -tube is then would into rolls of specified length and width on conventional wind-up apparatus.
Unvulcanized rubber can be advantageously packaged according to this invention. Representative of the various unvulcanized rubbers are na-tural rubber, synthetic cis-1,4-polyisoprene, rubbery polymers of l,~-butadiene, butadiene-styrene emulsion or solution ~ormed rubbery copolymers and copolymers of butadiene and acrylonitrile. All of these heretofore identified rubbers are of the high unsaturation type. Namely, they contain an appreciable amo~mt of carbon-to-carbon double bonds therein. A:Lthough -this invention is partly directed -to the packaging of the high unsatura-tion type rubbers, the low unsatura-tion type can also be packaged i~ desired.
Representative of such low unsaturation rubbers are rubbery terpolymers of ethylene, propylene and a minor amount o~ a conjugated diene. Representative of ..... .
,"~
~, :
i3'7 non-conjugated dienes are, :Eor example, 1,4-hsxadiene, dicyclopentadiene and 2,5~ethylidene bicyclohep-tene.
Various rubber co~pounding resins and ingredients especially resins such as hydrocarbon resins can also be packaged according to -this invention and then compounded with the unvulcanized rubber. Representative of -the various compounding ingredients are fillers, such as clay, silica-tes, calcium carbonate and the like; accelerators, such as, for example, cadmium diethyldithiocarbama-te, ;. 10 te-tramethyl thiuram disulfide, benzo-thiazyl disulfide and the like; antioxidan-ts, such as -the well known substitu-ted phenolic, substituted thio es-ters and amine type; anti-ozonants, such as aniline derivatives, diamines and thioureas; curatives, such as sulfur, sul.~ur providing compounds and peroxides; ultraviolet agents such as substituted benzotriazoles and substituted benzophenones;
~i color pigments, such as iron oxide, titanium dioxides and organlc dyes; rein~orcing pigmen-ts, such as carbon black, zinc oxide and hydrated silica compounds; and processing aids, such as polyethylenes, silicon dioxide, pumice and stearate.
The antiblock feature o~ the composite ~ilm of this invention ~or the preparation of films is particu-larly useful where the packaged ma-terials are stacked or ~ ;
"containerized't together and then stored at an elevated temperature in order to prevent thern ~rom sticking to each other and making them virtually impossible -to separate without actually destroying por-tions of the package and :
... .. . .
~ ~ 3~ 3 ~
material. A par-ticularly added benefi-t is -the effec-t of the sur~ace wax helping to protect against o~idation.
The importance of such a discovery is amplified by the ~ollowing discussion.
Polyethylene ~ilm tPE) is generally used -to overwrap bales of r~lbber -to simpli~y handling and use.
For most applications, -the overwrapped bale is used in-tact.
In man~v instances during proeessing (Banburies, mills, calenders, tire~building operations) -the PE overwrap survives as disere-te bits of film. It has been proven ~ that the PE bits form void areas where rubber/rubber - contaet is disrupted, leading to failure of -the end product, regarding burst pressure, mechanical weaknesses and related problems. The PE is not compatible with typieal rubbers, so that undispersed particles remain ~` as foreign areas. Also, it is k~own that the PE does not eure into, or become part of, the rubber matrix. / .
However, the composite film of the present inven-tion, having an additional enhanced structural stability, is soluble in styrene, dispersable in rubber eompounds - during eonventional mixing eyeles, and has the ability to . .
eo-eure in -the rubber matrix.
Beeause of its technical advantages 3 the film eomposite o~ this invention can readily be used for the paekaging of various eompounding ingredients ~or unvul-.
-~ eanized ru~ber and various plastics where (1) dispersi-bility, (2) ability to co-cure with rubber, or (3) styrene solubilit~ is a requisite.
~ .
.
, , .:
There~ore, in fur-ther accordance with this invention, a packaged un~ulcanized rubber, par-ticularly a high-unsatura-tion rubber as hereinbefore described and particularly a packaged unvulcanized rubber bale in-tended for s-torage, comprises such unvulcanized rubber substan~
tially encompassed with an overwrap of the ~ilm composi-te of this invention. Indeed, the inven-tion is especially useful for the s-torage o~ large unvulcanized rubber bales.
The term overwrap rela-tes to -the film as applied -to the unvulcanized rubber, especially when in bale form. For bale wrapping, two sheets of film can conveniently be used.
One sheet is applied to the top of the rectangular shaped bale and the other to its bottom. The sheets are then wrapped around the sides of the bale and their peripheries heat sealed together.
In additional accordance wi-th this in~ention7 a method of compounding rubber is provided, and the corres- ~
ponding compounded rubber is provided which comprises mixing, and the resulting admixture including the sulfur cured admixture, said method comprising mixing unvulcanized rubber, particularly hereinbefore described packaged high unsaturation rubber overwrapped with the film com-posite of t:his invention, and conventional compounding ingredients, par-ticularly such ingredients packaged in -the film composite of this invention, optionally followed by sulfur curing said prepared mixture of rubber, packaging film and packaged compounds.
The practice of this invention is further illus-trated ~y reference to -the following examples which are , , 363~
intended -to be represen-tative rather than restric-tive of the scope of the inven-tion. Unless~ o-therwise indica-ted, all par-ts and percentages are by weight.
A film was prepared by blending an unvulcanized s-tyrene-butadiene-s-tyrene block polymer, high impac-t polystyrene, wax, and other ingredients, and extruding the fluid blend to form a film having a -thickness of about 5 mils.
