CA1202745A - Blend of internally plasticized vinyl chloride copolymer and ethylene/carbon monoxide polymer - Google Patents
Blend of internally plasticized vinyl chloride copolymer and ethylene/carbon monoxide polymerInfo
- Publication number
- CA1202745A CA1202745A CA000395175A CA395175A CA1202745A CA 1202745 A CA1202745 A CA 1202745A CA 000395175 A CA000395175 A CA 000395175A CA 395175 A CA395175 A CA 395175A CA 1202745 A CA1202745 A CA 1202745A
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- CA
- Canada
- Prior art keywords
- brand
- carbon monoxide
- weight
- ethylene
- blend
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
Abstract
BLEND OF INTERNALLY PLASTICIZED VINYL CHLORIDE
COPOLYMER AND ETHYLENE/CARBON MONOXIDE POLYMER
Abstract of the Disclosure The blending of an effective amount of an ethyl-ene/carbon monoxide polymer with an internally plasti-cized vinyl chloride copolymer improves the low temperature flexibility and color stability during ageing of films made from the resulting blend as compared to films continuing the internally plasti-cized resin in the absence of the ethylene/carbon monoxide polymer.
COPOLYMER AND ETHYLENE/CARBON MONOXIDE POLYMER
Abstract of the Disclosure The blending of an effective amount of an ethyl-ene/carbon monoxide polymer with an internally plasti-cized vinyl chloride copolymer improves the low temperature flexibility and color stability during ageing of films made from the resulting blend as compared to films continuing the internally plasti-cized resin in the absence of the ethylene/carbon monoxide polymer.
Description
a,~!t ~
BLEND OF INTERNA:CLY PLASTICIZED VINYII CHLORIDE
COPOLYMER AND ETHYLENE/CARBON MONOXIDE POhYMER
Background of the Invention The present invention relates to a blend of poly-mers which is useful in making film products and WhiCh contains an internally plasticized vinyl chloride co-polymer.
Description of the Prior Art ~ . .
Externally plasticized vinyl chloride films have been used to make "coated fabrics" which, when bonded to a fabric substrate, for example, are useful as upholstery material. An example of such conventional technolo~y is described in U.S. Patent No. 3~988,519 to F. L. Stoller. Recently, it has been suggested to substitute the polyvinyl chloride polymer and external plastici.zer in such produc~s with an internally plasti-cized vinyl chloride copolymer resin ~European Patent No. 4/391). Although such products represent an im provement over externally plasticized films in regard to their lessened tendehcy to "fog" (due to the absence of transient external plasticizer), they still have certain drawbacks when intended for use in cer-tain commercial embodiments having rather stringent requirements regardin~ such combined characteristics as the pliability, strength and cold crack resistance of the product.
~`
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Summary of the Present Invention The present invention is a blend of internally plasticized vinyl chloride copolymer and an effective amount of an ethylene/carbon monoxide terpolymer to improve the physical properties of films ~ormed from the blend as compared to films containing the internal-ly plasticized vinyl chloride copolymer in the absence.
of the ethylene/carbon monoxide terpol~mer. In par-ticularr such properties as pliability, strength, lowtemperatuxe flexibility or cold crack resistance, and color stability during heat aging of the ~ilms are improved.
Description of the Present Invention The blend of the present invention comprises, as one component, a suitable internally plasticized vinyl chloride copolymer. Generally, this copolymer will comprise from about 40% to ahout 60%, by weight of the blend. The additional components of the ~lend will ~e an ethylene/carbon monoxide polymer additive, and, in preferred embodiments, one or more convention-al heat and light stab.ilizers, ultraviolet ~tabilizers, pigments, fillers, dyes, fungicides~ and the likel in amounts conventionally used. The blend can be used to make films, which when l~mi~ted to a suitable fabric ~ack~ng/ are useful as upholstery material.
.. For purposes o~ the present invention, the termin~
3n ology "internally plasticized" is to be construed as ` coverins copolymers having an agent incorporated in the resin itself during polymerization to provide the ~ .
C~61~
27~5 needed degree of flexibility to films made containing the copolymer rather than to conventional vinyl chlor-ide polymers or copolym~rs requiring a plasticizing amount (e.g., 25 to lQ0 parts by weight per lO0 parts by weight of resin) of external plasticizer during resin compounding to achieve such results.
Internally plasticized vinyl chloride copolymer resins suitable for use in the present invention can be formed by polymerizing ~inyl chloride monomer i~
the presence of an effective amount (10% to 50%, by weight) of at least one comonomer which function5 as an internal plasticizer. Included within this class of plasticizing comonomers are the alkyl acrylates and methacrylates containing up to about 18 carbon atom~ in their alkyl moieties, the vinyl esters of carboxylic acids and ethylenically unsaturated di-carboxylic acids, their anhydrides, and their mono-and dialkyl esters containing up to about 20 carbon atoms in their alkyl moietiesO
The internally plasticiæed resin suitable for u~e in the present invention should have a Tg of from about -10C. to about 30C. and should give a vinyl film having a Shore "A" Hardness of from about 70 to about 95 when in .he absence of functional additives and when no substantial amounts of plasticizer are present.
A preferred internally plasticized copolymer resin for use in the laminate of the present invention is described in U.S. Patent No~ 4,147,853 to ~. C.
Goswami et al~
~` This copolymer comprises: (l) from about 50~ to ab~ut 85%, ~y weight, vinyl chloride; (2) fxom about 3% to about 47%, by weight, of a C6-C10 alkyl 7~
acry].ate; and (3) from ~bout 47% to about 3%, by weiyh~, of a bis(hydrocarbyl)vinylphosphona~e of the formula:
X O OR'~
CH2=C P~ ,~
OR~
where X is selected from the group consisting of hydro gen, halogen, cyano, aryl (such as phenyl), C1-C18 alkyl and O / OR'~
_p op~o where R and R' are hydrocarbyl and substituted hydro-carbyl groups consisting essentially of hydrogen and carbon, and containing up to about 18 carbon atoms, inclusive, with the proviso that R and R' may be the same, different or conjoint, i.e., R and R' may com-bine to orm one single radical Preferred weight amounts for the comonomers used to make the above-descri~ed copolymer are: (1) from about 55~ to about80~r by weight, vinyl chloride; (2) from about 10~ to about 35~, by weight, o~ the acrylate; and (3) from about 5~ to about 25~ by weight o~ the vinylphosphon-ate~ A particularly pre~erred acrylate is 2-ethyl-hexyl acrylate, while paxticularly preferred vinyl-phosphonates are bis(beta-chloroethyl)vinylphosphon-ate and bis(2-ethylhexyl)vinylphosphonate~
p ;~ r7 ~
Irhe aforementioned internally plasticized copoly-mer can be formed by conventional bulk, emulsion, suspension, or solution polymerization procedures, although suspension polymerization is preferred.
Also useful in the present invention is the in-ternally plasticized resin described in U.S. Patent No. 4,210,739 to R. E. Gallagher et al. which com-prises from about 45% ~o a~ou~ 8Q~, by weight, vinyl chloride, from about 15% to about 54%, by weight, of a C2-C10 alkyl acrylate, and from about 10% to about 15%~ by weight, of at least one C8-C22 dialkyl maleate or fumarater The use o~ the above~described type of internal-ly plasticized resin allows for production of a ~ilm having the desired degree of ~lexibility without the use of any significant amount of external plasticizer such as employed in certain prior ar~ films. Gener-ally speaking, the amount of internally plasticized resin in the vin~l film can range from about 35% to about 75%, by weight of the film depending upon the type of film required.
The ethylene/carbon monoxide polymer which is xesponsible for the improved physical properties for films made from t~e blend of the present invention is a known material and has been suggested as an additive to conventional, non-internally plasticized polyvinyl chloride resins ~see U.S. Pa~ent ~lo. 3,780,140 to C. F. Hammer). It is a copolymer of: (a) from about 40% to about 80~ ethylene; (b) about 3~ to about 30%
carbon monoxide; and (c) from about 5% to about 60~, by weight of one or more termonomers copolymerizable therewith. Examples of suitable termonomers include l.~dqJ ~7~5 ~le C3-C~o unsaturated monv- and dicarboxylic acids and their esters; the C~-C~8 vinyl esters of saturated carboxylic acids; the vinyl C1-C 18 alkyl ethers, acrylonitrile; methacrylonitrile; the C3-C1 2 alpha olefins, and ring compounds such as norbornene and vinyl aromatic compounds. A preferred polymer com-prises 40-80% ethylene, 3 30% carbon monoxidet and 10-50% vinyl acetate. Ethylene/carbon monoxide poly-mers of this type are commercially available under the trademark EL~ALOY from E. Io DuPont de~emours and Company.
The weight amount of ethylene/carbon monoxide polymer which needs to be used in the blend is rela-ti~ely small in order to be effective to give the intended improvement in the physical properties for the films formed therefrom. Generallyl an amount of ethylene~carbon monoxide polymer ranying from about 5% to about 40%~ by weight of the blend of internally plasticized resin and ethylene/carbon monoxide ter-polymer will b~ sufficient. The use of harder inter- ' nally plasticized resins (which contain a higher vinyl chloride content) will require use of higher amounts of the ethylene/carbon monoxide polymex. Generally, the amount of internally plasticiæed copolymer will range from about 35~ to about 75%, by weight of the entire composition~ The weight ratio of internally plasticized copolymer to ethylene/carbon monoxide polymer will generally be within the range of from about 4:1 to a~out 1.5:1 with a higher ratio of internally plasticized resin being required when its vinyl chloride content is lower.
s ~ number of other additives are used in manufac-turing the ~inyl film component contained in the lam-inates of the present invention. Included as poten-tial additives are the following:
(a) fillers and/or pigments. The am~unt of filler that is chosen can range from about 0~ to about ~0~, by weight. Fillers and pigments are used to pro-vide desired color to the film, to provide opacity, and to aid in the calendering of the film forming composition. Representative pigments or fillers in-clude such inorganic materials as titanium dioxide, calcium carbonate, zinc oxide, white lead, gypsum, precipitated silica, carbon black, red iron oxide.
Others are well known by the person of ordinary skill in the art.
(b) monomeric and pol~meric process aids. These additives serve to aid in the processing of the cal-enderable film forming compositions as well as giving the film favorable visual appearance. Included are such polymeric additives as PVC/acrylate resin/
acrylate processing aids, and chlorinated polyethyl-ene, which produce a smooth surface on the calendered film, and alpha methyl styrene or acrylic polymers which also function as process aids. l`hese additives may be used at from about 2% to about 15%, by weight o~ the film.
(c) lubricants. These may be present at from about Q.5~ to a~out 3~, by weight of the film. In-cluded as representative lubricants are stearic acid, stearamide, the polyethylene waxes, hydrocarbon oils, and the like.
C-61~5 7~i ~ d) stabiliæers and antioxidants. These may be present at from about 3~ to about 10~, by weight of the film. Included are the stearate salts, the epoxi-dized vegetable oils, dibasic lead phosphite and di butyl tin dilaura~e, dimaleate or mercaptide. Others that may be selected are well known to persons of ordinary skill in the art.
Other functional addi~ives that can be present in relatively minor amount (under 2%J by weight, of the film) include ultraviolet light stabilizers, drying agents, and the like.
~ he first step in forming the vinyl film laminate of the present invention is the formation of a film forming composition which can be calendered and which has good chemical resistance and outdoor durability.
The aforementioned internally plasticized resin~ethyl-ene/carbon monoxide polymer, filler and/or pigment, monomeric and polymeric process aid, lubricant, or stabilizers and antioxidant components can be selected in the aforementioned amounts, if desired.
These selected ingredients are mixed until they are in the form of a homogeneous powdery composition. They can be then fluxed under sufficient heat and pressure to yield a composition of a dough-like consistency.
After passing t~rough a strainer apparatus they are ready for calendering.
This film ormulation is then calendered at a temperature and pressure which allows formation of a film h~ing a thickness of aboug 125 to 375 micron~.
A calendering temperature of from about 13Q to about 18QC. is recommended.
The film can be used to form laminate products ~which are useful in upholstery applications. These -p~7~5 laminates contain a suitable fabric substrate (e.g., woven, non-woven, blends of woven or non-woven, and so forth) attached to the vinyl film (for example, by means of a plastisol adhesive). The laminates can be formed by any means used to form conventional external-ly plasticized vinyl film/fabric substrate laminates.
Some examples of such procedures include: transfer coating, direct calender lamination, and post-lamina-tion.
The present invention is further illustrated by the Examples which follow.
7~
E%AMPLE 1 This Example illustrates the formation of a film and laminated produc~ in accordance wi~h the present invention.
The ingredient~ listed below were milled together on a two roll mill at a temperature of about 160 to 165C. for about 20 minutes to form a film:
Amount Ingredient(Parts by Wei~ht) Internally plasticized resin* 45,7 E~hylene/vinyl acetate/carb~
monoxide polymer (ELVALOY
741P brand) 23.2 15 Antimony oxide (CHEMTRON L brand) 2.5 Anhydrous ~ uminum silicate filler (BURGESS KE brand) 7.0 Bis-stearamide lubricant (AD~AWAX
240) 0 5 Dioctyl azelate plasticizer 4.0 20 Partially oxidized polyethylene lubricant 1.2 **
Zinc heat stabilizer (SYNPRON 1402 brand~ 3.0 Barium/cadlnium heat stabilizer ~SYNPRO~ ~517 brand) 1~0 Titanium dioxide~pigment (R-900 brand) 5-7 Epoxidized soya oil heat and light stabilizer (G-62 brand) 3.5 Stearic acid 0.7 Silica (FK-310 brand) 1.0 . Phenolic antioxidant tCYANAMID
- 2246 brand) 0.5 Calcium stearate lubricant 0.5 * a terpolymer which comprises about 75~, by weight, ** Tr~e~rk EXAMPLE 1 (cont'd.3 Footnote (cont'd.) vinyl chloride, about 18%, by weight, 2-ethylhexyl acrylate, and about 7%, by weight, bis(beta)chloro-ethyl)vinylphosphonate.
The film which was formed, as described above, had the following properties:
Test Value ___ Craves Tear Strength (~STM D 1004-66) 29.8/39.5 kg./cm.
Film Color (after 400(~ach dir./cross dir.) hrs. in ~TLAS FADE-O-METER apparatus) (ASTM G25-70) No change Film Color (after 40Q
hrs. in WEATHER-O-METER apparatus) (ASTM ~ 2565-27) No change T.~r; n~ted products wer~ made from the film by laminating the film to a non-woven polyester-poly-urethane substrate having a thickness of about 889-1016 microns (CAFJ-140 brand from Foss Manufacturing) at a temperature o~ a~out 150~C. using a plastisol adhe~ive at about 33O9 gm./m2 in a laminating/embos-sing apparatus. The laminates were then topcoated with. a blend of PVC and polymethylmethacrylate in a ratio o~ 3:2. The topcoated ~ilm/~abric lam.inate was then tested for its cold crack properties at -28.9C.
wikh:and without a heat ageing procedure (93.3C. for 6 days)o l.~qJ`~
EXAMPI,E 1 ~cont'd.~
Laminated Product Result Non-heat aged Pass Heat aged Fail "Pass" indicates no cracking when a 1.81 kg. weight falling through 20.3 cm. strikes the sample mounted on a 5.1 cm. thick foam mounted on wood. "Fail"
indicates cracking of the sample.
.
C-61~5 ~. ~d J~
This Example illustrates another embodiment of the present invention which is particularly preferred.
5A film forming composition was prepared as described in Example 1 from the following ingredients:
Amount Ingredient(Parts b~ Weight) 10 Internally plasticized resin* 45.7 Ethylene/vinyl acetate/carbon monoxide polymer (ELVALOY
741P brand) 25.2 Antimony oxide~flame retardant (CHEMTRON L brand) 2.5 15 Magnesium carbonate filler (MAGCARB L brand) 5.0 Octyl epoxy stearate heat and ligh~ stabilizer (DRAPEX 3.2 brand) 3.5 Bis-stearamide lubricant (AD~AWAX
240) 0 5 Dioctyl azelate plasticizer4.0 PartiaIly oxidized polyethylene lubricant 1.2 Zinc heat stabilizer (SYNPP~ON
1402 brand) 3.0 25 Barium/cadmium heat stabilizer ~SYNPRON 1517 brand~ 1 0 Titanium dioxide pigment (R-900 brand) 5.7 Stearic a id lubricant 0~7 Silica release agent (FK-310 brand) ~.0 : Phenolic antioxidant (C~ANAMID
3D 2246 brand) 0.5 Calcium stearate luhricant 0.5 * the terpolymer used in Example 1.