The following Table 1 more clearly shows the formulation:
Table 1 C~mp~ Parts Styrene/butadiene/styrene block copolymerl65.0 High Impac* Polystyrene2 35.0 Synthetic Hydrocarbon Wax3 5.0 Stearic Acid (lubricant) 0.25 Polyethylene (lubricant)4 0.50 ~; Anti-oxidanta 1.0 1 SBS block copolymer obtained as Solprene 414 from The Phillips Petroleum Company.
This invention rela-tes -to an elastomeric block polymer ~ilm having an anti~block proper-ty and par-ticularly to wrapped un~llc~nized rubber an~ to wrapped compounding ingredients -therefor wi-th such film. The inven-tion ~urther relates to cured or vulcanized rubber prepared -therewi-th.
Many films of unvulcanized block copolymers such as styrene-butadiene-styrene block copolymers -tend to block or ligh-tly s-tick toget,her when s-tacked or rolled against -themselves, This blocking or s-ticking phenomenon can resul-t in a tolerable nuisance or can amount to an intolerable problem. For example, such film wrapping of individual stacked bales o~ unvulcanized rubber has been observed to be separable only by rupture and tearing o~ the film. Pieces o~ the film remain stuck to the rubber.
Those having skill in the art are generally -~ continually seeking to enhance the storage capability o~
unvulcanized rubber. In this regard, it is desired to substantially reduce or eliminate blocking tendencies o~
~ilms and shee-ts o~ the various thermoplastic ~ilms, especially those such as the unvulcanized styrene-butadiene-styrene block polymers at production recov~ry temperatures such as 180F (82C.) or higher. Commonly used an-ti-blocking agents which may be compounded with such block polymers include various individual or combinations o~
waxes, soaps, silicones, pigments, vegetable leci-thins as well as selected mixtures o~ s-tearyl erucamide, oleyl palmitamide and behenamide. However, particularly for extrusion-prepared compounded films o~ unvulcanized styrene-butadiene-styrene, such anti-blocking agents are .
~ .
363~7 deficien-t when packaging ho-t productio~ rubber a-t 180F. (82C.) or higher to effec-tively prevent blocking or sticking -toge-ther of packaged unvulcanized rubber bales.
Therefore, i-t is an object of this inven-tion -to provide a compounded elastomeric block copolymer ~ilm having an antiblock propert;y and to provide packaged articles therewi-th.
In accordance with -this invention, i-t has been discovered that a ~ilm composi-tion having an antiblock property comprises an admixture of (1) 100 parts by weight of an unvulcanized elas-tomeric block copolymer having the general configuration A-B-A wherein each A is an independently selected nonelastomeric monovinyl aromatic hydrocarbon polymer block selected ~rom styrene, a-me-thyl styrene and vinyl toluene ha~ing an average molecular weight of about 7,000 to about 25,000 and a glass transi-tion temperature above about 25C., the -total block A
content being ~rom about 12to about 62 percent by weight of the copolymer~ and B is an elastomeric conjugated diene polymer bloc~ selected from 1,3-butadiene and isoprene having an average molecular weight from abou-t 30,000 to about 100,000 and a glass transition temperature below about 10C., said block copolymer being further charac-terized by having a melt viscosity in the range o~ about 0.1 to about 10 grams/10 minutes according to ASTM
#D-1238, (2) about 25 to about 120 parts by weight of a thermoplastic resin selected from at least one polymer of styrene, a-methyl styrene, styrene/a-methyl styrene, vinyl toluene, vinyl toluene/a-methyl styrene, indene ~3 ~ 3 ~
resins, alkyl phenolic resins, petroleum and coal -tar resins, and high impact po:lystyrene comprised of (a) abou-t 100 parts by weigh-t polystyrene having a molecular weight in the range of about 15,000 -to abou-t 50,000 and, dispersed therein, (b)about 3 -to abou-t 35, pre~erably about 3 to about lO, parts by weight of an elas-tomeric polymer selected from a-t leas-t one of polybutadiene, polyisoprene and bu-tadiene/styrene copolymers and (3) abou-t 0.5 to about lO par-ts by weight hydrocarbon paraffin ; 10 wax having a congealing point according to ASTM ~D-938-L~9 in the range of abou-t 190F. (88C.) to about 220~.
(105C.).
Preferably, -the film composi-tion has a thickness in the range of about 0.5 to about 20, and more preferably in the range of about l to about 10, mils.
It is understood that such film composite can desirably contain various typical lubricants, fillers, pigments, extenders and stabilizers.
The elastomeric block copolymers useful in the practice of this invention for the packaging of rubber or various compounding ingredients can be of the radial- -type or of the linear type. Generally, the linear styrene-butadiene-styrene block copolymer is desired.
The thermoplastic composition of this inven-tion is typically in the form of a film having a thickness of about 0.5 to abou-t 10 mils and characterized by having an antiblock property according -to an-tiblock test No. 2, hereinaf-ter described, of about 0 to about 10 grams.
.
~ ~3 ~'7 In general, -the radial-type block copolymers are prepared by coupling ~B block polymers with poly~unctional agents as described in U. ~. Pa-ten-t 3,2~1,382.
In general, the li~ear block copolymer type is prepared by any o~ -the me-thods commonly used for block copolymers o~ styrene and bu-tadiene, ~or example, (1) by ~irs-t preparing "living" polystyryl li-thium ~rom s-tyrene and an alkyl lithium and adding this to a mix-ture o~
styrene-butadiene, (2) by mixing either lit~ium me-tal or a dilithium alkyl (e.g., -tetrame-thylene dilithium), both o~ which are repor-ted to grow at both ends, (3) by pre-paring polystyryl li-thium and sequentially polymerizing butadiene and then styrene, or (L~) polymerizing butadiene with polystyryl li-thium and coupling with coupling agents known to those skilled in this art.