- \
EX~MPLE 2 (Cont'd.) The formulation mentioned above was fluxed on a two-roll mill for about 20 minutes at a temperature of about 160-165C. to generate a film having a thick-ness of about 254-305 microns for determination of physical property characteristics. The following was noted:
T _ Value Graves Tear Strength (ASTM D 1004-66) 26.4/35.2 kg./cm.
(mach. dir./cross dir.) T.~m; n~ted products were made from ~he film by l~in~ting the film to a non-woven polyester-poly-urethane substrate having a thickness of about 889-1016 microns at a temperature of about 150C. in a 1 ~m; n~ting/embossing apparatus n The laminates were then topcoated with a blend of PVC and polymethyl-methacrylate in a ratio of 3:2. The laminated film/fabric was then tested for its cold crack properties at -28.9C. with and without a heat aging procedure (93.3C. for 6 days) according to the test described in Example 1.
Laminated Product Result Non-heat aged Pass Heat aged Pass ~ `p~
- lS -These Examples illustrate the ~ormation of addi-tional films and laminated products. The same proced-ure used-in Ex~mples 1 and 2 was employed except where noted. The following ingredients were used to form the film forming composition:
Amount (Parts by Weight) Ingredient 3 Internally plasticized resin*~2.3 42.3 Ethylene/vinyl acetate/carbon monoxide polymer (ELVALOY
741P brand) 2002 20.2 Chlorinated polyethylene (Dow CPE 4213 brand) 8.4 8.4 Antimony oxide flame retardant (CHEMTRON L brand) 2.5 2.5 Magnesium ~arbonate filler (MAGCARB L brand) 5.5 5.5 Epoxidize~ soyabean oil (G-62 brand) 3.5 ---Octyl epoxy stearate*heat and light stabilizer (DRAPEX 3.2 brand) --- 3.5 Bis-stearamide lubricant (ADVAWAX
240) 0.5 0.5 Dioctyl azelate plasticizer 4.0 4.0 Partially oxidized polyethylene lubrica~t 1.2 1.2 zinc heat stabilizer (SYNPRON 1402 brand) 3.0 3.0 Barium/cadmium heat stabilizer (SYNPRON 1517 brand) 1.0 1.0 Titanium dioxide pigment ~R-900 brand) 5.7 5.7 Stearic acid lubricant 0.7 0.7 * Trademark 7~
EXAMP.~ES 3-6 (cont'd.) Amount (Parts by Weight) Ingredient 3 4 Silica release agent (FK-310 brand) 1.0 1.0 Calcium stearate lubricant 0.5 0.5 -* the terpolymer used in Example 1.
Amount ~Parts by Weight) Ingredient 5 6 Internally plasticized resin* 45.7 45.7 Ethylene/vinyl/acetate carbon monoxide polymer (ELVALOY
741P brand) 25.2 25.2 Chlorinated polyethylene (Dow CPE 4213 brand) Antimony oxide flame retardant (CHEMTRON L brand) 2.5 2.5 Magnesium carbonate ~iller (MAGCARB L brand) 5.0 5.0 Epoxidized soyabean oil (G-62 brand) 3-5 ~~~
Octyl epoxy stearate heat and light stabilizer (DRAPEX 3.2 brand) --- 3-5 25 Bis-stearamide lubricant 0.5 0.5 Dioctyl azelate plasti~izer 4.0 4.0 Partially oxidized polyethylene lubricant 1.2 1.2 Zinc heat sta~ilizer (SYNPRON
14Q2 brand) 3.0 3.0 30 Barium~cadmium heat stabilizer (SY~PRON 1517 brand) 1.0 1.0 Titanium dioxid~ pi~ment 5.7 5.7 (R-90Ø brand) EXAMPLES 3-6 (cont'd.) Amount ~ (Parts by Weight) Ingredie~t 5 6 Stearic acid lub.ricant 0.7 0.7 Silica release agent (FR-310 brand) 1.0 1.0 Calcium stearate lubricant 0.5 0~5 Phenolic antioxidant (AMERICAN
CYANAMID 2246) 0.5 0.5 *the terpol~mer used in Example lo The laminates from Examples 3 6 were subjected to various physical property tests with the following significant results being noted.
Laminate Example No.
Weight ~gm./m2) 467.8 498.3 518.7 508.5 Adhesion tMD~(1) CNS 1786 CNS CNS
Pliability (mm.) (2) 18.0320.129.98 20.42 Stretch (MD, ~) (3) 32~334.3 27.6 41.3 Set (MD, ~) (4) 8.0 8.0 9.3 8.0 Tensile Grab (MD) (5) 477J545 405 365 360 (MD/CD) Tongue Tear ~MD) (6) __~ 95 95 90 MVSS 302 ( 7) SE SE SE SE
. Abrasion, Wyzenbeek( 8 ~ OK OK OK OK
(,) Adhesion of the film to the fabric was tested in accordance with ASTM D 751-68~ The abbreviation CNS indicates that the film and fabric could not ~e separated. The rate of travel of the lower t74~
EXAMPLES 3~6 (cont'd.) Footnotes (con-t'd.) jaw of the tensile tester was 5.08 cm. per minute.
The abbreviations MD and CD stand for machine direction and cross-direction, respectively, and indicate the direction in which the force was applied. The laminate from Example No. 4 separ-ated at 1786 gm./cm~when tested in the machine direction~
0 (2) run at 21.1C., 50% relative humidi~y. This test d~termines the deflection imparted to a weighted (30 gm.) thickness gauge mounted on top of a loop of the sample when the sample is raised by one inch. The sample is 2.54 cm. x 7.62 cm. with the long dimension being the machine direction and the coating is on the outside. The higher the gauge deflection, the stif~er the material. A complete-ly rigid sample would give a value of 25.4 mm.
For comparison, typical values f~r conventional automobile upholstery will be higher than 19.05 mm.
with a 50 gm. weight; much higher for a 30 gm. wt.
(3) run in accordance with Chemlcal Fabrics and Film Assn. (CFFA)-19 test procedure. The percentage (4) for stretch figure represents the perc~ntage in-crease in length after 10 minu~es while under a load of 12.25 kg. The percentage for set indi-cates the i~crease in length after the load is removed and the samples are allowed to relax for 10 minutes.
( 5) the values are given in New~ons when tested in accordance with ASTM 751-68. It represents the te~sile or breaking strength of the samples.
(6) the values are given in Newtons when tested in accordance with Federal Standard 191, Mathod 5134.
It represents the tearing streng~h of the samples.
(~) MVSS 302 (Motor Vehicle Safety Standard 30Z) tests ~he fl~r~hility of the samples with '~SE"
denoting "self-extinguishingl'.
( 8 ) the Wyzenbeek method (Federal Standard Mo. 191, Method 5304) measures the abrasion resistance of coated fabrics using the Wyzenbeek and Staff abrasion wear tester. The results were -- lg --EX~MPLES 3-6 (cont'd.) Footnotes ~cont'd.) determined under standard test conditions after 25,000 double rubsO "OK" indicates no visible abrasion was noted.
The laminate ~rom Example 3 was also tested for its fogging characteristics. The sample was placed in a cylindrical holder about 15.24 cm. in diameter and heated to 71.1C. One end of the cylinder was closed, and the other sealed by a glass cap main-tained at 37.8C. Volatile material was collected on the glass cap reducing the light transmission to about ~0% after 72 hours. For comparison, standard externally plasticized automobile upholstery have a value of about 40% original light transmission after about 72 hours.
27~S
ExAMæLE 7 The laminates from Examples 5 and 6 were also tested for cold crack properties after being coated with two differing topcoats. Both topcoats wexe applied by 33.5 line per cm.pad rolls at room ~empera-ture followed by air drying.
Topcoat A was a vinyl/acrylic topcoat with a vinyl/
acrylate ratio of 3/2.
Topcoat B was a urethane topcoat sold under the trademark PE~MU~HANE U~10-046 by Beatrice Chemical Co.
A series of laminates were tested for its cold cracX properties at -28.gC. with and without heat aging at 93.3C. for 6 days.
Unheat Aged ~eat Aged T.. -in~te fxom Topcoat Topcoat Topcoat Topcoat Example A B A B
. 3 o~ ~ 2 of 2 1 of 4 2 o~ 2 passed passed passed passed 6 4 of 4 2 o~ 2 4 of 4 2 of 2 passed passed passed passed C-61~5 ~2~ S
BLEND OF INTERNA:CLY PLASTICIZED VINYII CHLORIDE
COPOLYMER AND ETHYLENE/CARBON MONOXIDE POhYMER
Background of the Invention The present invention relates to a blend of poly-mers which is useful in making film products and WhiCh contains an internally plasticized vinyl chloride co-polymer.
Description of the Prior Art ~ . .
Externally plasticized vinyl chloride films have been used to make "coated fabrics" which, when bonded to a fabric substrate, for example, are useful as upholstery material. An example of such conventional technolo~y is described in U.S. Patent No. 3~988,519 to F. L. Stoller. Recently, it has been suggested to substitute the polyvinyl chloride polymer and external plastici.zer in such produc~s with an internally plasti-cized vinyl chloride copolymer resin ~European Patent No. 4/391). Although such products represent an im provement over externally plasticized films in regard to their lessened tendehcy to "fog" (due to the absence of transient external plasticizer), they still have certain drawbacks when intended for use in cer-tain commercial embodiments having rather stringent requirements regardin~ such combined characteristics as the pliability, strength and cold crack resistance of the product.
~`
P~'7~
-- 2 ~
Summary of the Present Invention The present invention is a blend of internally plasticized vinyl chloride copolymer and an effective amount of an ethylene/carbon monoxide terpolymer to improve the physical properties of films ~ormed from the blend as compared to films containing the internal-ly plasticized vinyl chloride copolymer in the absence.
of the ethylene/carbon monoxide terpol~mer. In par-ticularr such properties as pliability, strength, lowtemperatuxe flexibility or cold crack resistance, and color stability during heat aging of the ~ilms are improved.
Description of the Present Invention The blend of the present invention comprises, as one component, a suitable internally plasticized vinyl chloride copolymer. Generally, this copolymer will comprise from about 40% to ahout 60%, by weight of the blend. The additional components of the ~lend will ~e an ethylene/carbon monoxide polymer additive, and, in preferred embodiments, one or more convention-al heat and light stab.ilizers, ultraviolet ~tabilizers, pigments, fillers, dyes, fungicides~ and the likel in amounts conventionally used. The blend can be used to make films, which when l~mi~ted to a suitable fabric ~ack~ng/ are useful as upholstery material.
.. For purposes o~ the present invention, the termin~
3n ology "internally plasticized" is to be construed as ` coverins copolymers having an agent incorporated in the resin itself during polymerization to provide the ~ .
C~61~
27~5 needed degree of flexibility to films made containing the copolymer rather than to conventional vinyl chlor-ide polymers or copolym~rs requiring a plasticizing amount (e.g., 25 to lQ0 parts by weight per lO0 parts by weight of resin) of external plasticizer during resin compounding to achieve such results.
Internally plasticized vinyl chloride copolymer resins suitable for use in the present invention can be formed by polymerizing ~inyl chloride monomer i~
the presence of an effective amount (10% to 50%, by weight) of at least one comonomer which function5 as an internal plasticizer. Included within this class of plasticizing comonomers are the alkyl acrylates and methacrylates containing up to about 18 carbon atom~ in their alkyl moieties, the vinyl esters of carboxylic acids and ethylenically unsaturated di-carboxylic acids, their anhydrides, and their mono-and dialkyl esters containing up to about 20 carbon atoms in their alkyl moietiesO
The internally plasticiæed resin suitable for u~e in the present invention should have a Tg of from about -10C. to about 30C. and should give a vinyl film having a Shore "A" Hardness of from about 70 to about 95 when in .he absence of functional additives and when no substantial amounts of plasticizer are present.
A preferred internally plasticized copolymer resin for use in the laminate of the present invention is described in U.S. Patent No~ 4,147,853 to ~. C.
Goswami et al~
~` This copolymer comprises: (l) from about 50~ to ab~ut 85%, ~y weight, vinyl chloride; (2) fxom about 3% to about 47%, by weight, of a C6-C10 alkyl 7~
acry].ate; and (3) from ~bout 47% to about 3%, by weiyh~, of a bis(hydrocarbyl)vinylphosphona~e of the formula:
X O OR'~
CH2=C P~ ,~
OR~
where X is selected from the group consisting of hydro gen, halogen, cyano, aryl (such as phenyl), C1-C18 alkyl and O / OR'~
_p op~o where R and R' are hydrocarbyl and substituted hydro-carbyl groups consisting essentially of hydrogen and carbon, and containing up to about 18 carbon atoms, inclusive, with the proviso that R and R' may be the same, different or conjoint, i.e., R and R' may com-bine to orm one single radical Preferred weight amounts for the comonomers used to make the above-descri~ed copolymer are: (1) from about 55~ to about80~r by weight, vinyl chloride; (2) from about 10~ to about 35~, by weight, o~ the acrylate; and (3) from about 5~ to about 25~ by weight o~ the vinylphosphon-ate~ A particularly pre~erred acrylate is 2-ethyl-hexyl acrylate, while paxticularly preferred vinyl-phosphonates are bis(beta-chloroethyl)vinylphosphon-ate and bis(2-ethylhexyl)vinylphosphonate~
p ;~ r7 ~
Irhe aforementioned internally plasticized copoly-mer can be formed by conventional bulk, emulsion, suspension, or solution polymerization procedures, although suspension polymerization is preferred.
Also useful in the present invention is the in-ternally plasticized resin described in U.S. Patent No. 4,210,739 to R. E. Gallagher et al. which com-prises from about 45% ~o a~ou~ 8Q~, by weight, vinyl chloride, from about 15% to about 54%, by weight, of a C2-C10 alkyl acrylate, and from about 10% to about 15%~ by weight, of at least one C8-C22 dialkyl maleate or fumarater The use o~ the above~described type of internal-ly plasticized resin allows for production of a ~ilm having the desired degree of ~lexibility without the use of any significant amount of external plasticizer such as employed in certain prior ar~ films. Gener-ally speaking, the amount of internally plasticized resin in the vin~l film can range from about 35% to about 75%, by weight of the film depending upon the type of film required.
The ethylene/carbon monoxide polymer which is xesponsible for the improved physical properties for films made from t~e blend of the present invention is a known material and has been suggested as an additive to conventional, non-internally plasticized polyvinyl chloride resins ~see U.S. Pa~ent ~lo. 3,780,140 to C. F. Hammer). It is a copolymer of: (a) from about 40% to about 80~ ethylene; (b) about 3~ to about 30%
carbon monoxide; and (c) from about 5% to about 60~, by weight of one or more termonomers copolymerizable therewith. Examples of suitable termonomers include l.~dqJ ~7~5 ~le C3-C~o unsaturated monv- and dicarboxylic acids and their esters; the C~-C~8 vinyl esters of saturated carboxylic acids; the vinyl C1-C 18 alkyl ethers, acrylonitrile; methacrylonitrile; the C3-C1 2 alpha olefins, and ring compounds such as norbornene and vinyl aromatic compounds. A preferred polymer com-prises 40-80% ethylene, 3 30% carbon monoxidet and 10-50% vinyl acetate. Ethylene/carbon monoxide poly-mers of this type are commercially available under the trademark EL~ALOY from E. Io DuPont de~emours and Company.
The weight amount of ethylene/carbon monoxide polymer which needs to be used in the blend is rela-ti~ely small in order to be effective to give the intended improvement in the physical properties for the films formed therefrom. Generallyl an amount of ethylene~carbon monoxide polymer ranying from about 5% to about 40%~ by weight of the blend of internally plasticized resin and ethylene/carbon monoxide ter-polymer will b~ sufficient. The use of harder inter- ' nally plasticized resins (which contain a higher vinyl chloride content) will require use of higher amounts of the ethylene/carbon monoxide polymex. Generally, the amount of internally plasticiæed copolymer will range from about 35~ to about 75%, by weight of the entire composition~ The weight ratio of internally plasticized copolymer to ethylene/carbon monoxide polymer will generally be within the range of from about 4:1 to a~out 1.5:1 with a higher ratio of internally plasticized resin being required when its vinyl chloride content is lower.
s ~ number of other additives are used in manufac-turing the ~inyl film component contained in the lam-inates of the present invention. Included as poten-tial additives are the following:
(a) fillers and/or pigments. The am~unt of filler that is chosen can range from about 0~ to about ~0~, by weight. Fillers and pigments are used to pro-vide desired color to the film, to provide opacity, and to aid in the calendering of the film forming composition. Representative pigments or fillers in-clude such inorganic materials as titanium dioxide, calcium carbonate, zinc oxide, white lead, gypsum, precipitated silica, carbon black, red iron oxide.