The thermoplastic aromatic resins useful in the preparat1on o~ -the ~ilms o~ this invention are aromatic resins desirably selec-ted ~rom a-t leas-t one of s-tyrene, ; a-methyl styrene, a-methyl styrene/vinyl toluene, a-methyl styrene/styrene, vinyl toluene, indenes, modified phenolics and~resins from petroleum and coal-derived monomers, characterized by having an intrinsic viscosity in toluene at 30C. of about 0.02 to about 0.50. High impact polystyrene has been ~ound to be particularly use~ul for extrusion-prepared compounded ~ilms.
In generali the arom~tic resins are prepared by conventional polymerization techniques, well known to those skilled in the art.
~-ligh impact po~Lys-tyrene is prepared by conven--tional -techniques and is -t~Jpically comprised o~ about lO0 parts by ~eigh-t polystyrene having a molecular weight in the range of abou-t 15,000 to about 50,000 and having dispersed -therein about 5 -to abou-t 20 parts by weight of an elastomer selec-ted from a-t leas-t one o~ polybutadiene, polyisoprene and butadiene/styrene copolymers.
In the practice of -this inven-tion, the styrene-butadiene-styrene block polymer/resin blend composition can be prepared by extrusion or by solution cast tech-niques. Extrusion is generally pre~erred because of more ~avorable processing economics, versatili-ty of produc-tion (flat film or collapsed tube method) and less health and hazard problems due to absence of solvent in the extru-sion process. However, extrusion typically presents production problems for producing an effective film not found in solution cast methods.
In the solution cast method o~ preparation, a blend of the block polymer, thermoplastic resin can conveniently be dissolved in an organic solvent at a -tem-perature in -the range of about 40C. to about 80C.
~ollowed by mixing therewith the selected wax. The mixture is desirably cast as a ~ilm onto a substrate, dried by evaporating the organic solvent to yield -the - 25 required composition in the form of a film which is then stripped from the casting substrate. Typically, the mixture can be dried a-t a temperature of about 40~C. to about 150C., depending primarily upon the organic solvent used. It should be readily understood that if the '' ' ' ' ' ' 31F~3'7 composi-tion is to be drled as a film, substantially reduced temperatures and times can be used such as temperature in -the range of abou-t 70C. -to about 90C. for a period of about 15 to about 60 minutes.
In the extrusion method of preparation, the following -techni~ue can con~eniently be used. The compo-sition is melted in a conventional ex-truder, preferably with a 24/1 length/diame-ter ratio. The melt passes upward through a circular die, forming a "bubble" which is -then collapsed in a cooling tower. The collapsed "bubble" is either slit -to form a single web or no-t slit to remain as a coll~psed tube. The film or -tube is then would into rolls of specified length and width on conventional wind-up apparatus.
Unvulcanized rubber can be advantageously packaged according to this invention. Representative of the various unvulcanized rubbers are na-tural rubber, synthetic cis-1,4-polyisoprene, rubbery polymers of l,~-butadiene, butadiene-styrene emulsion or solution ~ormed rubbery copolymers and copolymers of butadiene and acrylonitrile. All of these heretofore identified rubbers are of the high unsaturation type. Namely, they contain an appreciable amo~mt of carbon-to-carbon double bonds therein. A:Lthough -this invention is partly directed -to the packaging of the high unsatura-tion type rubbers, the low unsatura-tion type can also be packaged i~ desired.
Representative of such low unsaturation rubbers are rubbery terpolymers of ethylene, propylene and a minor amount o~ a conjugated diene. Representative of ..... .
,"~
~, :
i3'7 non-conjugated dienes are, :Eor example, 1,4-hsxadiene, dicyclopentadiene and 2,5~ethylidene bicyclohep-tene.
Various rubber co~pounding resins and ingredients especially resins such as hydrocarbon resins can also be packaged according to -this invention and then compounded with the unvulcanized rubber. Representative of -the various compounding ingredients are fillers, such as clay, silica-tes, calcium carbonate and the like; accelerators, such as, for example, cadmium diethyldithiocarbama-te, ;. 10 te-tramethyl thiuram disulfide, benzo-thiazyl disulfide and the like; antioxidan-ts, such as -the well known substitu-ted phenolic, substituted thio es-ters and amine type; anti-ozonants, such as aniline derivatives, diamines and thioureas; curatives, such as sulfur, sul.~ur providing compounds and peroxides; ultraviolet agents such as substituted benzotriazoles and substituted benzophenones;
~i color pigments, such as iron oxide, titanium dioxides and organlc dyes; rein~orcing pigmen-ts, such as carbon black, zinc oxide and hydrated silica compounds; and processing aids, such as polyethylenes, silicon dioxide, pumice and stearate.
The antiblock feature o~ the composite ~ilm of this invention ~or the preparation of films is particu-larly useful where the packaged ma-terials are stacked or ~ ;
"containerized't together and then stored at an elevated temperature in order to prevent thern ~rom sticking to each other and making them virtually impossible -to separate without actually destroying por-tions of the package and :
... .. . .
~ ~ 3~ 3 ~
material. A par-ticularly added benefi-t is -the effec-t of the sur~ace wax helping to protect against o~idation.