Others are well known by the person of ordinary skill in the art.
(b) monomeric and pol~meric process aids. These additives serve to aid in the processing of the cal-enderable film forming compositions as well as giving the film favorable visual appearance. Included are such polymeric additives as PVC/acrylate resin/
acrylate processing aids, and chlorinated polyethyl-ene, which produce a smooth surface on the calendered film, and alpha methyl styrene or acrylic polymers which also function as process aids. l`hese additives may be used at from about 2% to about 15%, by weight o~ the film.
(c) lubricants. These may be present at from about Q.5~ to a~out 3~, by weight of the film. In-cluded as representative lubricants are stearic acid, stearamide, the polyethylene waxes, hydrocarbon oils, and the like.
C-61~5 7~i ~ d) stabiliæers and antioxidants. These may be present at from about 3~ to about 10~, by weight of the film. Included are the stearate salts, the epoxi-dized vegetable oils, dibasic lead phosphite and di butyl tin dilaura~e, dimaleate or mercaptide. Others that may be selected are well known to persons of ordinary skill in the art.
Other functional addi~ives that can be present in relatively minor amount (under 2%J by weight, of the film) include ultraviolet light stabilizers, drying agents, and the like.
~ he first step in forming the vinyl film laminate of the present invention is the formation of a film forming composition which can be calendered and which has good chemical resistance and outdoor durability.
The aforementioned internally plasticized resin~ethyl-ene/carbon monoxide polymer, filler and/or pigment, monomeric and polymeric process aid, lubricant, or stabilizers and antioxidant components can be selected in the aforementioned amounts, if desired.
These selected ingredients are mixed until they are in the form of a homogeneous powdery composition. They can be then fluxed under sufficient heat and pressure to yield a composition of a dough-like consistency.
After passing t~rough a strainer apparatus they are ready for calendering.
This film ormulation is then calendered at a temperature and pressure which allows formation of a film h~ing a thickness of aboug 125 to 375 micron~.
A calendering temperature of from about 13Q to about 18QC. is recommended.
The film can be used to form laminate products ~which are useful in upholstery applications. These -p~7~5 laminates contain a suitable fabric substrate (e.g., woven, non-woven, blends of woven or non-woven, and so forth) attached to the vinyl film (for example, by means of a plastisol adhesive). The laminates can be formed by any means used to form conventional external-ly plasticized vinyl film/fabric substrate laminates.
Some examples of such procedures include: transfer coating, direct calender lamination, and post-lamina-tion.
The present invention is further illustrated by the Examples which follow.
7~
E%AMPLE 1 This Example illustrates the formation of a film and laminated produc~ in accordance wi~h the present invention.
The ingredient~ listed below were milled together on a two roll mill at a temperature of about 160 to 165C. for about 20 minutes to form a film:
Amount Ingredient(Parts by Wei~ht) Internally plasticized resin* 45,7 E~hylene/vinyl acetate/carb~
monoxide polymer (ELVALOY
741P brand) 23.2 15 Antimony oxide (CHEMTRON L brand) 2.5 Anhydrous ~ uminum silicate filler (BURGESS KE brand) 7.0 Bis-stearamide lubricant (AD~AWAX
240) 0 5 Dioctyl azelate plasticizer 4.0 20 Partially oxidized polyethylene lubricant 1.2 **
Zinc heat stabilizer (SYNPRON 1402 brand~ 3.0 Barium/cadlnium heat stabilizer ~SYNPRO~ ~517 brand) 1~0 Titanium dioxide~pigment (R-900 brand) 5-7 Epoxidized soya oil heat and light stabilizer (G-62 brand) 3.5 Stearic acid 0.7 Silica (FK-310 brand) 1.0 . Phenolic antioxidant tCYANAMID
- 2246 brand) 0.5 Calcium stearate lubricant 0.5 * a terpolymer which comprises about 75~, by weight, ** Tr~e~rk EXAMPLE 1 (cont'd.3 Footnote (cont'd.) vinyl chloride, about 18%, by weight, 2-ethylhexyl acrylate, and about 7%, by weight, bis(beta)chloro-ethyl)vinylphosphonate.
The film which was formed, as described above, had the following properties:
Test Value ___ Craves Tear Strength (~STM D 1004-66) 29.8/39.5 kg./cm.
Film Color (after 400(~ach dir./cross dir.) hrs. in ~TLAS FADE-O-METER apparatus) (ASTM G25-70) No change Film Color (after 40Q
hrs. in WEATHER-O-METER apparatus) (ASTM ~ 2565-27) No change T.~r; n~ted products wer~ made from the film by laminating the film to a non-woven polyester-poly-urethane substrate having a thickness of about 889-1016 microns (CAFJ-140 brand from Foss Manufacturing) at a temperature o~ a~out 150~C. using a plastisol adhe~ive at about 33O9 gm./m2 in a laminating/embos-sing apparatus. The laminates were then topcoated with. a blend of PVC and polymethylmethacrylate in a ratio o~ 3:2. The topcoated ~ilm/~abric lam.inate was then tested for its cold crack properties at -28.9C.
wikh:and without a heat ageing procedure (93.3C. for 6 days)o l.~qJ`~
EXAMPI,E 1 ~cont'd.~
Laminated Product Result Non-heat aged Pass Heat aged Fail "Pass" indicates no cracking when a 1.81 kg. weight falling through 20.3 cm. strikes the sample mounted on a 5.1 cm. thick foam mounted on wood. "Fail"
indicates cracking of the sample.
.
C-61~5 ~. ~d J~
This Example illustrates another embodiment of the present invention which is particularly preferred.
5A film forming composition was prepared as described in Example 1 from the following ingredients:
Amount Ingredient(Parts b~ Weight) 10 Internally plasticized resin* 45.7 Ethylene/vinyl acetate/carbon monoxide polymer (ELVALOY
741P brand) 25.2 Antimony oxide~flame retardant (CHEMTRON L brand) 2.5 15 Magnesium carbonate filler (MAGCARB L brand) 5.0 Octyl epoxy stearate heat and ligh~ stabilizer (DRAPEX 3.2 brand) 3.5 Bis-stearamide lubricant (AD~AWAX
240) 0 5 Dioctyl azelate plasticizer4.0 PartiaIly oxidized polyethylene lubricant 1.2 Zinc heat stabilizer (SYNPP~ON
1402 brand) 3.0 25 Barium/cadmium heat stabilizer ~SYNPRON 1517 brand~ 1 0 Titanium dioxide pigment (R-900 brand) 5.7 Stearic a id lubricant 0~7 Silica release agent (FK-310 brand) ~.0 : Phenolic antioxidant (C~ANAMID
3D 2246 brand) 0.5 Calcium stearate luhricant 0.5 * the terpolymer used in Example 1.
- \
EX~MPLE 2 (Cont'd.) The formulation mentioned above was fluxed on a two-roll mill for about 20 minutes at a temperature of about 160-165C. to generate a film having a thick-ness of about 254-305 microns for determination of physical property characteristics. The following was noted:
T _ Value Graves Tear Strength (ASTM D 1004-66) 26.4/35.2 kg./cm.
(mach. dir./cross dir.) T.~m; n~ted products were made from ~he film by l~in~ting the film to a non-woven polyester-poly-urethane substrate having a thickness of about 889-1016 microns at a temperature of about 150C. in a 1 ~m; n~ting/embossing apparatus n The laminates were then topcoated with a blend of PVC and polymethyl-methacrylate in a ratio of 3:2. The laminated film/fabric was then tested for its cold crack properties at -28.9C. with and without a heat aging procedure (93.3C. for 6 days) according to the test described in Example 1.
Laminated Product Result Non-heat aged Pass Heat aged Pass ~ `p~
- lS -These Examples illustrate the ~ormation of addi-tional films and laminated products. The same proced-ure used-in Ex~mples 1 and 2 was employed except where noted. The following ingredients were used to form the film forming composition:
Amount (Parts by Weight) Ingredient 3 Internally plasticized resin*~2.3 42.3 Ethylene/vinyl acetate/carbon monoxide polymer (ELVALOY
741P brand) 2002 20.2 Chlorinated polyethylene (Dow CPE 4213 brand) 8.4 8.4 Antimony oxide flame retardant (CHEMTRON L brand) 2.5 2.5 Magnesium ~arbonate filler (MAGCARB L brand) 5.5 5.5 Epoxidize~ soyabean oil (G-62 brand) 3.5 ---Octyl epoxy stearate*heat and light stabilizer (DRAPEX 3.2 brand) --- 3.5 Bis-stearamide lubricant (ADVAWAX
240) 0.5 0.5 Dioctyl azelate plasticizer 4.0 4.0 Partially oxidized polyethylene lubrica~t 1.2 1.2 zinc heat stabilizer (SYNPRON 1402 brand) 3.0 3.0 Barium/cadmium heat stabilizer (SYNPRON 1517 brand) 1.0 1.0 Titanium dioxide pigment ~R-900 brand) 5.7 5.7 Stearic acid lubricant 0.7 0.7 * Trademark 7~
EXAMP.~ES 3-6 (cont'd.) Amount (Parts by Weight) Ingredient 3 4 Silica release agent (FK-310 brand) 1.0 1.0 Calcium stearate lubricant 0.5 0.5 -* the terpolymer used in Example 1.
Amount ~Parts by Weight) Ingredient 5 6 Internally plasticized resin* 45.7 45.7 Ethylene/vinyl/acetate carbon monoxide polymer (ELVALOY
741P brand) 25.2 25.2 Chlorinated polyethylene (Dow CPE 4213 brand) Antimony oxide flame retardant (CHEMTRON L brand) 2.5 2.5 Magnesium carbonate ~iller (MAGCARB L brand) 5.0 5.0 Epoxidized soyabean oil (G-62 brand) 3-5 ~~~
Octyl epoxy stearate heat and light stabilizer (DRAPEX 3.2 brand) --- 3-5 25 Bis-stearamide lubricant 0.5 0.5 Dioctyl azelate plasti~izer 4.0 4.0 Partially oxidized polyethylene lubricant 1.2 1.2 Zinc heat sta~ilizer (SYNPRON
14Q2 brand) 3.0 3.0 30 Barium~cadmium heat stabilizer (SY~PRON 1517 brand) 1.0 1.0 Titanium dioxid~ pi~ment 5.7 5.7 (R-90Ø brand) EXAMPLES 3-6 (cont'd.) Amount ~ (Parts by Weight) Ingredie~t 5 6 Stearic acid lub.ricant 0.7 0.7 Silica release agent (FR-310 brand) 1.0 1.0 Calcium stearate lubricant 0.5 0~5 Phenolic antioxidant (AMERICAN
CYANAMID 2246) 0.5 0.5 *the terpol~mer used in Example lo The laminates from Examples 3 6 were subjected to various physical property tests with the following significant results being noted.
Laminate Example No.
Weight ~gm./m2) 467.8 498.3 518.7 508.5 Adhesion tMD~(1) CNS 1786 CNS CNS
Pliability (mm.) (2) 18.0320.129.98 20.42 Stretch (MD, ~) (3) 32~334.3 27.6 41.3 Set (MD, ~) (4) 8.0 8.0 9.3 8.0 Tensile Grab (MD) (5) 477J545 405 365 360 (MD/CD) Tongue Tear ~MD) (6) __~ 95 95 90 MVSS 302 ( 7) SE SE SE SE
. Abrasion, Wyzenbeek( 8 ~ OK OK OK OK
(,) Adhesion of the film to the fabric was tested in accordance with ASTM D 751-68~ The abbreviation CNS indicates that the film and fabric could not ~e separated. The rate of travel of the lower t74~
EXAMPLES 3~6 (cont'd.) Footnotes (con-t'd.) jaw of the tensile tester was 5.08 cm. per minute.
The abbreviations MD and CD stand for machine direction and cross-direction, respectively, and indicate the direction in which the force was applied. The laminate from Example No. 4 separ-ated at 1786 gm./cm~when tested in the machine direction~
0 (2) run at 21.1C., 50% relative humidi~y. This test d~termines the deflection imparted to a weighted (30 gm.) thickness gauge mounted on top of a loop of the sample when the sample is raised by one inch. The sample is 2.54 cm. x 7.62 cm. with the long dimension being the machine direction and the coating is on the outside. The higher the gauge deflection, the stif~er the material. A complete-ly rigid sample would give a value of 25.4 mm.
For comparison, typical values f~r conventional automobile upholstery will be higher than 19.05 mm.
with a 50 gm. weight; much higher for a 30 gm. wt.
(3) run in accordance with Chemlcal Fabrics and Film Assn. (CFFA)-19 test procedure. The percentage (4) for stretch figure represents the perc~ntage in-crease in length after 10 minu~es while under a load of 12.25 kg. The percentage for set indi-cates the i~crease in length after the load is removed and the samples are allowed to relax for 10 minutes.
( 5) the values are given in New~ons when tested in accordance with ASTM 751-68. It represents the te~sile or breaking strength of the samples.
(6) the values are given in Newtons when tested in accordance with Federal Standard 191, Mathod 5134.
It represents the tearing streng~h of the samples.
(~) MVSS 302 (Motor Vehicle Safety Standard 30Z) tests ~he fl~r~hility of the samples with '~SE"
denoting "self-extinguishingl'.
( 8 ) the Wyzenbeek method (Federal Standard Mo. 191, Method 5304) measures the abrasion resistance of coated fabrics using the Wyzenbeek and Staff abrasion wear tester. The results were -- lg --EX~MPLES 3-6 (cont'd.) Footnotes ~cont'd.) determined under standard test conditions after 25,000 double rubsO "OK" indicates no visible abrasion was noted.
The laminate ~rom Example 3 was also tested for its fogging characteristics. The sample was placed in a cylindrical holder about 15.24 cm. in diameter and heated to 71.1C. One end of the cylinder was closed, and the other sealed by a glass cap main-tained at 37.8C. Volatile material was collected on the glass cap reducing the light transmission to about ~0% after 72 hours. For comparison, standard externally plasticized automobile upholstery have a value of about 40% original light transmission after about 72 hours.
27~S
ExAMæLE 7 The laminates from Examples 5 and 6 were also tested for cold crack properties after being coated with two differing topcoats. Both topcoats wexe applied by 33.5 line per cm.pad rolls at room ~empera-ture followed by air drying.
Topcoat A was a vinyl/acrylic topcoat with a vinyl/
acrylate ratio of 3/2.
Topcoat B was a urethane topcoat sold under the trademark PE~MU~HANE U~10-046 by Beatrice Chemical Co.
A series of laminates were tested for its cold cracX properties at -28.gC. with and without heat aging at 93.3C. for 6 days.