The importance of such a discovery is amplified by the ~ollowing discussion.
Polyethylene ~ilm tPE) is generally used -to overwrap bales of r~lbber -to simpli~y handling and use.
For most applications, -the overwrapped bale is used in-tact.
In man~v instances during proeessing (Banburies, mills, calenders, tire~building operations) -the PE overwrap survives as disere-te bits of film. It has been proven ~ that the PE bits form void areas where rubber/rubber - contaet is disrupted, leading to failure of -the end product, regarding burst pressure, mechanical weaknesses and related problems. The PE is not compatible with typieal rubbers, so that undispersed particles remain ~` as foreign areas. Also, it is k~own that the PE does not eure into, or become part of, the rubber matrix. / .
However, the composite film of the present inven-tion, having an additional enhanced structural stability, is soluble in styrene, dispersable in rubber eompounds - during eonventional mixing eyeles, and has the ability to . .
eo-eure in -the rubber matrix.
Beeause of its technical advantages 3 the film eomposite o~ this invention can readily be used for the paekaging of various eompounding ingredients ~or unvul-.
-~ eanized ru~ber and various plastics where (1) dispersi-bility, (2) ability to co-cure with rubber, or (3) styrene solubilit~ is a requisite.
~ .
.
, , .:
There~ore, in fur-ther accordance with this invention, a packaged un~ulcanized rubber, par-ticularly a high-unsatura-tion rubber as hereinbefore described and particularly a packaged unvulcanized rubber bale in-tended for s-torage, comprises such unvulcanized rubber substan~
tially encompassed with an overwrap of the ~ilm composi-te of this invention. Indeed, the inven-tion is especially useful for the s-torage o~ large unvulcanized rubber bales.
The term overwrap rela-tes to -the film as applied -to the unvulcanized rubber, especially when in bale form. For bale wrapping, two sheets of film can conveniently be used.
One sheet is applied to the top of the rectangular shaped bale and the other to its bottom. The sheets are then wrapped around the sides of the bale and their peripheries heat sealed together.
In additional accordance wi-th this in~ention7 a method of compounding rubber is provided, and the corres- ~
ponding compounded rubber is provided which comprises mixing, and the resulting admixture including the sulfur cured admixture, said method comprising mixing unvulcanized rubber, particularly hereinbefore described packaged high unsaturation rubber overwrapped with the film com-posite of t:his invention, and conventional compounding ingredients, par-ticularly such ingredients packaged in -the film composite of this invention, optionally followed by sulfur curing said prepared mixture of rubber, packaging film and packaged compounds.
The practice of this invention is further illus-trated ~y reference to -the following examples which are , , 363~
intended -to be represen-tative rather than restric-tive of the scope of the inven-tion. Unless~ o-therwise indica-ted, all par-ts and percentages are by weight.
A film was prepared by blending an unvulcanized s-tyrene-butadiene-s-tyrene block polymer, high impac-t polystyrene, wax, and other ingredients, and extruding the fluid blend to form a film having a -thickness of about 5 mils.
The following Table 1 more clearly shows the formulation:
Table 1 C~mp~ Parts Styrene/butadiene/styrene block copolymerl65.0 High Impac* Polystyrene2 35.0 Synthetic Hydrocarbon Wax3 5.0 Stearic Acid (lubricant) 0.25 Polyethylene (lubricant)4 0.50 ~; Anti-oxidanta 1.0 1 SBS block copolymer obtained as Solprene 414 from The Phillips Petroleum Company.
2 High impact polystyrene obtained as Styron 475U from The Dow Chemical Company.
3 Synthetic hydrocarbon wax having a congealing point in the range of about 200~210F. (93-100C.) obtained as Paraflint HI-NI from The Moore and Munger Company.
4 A low molecular weight polye-thylene obtained as Epolene C10-P from me Eastman Chemical Comp-ny.
', ~ ', :~ .
~ 7 Packages of unvulcanized polybuta~iene wi-th this film were observe~ to be rel.at:ively easily separable even after s-tacking packaged 80 pound bales -three high on top of each other for a-t least 72 hours at a -tempera-ture of 190F~
: 5 In fur-ther accordance wi-th -this inven-tion, a polystyrene, particularly a high impact--type polys-tyrene, and method of i-ts preparation7 is provided. I~ such a utili-ty, a packaged rubber, particularly a rubber such as polybutadiene or styrene/butadie.ne copolymer (SBR), is packaged according to this inven-tion with the unvulcanized film composi-te overwrap, the packaged mixed and dissolved : in s-tyrene monomer and the s-tyrene polymerized by free radical catalysis, such as, for example with a peroxide catalyst by methods well known in -the s-tyrerepolymerization art. The end product, a high impact-type polystyrene, can be equivalent in specification to high impact polystyrene made without using the film overwrap in its preparation.
Exemplary of such a polystyrene and method of preparation is -the following example in which -the parts and percentages are by weight unless otherwise indicated.
.`
. EXAMPLE II
.
A high impact-type polys-tyrene is prepared in the following manner:
In a suitable vessel 100 parts of a rubbery poly-butadiene which is overwrapped with an unvulcanized styrene/
butadiene/styrene film of the type used in Example l is added ... ~ , . ~ .
~ .
:
~3~i3'7 with s-tirring -to 15~6.6 par-ts styrene monomer. The solution is agi-ta-ted un-til a homogeneous mix-ture is formed. Dis-solved in 40 parts by weigh-t o~ s-tyrene monomer is 1.02 parts benzoyl peroxide and ~.14 par-t by weight o~ mercap-tan modi~ier which is added to -the homogeneous mixture.
After these ingredien-ts are dispersed 7 -the agita-tion is continued but the -tempera-ture is increased -to and main-tained a-t 80C. ~or 4 hours. The -temperature is -then lowered to and is maintained at 75C. for an additional three hours. The reac-tion mass is removed ~rom the mixing vessel and is placed in a closed con-tainer ~or 17 hours at 100C. and 17 hours at 150C. Five parts by weight of stearic acid and two parts of alkylated aryl phosphate are evenly blended into the mass.
In this example, instead of conventional poly-butadiene, rubbers such as 1,4-polybutadiene, SBR, and polybutadiene or graft interpolymers o~ polybu-tadiene or ` even SBS block polymers can be used. The initiators for the polymerization could be lauroyl peroxide, 2-azo-bis-;~ 20 isobutyronitrile, hydroxyheptyl peroxide 9 methyl e-thyl ketone peroxide, caprylyl peroxide, ace-tyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichloro benzoyl peroxide, ' di-t-butyl peroxide, tertiary butyl perbenzoate and tertiary butyl peracetate or di-cumyl peroxide.
:Cn the practice o~ this invention, a ~ilm prepared according to Example I was tested for anti-block by its resistance to sticking, or adhesion, to itsel~.
The test was conducted by placing two film samples together so that a two-ply specimen was obtained in a square shape ;
~363~
of abou-t 2 inches in leng-th on a side. The specimen was placed between -two me-tal plates in a horizontal position and about 1.5 pounds per square inch pressure exerted on the plate. The resul-ting assembly was placed in a hot air oven at abou-t 190F. (88C.) ~or about 72 hours. The assembly was -then removed from the oven, and the film - tested ~or blocking (sticking or adhesion) rasistance b~ -manually pulling the films apar-t a-t abou-t a 180 angle.
In the tests conducted upon a number of samples of dif-ferent film formulations, a rating was established having the values of excellen-t, sa-tisfac-tory, and unsatisfactory.
The film of this example was given an excellent rating by this test with no noticeable tendency of the film -to block or stick -together.
; 15 While certain represen-tative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope Z0 of the invention.
:
'~ .
, , ,
', ~ ', :~ .
~ 7 Packages of unvulcanized polybuta~iene wi-th this film were observe~ to be rel.at:ively easily separable even after s-tacking packaged 80 pound bales -three high on top of each other for a-t least 72 hours at a -tempera-ture of 190F~
: 5 In fur-ther accordance wi-th -this inven-tion, a polystyrene, particularly a high impact--type polys-tyrene, and method of i-ts preparation7 is provided. I~ such a utili-ty, a packaged rubber, particularly a rubber such as polybutadiene or styrene/butadie.ne copolymer (SBR), is packaged according to this inven-tion with the unvulcanized film composi-te overwrap, the packaged mixed and dissolved : in s-tyrene monomer and the s-tyrene polymerized by free radical catalysis, such as, for example with a peroxide catalyst by methods well known in -the s-tyrerepolymerization art. The end product, a high impact-type polystyrene, can be equivalent in specification to high impact polystyrene made without using the film overwrap in its preparation.
Exemplary of such a polystyrene and method of preparation is -the following example in which -the parts and percentages are by weight unless otherwise indicated.
.`
. EXAMPLE II
.
A high impact-type polys-tyrene is prepared in the following manner:
In a suitable vessel 100 parts of a rubbery poly-butadiene which is overwrapped with an unvulcanized styrene/
butadiene/styrene film of the type used in Example l is added ... ~ , . ~ .
~ .
:
~3~i3'7 with s-tirring -to 15~6.6 par-ts styrene monomer. The solution is agi-ta-ted un-til a homogeneous mix-ture is formed. Dis-solved in 40 parts by weigh-t o~ s-tyrene monomer is 1.02 parts benzoyl peroxide and ~.14 par-t by weight o~ mercap-tan modi~ier which is added to -the homogeneous mixture.
After these ingredien-ts are dispersed 7 -the agita-tion is continued but the -tempera-ture is increased -to and main-tained a-t 80C. ~or 4 hours. The -temperature is -then lowered to and is maintained at 75C. for an additional three hours. The reac-tion mass is removed ~rom the mixing vessel and is placed in a closed con-tainer ~or 17 hours at 100C. and 17 hours at 150C. Five parts by weight of stearic acid and two parts of alkylated aryl phosphate are evenly blended into the mass.
In this example, instead of conventional poly-butadiene, rubbers such as 1,4-polybutadiene, SBR, and polybutadiene or graft interpolymers o~ polybu-tadiene or ` even SBS block polymers can be used. The initiators for the polymerization could be lauroyl peroxide, 2-azo-bis-;~ 20 isobutyronitrile, hydroxyheptyl peroxide 9 methyl e-thyl ketone peroxide, caprylyl peroxide, ace-tyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichloro benzoyl peroxide, ' di-t-butyl peroxide, tertiary butyl perbenzoate and tertiary butyl peracetate or di-cumyl peroxide.
:Cn the practice o~ this invention, a ~ilm prepared according to Example I was tested for anti-block by its resistance to sticking, or adhesion, to itsel~.
The test was conducted by placing two film samples together so that a two-ply specimen was obtained in a square shape ;
~363~
of abou-t 2 inches in leng-th on a side. The specimen was placed between -two me-tal plates in a horizontal position and about 1.5 pounds per square inch pressure exerted on the plate. The resul-ting assembly was placed in a hot air oven at abou-t 190F. (88C.) ~or about 72 hours. The assembly was -then removed from the oven, and the film - tested ~or blocking (sticking or adhesion) rasistance b~ -manually pulling the films apar-t a-t abou-t a 180 angle.
In the tests conducted upon a number of samples of dif-ferent film formulations, a rating was established having the values of excellen-t, sa-tisfac-tory, and unsatisfactory.
The film of this example was given an excellent rating by this test with no noticeable tendency of the film -to block or stick -together.
; 15 While certain represen-tative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope Z0 of the invention.
:
'~ .
, , ,
Claims (20)
1. A film composite, having a thickness of about 0.5 to about 10 mils, comprised of an admixture of (1) 100 parts by weight unvulcanized elastomeric block copolymer having the general configuration A-B-A where A is an independently selected nonelastomeric monovinyl aromatic hydrocarbon polymer block selected from styrene, .alpha.-methyl styrene or vinyl toluene having an average molecular weight of about 7,000 to about 25,000 and a glass transition temperature above about 25°C., the total block A content being about 12 to about 62 weight percent of the copolymer, and B is an elastomeric conjugated diene polymer block selected from 1,3-butadiene and isoprene having an average molecular weight of about 30,000 to about 100,000 and a glass transition temperature below about 10°C., said block copolymer having a melt viscosity in the range of about 0.1 to about 10 grams/10 minutes by ASTM No. D-1238, (2) about 25 to about 120 parts by weight thermoplastic resin selected from at least one polymer of styrene, .alpha.-methyl styrene, styrene/.alpha.-methyl styrene, vinyl toluene, vinyl toluene/
.alpha.-methyl styrene, indene resins, alkyl phenolic resins, petroleum and coal tar resins, or high impact polystyrene comprises of (a) about 100 parts by weight polystyrene having a molecular weight in the range of about 15,000 to about 50,000 and, dispersed therein, (b) about 3 to about 15 parts by weight elastomeric polymer selected from at least one of polybutadiene, polyisoprene and butadiene/styrene copolymers and (3) about 3 to about 10 parts by weight hydrocarbon paraffin wax having a cogealing point ASTM No. D-938-49 in the range of about 88°C. to about 105°C.
.alpha.-methyl styrene, indene resins, alkyl phenolic resins, petroleum and coal tar resins, or high impact polystyrene comprises of (a) about 100 parts by weight polystyrene having a molecular weight in the range of about 15,000 to about 50,000 and, dispersed therein, (b) about 3 to about 15 parts by weight elastomeric polymer selected from at least one of polybutadiene, polyisoprene and butadiene/styrene copolymers and (3) about 3 to about 10 parts by weight hydrocarbon paraffin wax having a cogealing point ASTM No. D-938-49 in the range of about 88°C. to about 105°C.
2. In a package of an article wrapped in a film of an unvulcanized block copolymer, the improvement in which a package is comprised of an article selected from unvulcanized rubber, compounding ingredients for unvulcanized rubber, and compounding ingredients for thermoplastic polymers wrapped in a protective film composite compatible with said unvulcanized rubber or thermoplastic polymer, respectively, having a thickness of about 0.5 to about 10 mils comprised of an admixture of (1) 100 parts by weight of an unvulcanized elastomeric block copolymer having the general configuration A-B-A
wherein each A is an independently selected nonelastomeric monovinyl aromatic hydrocarbon polymer block selected from styrene, .alpha.-methyl styrene or vinyl toluene having an average molecular weight of about 7,000 to about 25,000 and a glass transition temperature above about 25°C., the total block A content being from about 12 to about 62 weight percent by weight of the copolymer, and B
is an elastomeric conjugated diene polymer block selected from 1,3-butadiene and isoprene having an average molecular weight from about 30,000 to about 100,000 and a glass transition temperature below about 10°C., said block copolymer being further characterized by having a melt viscosity in the range of about 0.1 to about 10 grams/10 minutes according to ASTM No. D-1238, (2) about 25 to about 120 parts by weight of a thermoplastic resin selected from at least one polymer of styrene, .alpha.-methyl styrene, styrene/
.alpha.-methyl styrene, vinyl toluene, vinyl toluene/.alpha.-methyl styrene, indene resins, alkyl phenolic resins, petroleum and coal tar resins, or high impact polystyrene comprised of (a) about 100 parts by weight polystyrene having a molecular weight in the range of about 15,000 to about 50,000 and, dispersed therein, (b) about 3 to about 15 preferably about 3 to about 10, parts by weight of an elastomeric polymer selected from at least one of poly-butadiene, polyisoprene and butadiene/styrene copolymers and (3) about 3 to about 10 parts by weight hydrocarbon paraffin wax having a congealing point according to ASTM
#D-938-49 in the range of about 190°F. (88°C.) to about 220°F. (105°C.).
wherein each A is an independently selected nonelastomeric monovinyl aromatic hydrocarbon polymer block selected from styrene, .alpha.-methyl styrene or vinyl toluene having an average molecular weight of about 7,000 to about 25,000 and a glass transition temperature above about 25°C., the total block A content being from about 12 to about 62 weight percent by weight of the copolymer, and B
is an elastomeric conjugated diene polymer block selected from 1,3-butadiene and isoprene having an average molecular weight from about 30,000 to about 100,000 and a glass transition temperature below about 10°C., said block copolymer being further characterized by having a melt viscosity in the range of about 0.1 to about 10 grams/10 minutes according to ASTM No. D-1238, (2) about 25 to about 120 parts by weight of a thermoplastic resin selected from at least one polymer of styrene, .alpha.-methyl styrene, styrene/
.alpha.-methyl styrene, vinyl toluene, vinyl toluene/.alpha.-methyl styrene, indene resins, alkyl phenolic resins, petroleum and coal tar resins, or high impact polystyrene comprised of (a) about 100 parts by weight polystyrene having a molecular weight in the range of about 15,000 to about 50,000 and, dispersed therein, (b) about 3 to about 15 preferably about 3 to about 10, parts by weight of an elastomeric polymer selected from at least one of poly-butadiene, polyisoprene and butadiene/styrene copolymers and (3) about 3 to about 10 parts by weight hydrocarbon paraffin wax having a congealing point according to ASTM
#D-938-49 in the range of about 190°F. (88°C.) to about 220°F. (105°C.).
3. The package of claim 2, wherein said article is a high unsatutation rubber and where said protective film composite is comprised of an unvulcanized styrene/
butadiene/styrene block copolymer and a thermoplastic resin selected from poly(.alpha.-methyl-styrene, polystyrene or high impact polystyrene.
butadiene/styrene block copolymer and a thermoplastic resin selected from poly(.alpha.-methyl-styrene, polystyrene or high impact polystyrene.
4. The package of claim 2 wherein said article is selected from butadiene/styrene copolymers, polybutadiene and cis-1,4-polyisoprene and where said article is tightly wrapped with a heated sealed protective film composite having a thickness in the range of 0.75 to about 5.0 mils and comprised of an unvulcanized styrene/butadiene/styrene block copolymer and a thermoplastic resin selected from polystyrene, poly(.alpha.-methyl styrene), styrene/.alpha.-methyl
5. The package of claim 2 where said high impact polystyrene is comprises of about 100 parts by weight polystyrene having a molecular weight in the range of about 15,000 to about 50,000 and having dispersed therein about 5 to about 20 parts by weight of an elastomer selected from at least one of polybutadiene, polyisoprene or butadiene/styrene copolymers.
6. The package of claim 2 wherein said article is at least one compounding ingredient for unvulcanized rubber.
7. The package of claim 3 where said article is at least one compounding ingredient for thermoplastic polymers.
8. The package of claim 7 where said thermo-plastic polymer is polystyrene.
9. In a method of preparing a package of an article wrapped in a film of an unvulcanized block copoly-mer, the improvement which comprises wrapping an article selected from unvulcanized rubber, compounding ingredients for unvulcanized rubber, and compounding ingredients for thermoplastic polymers with a protective film composite compatible with said unvulcanized rubber or thermoplastic polymer, respectively, having a thickness of about 0.5 to about 10 mils comprised of an admixture of (l) 100 parts by weight of an unvulcanized elastomeric block copolymer having the general configuration A-B-A wherein each A is an independently selected nonelastomeric mono vinyl aromatic hydrocarbon polymer block selected from styrene, .alpha.-methyl styrene and vinyl toluene having an average molecular weight of about 7,000 to about 25,000 and a glass transition tem-perature above about 25°C., the total block A content being from about 20 to about 40 percent by weight of the copoly-mer, and B is an elastomeric conjugated diene polymer block selected from 1,3-butadine and isoprene having an average molecular weight from about 30,000 to about 100,000 and a glass transition temperature below about 10°C., said block copolymer being further characterized by having a melt viscosity in the range of about 0.1 to about 10 grams/10 minutes according to ASTM No. D-1238, (2) about 25 to about 120 parts by weight of at least one thermoplastic aromatic group-containing resin selected from at least one polymer of styrene, .alpha.-methyl styrene, styrene/.alpha.-methyl styrene, vinyl toluene, vinyl toluene/.alpha.-mehtyl styrene, indene resins, alkyl phenolic resins, petroleum resins, alkyl phenolic resins, petroleum and coal tar resins, or high impact polystyrene comprised of (a) about 100 parts by weight polystyrene having a molecular weight in the range of about 15,000 to about 50,000 and, dispersed therein, (b) by weight of an elastomeric polymer selected from at least one of polybutadiene, polyisoprene and butadiene/styrene copolymers and (3) about 3 to about 10 parts by weight hydrocarbon paraffin wax having a congealing point accord-ing to ASTM #D-938-49 in the range of about 190°F. (88°C.) to about 220°F. (105°C.).
10. A compounded high unsaturation rubber pre-pared by mixing a package of claim 2 wherein said article is an unvulcanized high unsaturation rubber with an addi-tional package of claim 1 wherein said article is at least one compounding ingredient for said unvulcanized high unsaturation rubber.
11. The compounded rubber of claim 10, wherein said compounding ingredient at least comprises sulfur, sulfur cured.
12. A compounded high unsaturation rubber pre-pared by mixing a package of claim 2 wherein said article is an unvulcanized high unsaturation rubber with at least one compounding ingredient comprised of sulfur.
13. The compounded rubber of claim 12, sulfur cured.
14. A compounded high unsaturation rubber pre-pared by mixing an unvulcanized high unsaturation rubber with a package of claim 2 where said article is at least one compounding ingredient for said unvulcanized high unsaturation rubber at least containing sulfur.
15. The compounded rubber of claim 14, sulfur cured.
16. A thermoplastic polymer prepared by (A) mixing and at least partially dissolving a package of claim 2 in styrene monomer, wherein said article is an unvulcanized rubber, and (B) polymerizing the styrene by free radical catalysis.
17. The film composite of claim 1 characterized by not tending to stick to itself according to the test conducted by placing two film samples together to form a two-ply specimen in a square shape of about 2 inches in length on a side, placing the specimen between two metal plates in a horizontal position, exerting about 1.5 pounds per square inch pressure on the plate, placing the resulting assembly in a hot air oven at about 190°F. (88°C.) for about 72 hours, removing the assembly from the oven, and testing the film for sticking resistance by manually pulling the films apart at about a 180° angle.
18. The package of claim 2, where said film composite wrap is characterized by not tending to stick to itself according to the test conducted by placing two film samples together to form a two-ply specimen in a square shape of about 2 inches in length on a side, placing the specimen between two metal plates in a horizontal position, exerting about 1.5 pounds per square inch pressure on the plate, placing the resulting assembly in a hot air oven at about 190°F. (88°C.) for about 72 hours, removing the assembly from the oven and testing the film for sticking resistance by manually pulling the films apart at about a 180° angle.
19. The compounded high unsaturation rubber of claim 10, where said package is the article wrapped in the film composite, with the film composite characterized by not tending to stick to itself according to the test con-ducted by placing two film samples together to form a two-ply specimen in a square shape of about 2 inches in length on a side, placing the specimen between two metal plates in a horizontal position, exerting about 1.5 pounds per square inch pressure on the plate, placing the resulting assembly in a hot air oven at about 190°F. (88°C.) for about 72 hours, removing the assembly from the oven, and testing the film for sticking resistance by manually pulling the films apart at about 180° angle.
20. The thermoplastic polymer of claim 16 where said package is the article wrapped in the film composite, with the film composite characterized by not tending to stick to itself according to the test conducted by placing two film samples together to form a two-ply specimen in a square shape of about 2 inches in length on a side, placing the specimen between two metal plates in a hor-zontal position, exerting about 1.5 pounds per square inch pressure on the plate, placing the resulting assembly in a hot air oven about 190°F. (88°C.) for about 72 hours, removing the assembly from the oven, and testing the film for sticking resistance by manually pulling the films apart at about a 180° angle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86383377A | 1977-12-23 | 1977-12-23 | |
| US863,833 | 1997-05-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1113637A true CA1113637A (en) | 1981-12-01 |
Family
ID=25341894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA312,577A Expired CA1113637A (en) | 1977-12-23 | 1978-10-03 | Film composite and packaged articles therewith |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS6011982B2 (en) |
| AU (1) | AU521123B2 (en) |
| BR (1) | BR7808160A (en) |
| CA (1) | CA1113637A (en) |
| DE (1) | DE2854640A1 (en) |
| FR (1) | FR2412578A1 (en) |
| GB (1) | GB2010862B (en) |
| MY (1) | MY8300157A (en) |
| ZA (1) | ZA786623B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337188A (en) | 1979-12-17 | 1982-06-29 | Du Pont Canada Inc. | Polyolefin composition for manufacture of film having cling properties |
| JPS57212249A (en) * | 1981-06-23 | 1982-12-27 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomeric composition |
| EP0385599A3 (en) * | 1989-02-13 | 1992-08-05 | Exxon Chemical Patents Inc. | Film and polymer composition for film |
| JPH0567792U (en) * | 1992-02-21 | 1993-09-10 | 千代▲吉▼ 星 | Shutters |
| JPH0631864A (en) * | 1992-06-23 | 1994-02-08 | Alusuisse Lonza Services Ag | Co-extruded heat-seal lacquer-coated synthetic resin composite |
| TR199600222A2 (en) * | 1995-03-24 | 1996-10-21 | Shell Int Research | Compositions containing monovinyl aromatic block copolymer and microgranules and powders derived therefrom, suitable for use in rotary molding and similar processes. |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1073570A (en) * | 1975-09-29 | 1980-03-11 | William A. Watts | Packaged articles |
| CA1073571A (en) * | 1975-09-29 | 1980-03-11 | Goodyear Tire And Rubber Company (The) | Packaging films and packaged articles therewith |
-
1978
- 1978-10-03 CA CA312,577A patent/CA1113637A/en not_active Expired
- 1978-11-24 ZA ZA00786623A patent/ZA786623B/en unknown
- 1978-11-24 AU AU41920/78A patent/AU521123B2/en not_active Expired
- 1978-11-27 GB GB7846243A patent/GB2010862B/en not_active Expired
- 1978-12-13 BR BR7808160A patent/BR7808160A/en unknown
- 1978-12-13 FR FR7835041A patent/FR2412578A1/en active Granted
- 1978-12-18 DE DE19782854640 patent/DE2854640A1/en not_active Withdrawn
- 1978-12-23 JP JP53159116A patent/JPS6011982B2/en not_active Expired
-
1983
- 1983-12-30 MY MY157/83A patent/MY8300157A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR7808160A (en) | 1979-08-07 |
| GB2010862A (en) | 1979-07-04 |
| JPS6011982B2 (en) | 1985-03-29 |
| AU521123B2 (en) | 1982-03-18 |
| MY8300157A (en) | 1983-12-31 |
| AU4192078A (en) | 1979-06-28 |
| GB2010862B (en) | 1982-04-28 |
| FR2412578B1 (en) | 1984-03-16 |
| ZA786623B (en) | 1979-10-31 |
| FR2412578A1 (en) | 1979-07-20 |
| DE2854640A1 (en) | 1979-07-05 |
| JPS5499155A (en) | 1979-08-04 |
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