Unheat Aged ~eat Aged T.. -in~te fxom Topcoat Topcoat Topcoat Topcoat Example A B A B
. 3 o~ ~ 2 of 2 1 of 4 2 o~ 2 passed passed passed passed 6 4 of 4 2 o~ 2 4 of 4 2 of 2 passed passed passed passed C-61~5 ~2~ S
- 2~ -This Example illustrates three additional films formed in accordance with the present invention using the process of Example 1:
~moun~ (Parts by Weight) Ingredient A B C
In~ernally plasticized re~in* 42.5 42.5 42.5 Ethylene/vinyl acetate/
carbon monoxide polymer (ELV~LOY 741 P brand) 20.2 20.2 20.2 **
Silica (C~B-O-SIL, M-5 brand) 0.6 0.6 0.6 Calcium Carbonate (ATOMITE
brand) 7.8 Chlorinated polyethylene (CPE-4213 brand) -- 7.8 7.8 Magnesium Carbonate (MAGCARB L brand) 7.1 7.1 7.1 ~ntimony oxide (CHEMTRON
L brand) 2.5 2.5 2~5 Bis-stearamide lubrican~
(ADVAWAX 240 brand) n.6 006 0.6 Partially oxidized poly-ethylene lubricant 2.0 2.0 2.0 ~25 Dioctyl azelate plasticizer
~moun~ (Parts by Weight) Ingredient A B C
In~ernally plasticized re~in* 42.5 42.5 42.5 Ethylene/vinyl acetate/
carbon monoxide polymer (ELV~LOY 741 P brand) 20.2 20.2 20.2 **
Silica (C~B-O-SIL, M-5 brand) 0.6 0.6 0.6 Calcium Carbonate (ATOMITE
brand) 7.8 Chlorinated polyethylene (CPE-4213 brand) -- 7.8 7.8 Magnesium Carbonate (MAGCARB L brand) 7.1 7.1 7.1 ~ntimony oxide (CHEMTRON
L brand) 2.5 2.5 2~5 Bis-stearamide lubrican~
(ADVAWAX 240 brand) n.6 006 0.6 Partially oxidized poly-ethylene lubricant 2.0 2.0 2.0 ~25 Dioctyl azelate plasticizer
3.5 3.5 3.5 Zi~c heat sta~ilizer (SYNPRON 14a2 brand) 3.0 3.0 3.0 Bariumjcadmium heat stabilizer ~SYNPRO~
3-~6 brand) 1.0 1.0 1.0 Titanium dioxide pigment ~R~900 brand) 5.7 5.7 5.7 ** Trademark 7~
EXAMPLE 8 (cont'd.) Amount (Parts by Weight) Ingrédlent A B C
Polyvinyl chloride sus pension resin (SCC-20 brand) 0.3 0-3 ~~
Epoxidized soya oil heat and light s~abilizer G-62 brand) 3.2 3.2 3.5 10 * the terpolymer used in Example 1.
The Shore "A" hardness (10 sec.) of each of the film~ made from ~he above formula~ions were as follows:
A B C
Shore "A" Hardness" 58 66 62 .
C-61~5 7~5 - 23 ~
This Example gives a particularly preferred embodiment of the present invention. The following formulation was c~lendered into films having thickness-es of 203.2 and 254 microns, respectively, Ingredient Amount by Weight Internally plasticized re~in* ~5 . O
lQ Ethylene/vinyl acetate/carbon monoxide polymer (ELVALOY
741 P brand) 25.4 Dilauryl thiodipropionate (DLTD) 0~5 Octyl epoxy tallate stabillzer (DRAPEX 44 brand) 3~5 15 -Bis-stearamide lubricant ~ADVAWAX
240 brand) 0 7 Stearic acid lubxicant 0.5 Dioc~yl azelate plas~icizer 3.65 Barium/cadmium stabilizer (SYNPRON
1517 ~rand) 5.0 Liquid phosphite heat stabilizer (SYNPRON 1535 brand) 1.0 Magnesium ~ide stahilizer (MAGLITE D) 0.5 Magnesium carbonate ~MAGCARB L brand) 4.25 25 Antimony oxide fire retardant (CHEMTRON L brand~ 2~00 Silica (CAB-O-SIL, EH-5 brand) 0.50 Acrylic/PVC Process Aid (SCC-7149 brand~ 3.00 Polyethylene lubrica~t (PE-190 brand) 1.00 .
*** Trademark 2~91S
- 2~ -EXAMPLE 9 (cont'd.) IngredientAmount by Weight Ultraviolet absorber (CYASORB
531 brand) 0-50 Pigment paste** 3.00 * the terpolymer used in Example 1.
**45.2 wt. % pigment dispersed in 54.8 wt. ~ dioctyl a~elate~
*** Trademark All of the ingredients except the ethylene/carbon monoxide polymer were added to a cooled ribbon blender and were mixed for 30 minutes. The ethylene~carbon monoxide polymer was ~hen added, and mixing was con-tinued for an additional 30 minutes. The resulting powdery mixture was charged to an INTERMIX brand mixer where it was subjected to a temperature of approxi-mately 148.9C. for about five minutes. The resulting dough-like composition was ~xtruded into a ribbon and fed to a 4-roll inverted L calender. The calendering temperatures were 148.~-176.7C. resulting in a 76.2 micron thick film.
This film was printed on laboratory equipment with a vinyl resin based ink, topcoated with a PVC/
2 acrylic resin and laminated to a non-woven fabric using pressure and a temperature of about 135.1C.
Physical properties of the laminate so produced, in comparison to a conventional automotive upholstery product are given below:
..
EXAMPI.E 9 (con-t'd.) Example 9 Conventional Weight (gm./m2) 491.6 847.5 Pliability* 170 650 Cold Crack (-28.9C.~
Initial Pass Pass ~fter 6 days at 93.3C.) Pass Pass * Gurley Pliability as determined on a No. 4171 appar-a~us manufactured by Testing Machines, Inc. of Amityville, N.YA The procedure is PSSMA of TAPPI
~Tech. Assoc. of the Pulp and Paper Institute.
Lower numbers indicate a more pliable sample.
The values express mg. of stif~ness.
C~6165 .~`fP~ 7~5 ~- 26 ~ ihe foregoing Examples illustra-te certain pre-~erred embodiments of the present invention and should not be construed in a lirniting sense. The scope o:E
protection which is sought is set forth in the claims which follow.
3-~6 brand) 1.0 1.0 1.0 Titanium dioxide pigment ~R~900 brand) 5.7 5.7 5.7 ** Trademark 7~
EXAMPLE 8 (cont'd.) Amount (Parts by Weight) Ingrédlent A B C
Polyvinyl chloride sus pension resin (SCC-20 brand) 0.3 0-3 ~~
Epoxidized soya oil heat and light s~abilizer G-62 brand) 3.2 3.2 3.5 10 * the terpolymer used in Example 1.
The Shore "A" hardness (10 sec.) of each of the film~ made from ~he above formula~ions were as follows:
A B C
Shore "A" Hardness" 58 66 62 .
C-61~5 7~5 - 23 ~
This Example gives a particularly preferred embodiment of the present invention. The following formulation was c~lendered into films having thickness-es of 203.2 and 254 microns, respectively, Ingredient Amount by Weight Internally plasticized re~in* ~5 . O
lQ Ethylene/vinyl acetate/carbon monoxide polymer (ELVALOY
741 P brand) 25.4 Dilauryl thiodipropionate (DLTD) 0~5 Octyl epoxy tallate stabillzer (DRAPEX 44 brand) 3~5 15 -Bis-stearamide lubricant ~ADVAWAX
240 brand) 0 7 Stearic acid lubxicant 0.5 Dioc~yl azelate plas~icizer 3.65 Barium/cadmium stabilizer (SYNPRON
1517 ~rand) 5.0 Liquid phosphite heat stabilizer (SYNPRON 1535 brand) 1.0 Magnesium ~ide stahilizer (MAGLITE D) 0.5 Magnesium carbonate ~MAGCARB L brand) 4.25 25 Antimony oxide fire retardant (CHEMTRON L brand~ 2~00 Silica (CAB-O-SIL, EH-5 brand) 0.50 Acrylic/PVC Process Aid (SCC-7149 brand~ 3.00 Polyethylene lubrica~t (PE-190 brand) 1.00 .
*** Trademark 2~91S
- 2~ -EXAMPLE 9 (cont'd.) IngredientAmount by Weight Ultraviolet absorber (CYASORB
531 brand) 0-50 Pigment paste** 3.00 * the terpolymer used in Example 1.
**45.2 wt. % pigment dispersed in 54.8 wt. ~ dioctyl a~elate~
*** Trademark All of the ingredients except the ethylene/carbon monoxide polymer were added to a cooled ribbon blender and were mixed for 30 minutes. The ethylene~carbon monoxide polymer was ~hen added, and mixing was con-tinued for an additional 30 minutes. The resulting powdery mixture was charged to an INTERMIX brand mixer where it was subjected to a temperature of approxi-mately 148.9C. for about five minutes. The resulting dough-like composition was ~xtruded into a ribbon and fed to a 4-roll inverted L calender. The calendering temperatures were 148.~-176.7C. resulting in a 76.2 micron thick film.
This film was printed on laboratory equipment with a vinyl resin based ink, topcoated with a PVC/
2 acrylic resin and laminated to a non-woven fabric using pressure and a temperature of about 135.1C.
Physical properties of the laminate so produced, in comparison to a conventional automotive upholstery product are given below:
..
EXAMPI.E 9 (con-t'd.) Example 9 Conventional Weight (gm./m2) 491.6 847.5 Pliability* 170 650 Cold Crack (-28.9C.~
Initial Pass Pass ~fter 6 days at 93.3C.) Pass Pass * Gurley Pliability as determined on a No. 4171 appar-a~us manufactured by Testing Machines, Inc. of Amityville, N.YA The procedure is PSSMA of TAPPI
~Tech. Assoc. of the Pulp and Paper Institute.
Lower numbers indicate a more pliable sample.
The values express mg. of stif~ness.
C~6165 .~`fP~ 7~5 ~- 26 ~ ihe foregoing Examples illustra-te certain pre-~erred embodiments of the present invention and should not be construed in a lirniting sense. The scope o:E
protection which is sought is set forth in the claims which follow.
Claims (3)
1. A film-forming blend containing an internally plasticized vinyl chlorlde copolymer which comprises from about 50% to about 85%, by weight, vinyl chloride, from about 3% to about 47%, by weight, of a C6-C10 alkyl acrylate, and from about 47% to about 3%, by weight, of a bis(hydrocarbyl)vinylphosphonate with about 5% to about 40%, by weight of an ethylene/carbon monoxide terpolymer.
2. A blend as claimed in claim 1 wherein the weight ratio of internally plasticized copolymer to ethylene/carbon monoxide terpolymer ranges from about 4:1 to about 1.5:1 and wherein the internally plasticized copolymer comprises from about 40% to about 60%, by weight of the blend.
3. A film formed from the blend of either claims 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/229,818 US4489193A (en) | 1981-01-30 | 1981-01-30 | Blend of internally plasticized vinyl chloride copolymer and ethylene/carbon monoxide polymer |
| US229,818 | 1981-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1202745A true CA1202745A (en) | 1986-04-01 |
Family
ID=22862791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000395175A Expired CA1202745A (en) | 1981-01-30 | 1982-01-29 | Blend of internally plasticized vinyl chloride copolymer and ethylene/carbon monoxide polymer |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4489193A (en) |
| JP (1) | JPS57147538A (en) |
| CA (1) | CA1202745A (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5971355A (en) * | 1982-10-18 | 1984-04-23 | Sekisui Chem Co Ltd | Resin composition for medical appliance |
| JPS58168646A (en) * | 1982-03-31 | 1983-10-05 | Du Pont Mitsui Polychem Co Ltd | Vinyl chloride resin composition |
| JPS58168644A (en) * | 1982-03-31 | 1983-10-05 | Mitsui Toatsu Chem Inc | Composition having excellent gelling characteristics and consisting of polyvinyl chloride and high-molecular plasticizer |
| DE3473780D1 (en) * | 1983-02-11 | 1988-10-06 | Stauffer Chemical Co | Roof containing plastic membrane |
| US4847155A (en) * | 1983-09-12 | 1989-07-11 | The Dow Chemical Company | Barrier film structures |
| US4795665A (en) * | 1983-09-12 | 1989-01-03 | The Dow Chemical Company | Containers having internal barrier layers |
| US4640865A (en) * | 1984-08-31 | 1987-02-03 | The Dow Chemical Company | Barrier film structures |
| US4678713A (en) * | 1984-08-31 | 1987-07-07 | The Dow Chemical Company | Co-extruded laminates containing carbon monoxide interpolymers |
| US4766035A (en) * | 1985-05-28 | 1988-08-23 | The Dow Chemical Company | Barrier film structures |
| JPS61113637A (en) * | 1984-11-08 | 1986-05-31 | Du Pont Mitsui Polychem Co Ltd | Vinyl chloride resin composition |
| US4774294A (en) * | 1986-03-31 | 1988-09-27 | Dow Chemical Company | Electromagnetic shielded body |
| NZ220762A (en) * | 1986-07-07 | 1989-05-29 | Chisso Corp | Coated fertiliser with polyolefinic coating |
| US4778856A (en) * | 1987-05-26 | 1988-10-18 | E. I. Du Pont De Nemours And Company | Blend of polyvinyl chloride, chlorinated or chlorosulfonated polyethylene and ethylene-containing terpolymer |
| FR2618441B1 (en) * | 1987-07-24 | 1989-10-27 | Solvay | FLEXIBLE COMPOSITIONS BASED ON VINYL CHLORIDE POLYMERS COMPRISING POLY-EPSILON-CAPROLACTONE |
| US4874801A (en) * | 1987-12-21 | 1989-10-17 | Shell Oil Company | Polymer blend |
| US4954570A (en) * | 1988-05-24 | 1990-09-04 | Shell Oil Company | Polyketone polymer blend |
| US4874819A (en) * | 1987-12-21 | 1989-10-17 | Shell Oil Company | Polymer blend |
| BR9007349A (en) * | 1989-05-04 | 1992-04-28 | Du Pont | POLYMERIC PLASTIFIERS FOR POLY (VINYL CHLORIDE) |
| GB2249549A (en) * | 1990-11-08 | 1992-05-13 | Shell Int Research | Stabilised copolymer compositions |
| JPH04216848A (en) * | 1990-12-19 | 1992-08-06 | Yazaki Corp | Polyvinyl chloride resin composition |
| US5206058A (en) * | 1992-02-26 | 1993-04-27 | Eastman Kodak Company | Process for painting polypropylene |
| US5209983A (en) * | 1992-06-26 | 1993-05-11 | E. I. Du Pont De Nemours And Company | Adhesives for laminating vinyl to various substrates |
| US5270366A (en) * | 1992-12-16 | 1993-12-14 | Vista Chemical Company | Lead stabilized, flexible polymeric blends containing polyvinylchloride |
| EP0627465B1 (en) * | 1993-06-03 | 1998-11-25 | W.R. Grace & Co.-Conn. | Barrier blend and food packaging film containing the blend |
| US5843581A (en) * | 1993-06-03 | 1998-12-01 | Cryovac, Inc. | Barrier blend and food packaging film containing the blend |
| US5447789A (en) * | 1993-09-30 | 1995-09-05 | E. I. Du Pont De Nemours And Company | Adhesion promoter for PVC compounds |
| USH1437H (en) * | 1994-03-04 | 1995-05-02 | Spelthann Heinz H | Grafted copolymers |
| US6348679B1 (en) * | 1998-03-17 | 2002-02-19 | Ameritherm, Inc. | RF active compositions for use in adhesion, bonding and coating |
| US6333115B1 (en) | 1998-08-24 | 2001-12-25 | Premark Rwp Holdings, Inc. | Thin film adhesive, method of making, products made therefrom |
| US6333073B1 (en) | 1999-02-25 | 2001-12-25 | Premark Rwp Holdings, Inc. | Adhesive tape and products made therefrom |
| US6649888B2 (en) * | 1999-09-23 | 2003-11-18 | Codaco, Inc. | Radio frequency (RF) heating system |
| US6825256B2 (en) * | 2002-01-14 | 2004-11-30 | Crompton Corporation | Stability improvement of carbon monoxide ethylene copolymer in pvc compound |
| WO2009045459A1 (en) * | 2007-10-02 | 2009-04-09 | Seaman Corporation | Polyvinylchloride-based polymer alloys |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3780140A (en) * | 1971-08-06 | 1973-12-18 | Du Pont | Ethylene/carbon monoxide polymer compositions |
| DE2433722A1 (en) * | 1974-07-13 | 1976-01-29 | Henkel & Cie Gmbh | PROCESS FOR IMPROVED THERMOPLASTIC HOT DEFORMING OF POLYVINYL CHLORIDE |
| US3988519A (en) * | 1975-01-13 | 1976-10-26 | Phillips Petroleum Company | Laminates of a polymeric film and a nonwoven fabric |
| US4147853A (en) * | 1977-05-31 | 1979-04-03 | Stauffer Chemical Company | Internally plasticized vinyl chloride copolymer |
| US4123585A (en) * | 1978-03-17 | 1978-10-31 | Western Electric Company, Inc. | Polymeric composition comprising a halide polymer, an ethylene terpolymer and an alkyl acrylate copolymer |
-
1981
- 1981-01-30 US US06/229,818 patent/US4489193A/en not_active Expired - Fee Related
-
1982
- 1982-01-29 CA CA000395175A patent/CA1202745A/en not_active Expired
- 1982-01-30 JP JP57012579A patent/JPS57147538A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57147538A (en) | 1982-09-11 |
| US4489193A (en) | 1984-12-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |