CA2025442A1 - Stabilizing system for eva hot melt compositions and eva hot melt compositions containing them - Google Patents

Stabilizing system for eva hot melt compositions and eva hot melt compositions containing them

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Publication number
CA2025442A1
CA2025442A1 CA002025442A CA2025442A CA2025442A1 CA 2025442 A1 CA2025442 A1 CA 2025442A1 CA 002025442 A CA002025442 A CA 002025442A CA 2025442 A CA2025442 A CA 2025442A CA 2025442 A1 CA2025442 A1 CA 2025442A1
Authority
CA
Canada
Prior art keywords
copolymer
hot melt
fatty acid
acid amides
parts
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.)
Abandoned
Application number
CA002025442A
Other languages
French (fr)
Inventor
Glenn Gerhardt
Joel A. Gribens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WR Grace and Co Conn
Original Assignee
WR Grace and Co Conn
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by WR Grace and Co Conn filed Critical WR Grace and Co Conn
Publication of CA2025442A1 publication Critical patent/CA2025442A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04Homopolymers or copolymers of ethene
    • C09J123/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/28Non-macromolecular organic substances

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE

A stabilizing system for ethylene vinyl acetate copolymers (EVA copolymers) and hot melts based upon them.
The stabilizing system comprises one or more fatty acid amides in an amount of from about 1 to about 10 parts per 100 parts of EVA copolymer and/or an epoxidized soya oil in an amount of from about 1 to about 15 parts per 100 parts of EVA
copolymer. The stabilizing system inhibits the decomposition of the EVA copolymer which decomposition includes the generation of acetic acid.

Description

20~5 i42 CASE 31~4 A STABILIZING SYSTEM FOR EVA HOT MELT COMPOSITIONS
AND EVA HOT MELT COMPOSITIONS CONTAINING THEM
The present invention relates to a stabilizing system for ethylene vinyl acetate copolymers and such hot melts containing them. More specifically, the present invention relates to stabilizing systems based upon fatty acid amides, epoxidized soya oils and blends thereof and ethylene vinyl acetate copolymer hot melt compositions containing them.

BACKGROUND OF THE INVENTION
Hot melt materials are typically thermoplastics which are in solid form at room temperature and are in a liquid molten form at higher temperatures. Hot melts are widely used because of this property.
Ethylene vinyl acetate copolymers (EVAs) are well known and widely used in hot melt compositions. EVA based hot melt compositions are used for a variety of uses including adhesives, book bindings, coatings, sealants and closure gaskets.
EVA copolymers, per se, when melted and maintained above their melting point for an extended period of time (two or more hours) tend to become unstable and decompose. One of its decomposition products is acetic acid. For example, when an EVA copolymer is held at a temperature of 216C ~420F) for two hours, it has been found that 0.3% by weight of acetic acid per weight of EVA copolymer (0.3% wt./wt.) is produced.
When an EVA copolymer is compounded with other ingredients such as oils, waxes, and other lubricants, low molecular weight polystyrenes and other tackifier resins, surfactants, etc., the generation of acetic acid doubles to 0.7% wt./w after two hourr at 216C (420'F).

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The acetic acid evolved from the decomposition of the EVA copolymer corrodes the hot melt application equipment, especially the pump systems, causing the equipment to fail in as little as 100 hours of use.
This corrosion by the acid is not acceptable to the hot melt industry in that the replacement of equipment is expensive, both in terms of money and of time. The cost of replacing various components such as pumps, lines, melt tanks and nozzles is quite high for the useful life obtained from those components. Additionally, their replacement cal~ses down time of the hot melt applicator and operator which adds to the cost of the finished product.
There is a need in the hot melt industry for a system which prevents or inhibits the decomposition of the EVA
copolymer, so as to extend the useful life of the application equipment. ¦
The present invention provides a stabilizing system for EVA hot melt compositions which substantially ~xtend the useful life of the hot melt equipment.

SUMMARY OF THE INVENTION
The present invention is a stabilizing system for ~VA
copolymers and EVA copolymer based hot melt compositions. The composition may contain only the EVA copolymer and the stabilizing system, though preferably the composition contains other traditional hot melt additives such as tackifier resins and lubricants. The stabilizing system is comprised of a fatty acid amide and/or an epoxidized soya oil. Preferably the system is formed of at least one fatty acid amide and an ,-,;;.

epoxized soya oil. More preferably, the system comprises 202S~2 about 8 parts per 100 parts of EVA copolymer of one or more fatty acid amides and about 5 parts per 100 parts of EVA
copolymer of an epoxidized soya oil.

DETAILED DESCRIPTION OF THE INVENTION
The present invention is a stabilizing system for EVA
copolymers and hot melt compositions based on EVA copolymers.
EVA copolymers are well known and widely used in hot melt applications due to their cost, compatability with other components and their processing and handling characteristics.
The term ~hot melts~ as used herein, is meant to apply to EVA copolymers, per se, as well as to any hot melt composition that is based in whole or in part on EVA
copolymers.
Most EVA copolymers have a vinyl acetate content of from about 2% to about 55% by weight of the copolymer.
Preferred EVA copolymers generally have a vinyl acetate content of less than 30~ as copolymers having vinyl acetate contents above 30% exhibit poor adhesion characteristics especially to plastics such as polypropylene. Of course such EVA copolymers have uses where adhesion properties are `
secondary or where a tackifier resin can be blended with the copolymer to increase its adhesive properties.
Examples of commercially available EVA copolymers include ELVAX~ EVA copolymer, available from E. I. DuPont de Nemours and Co., Inc.; and ULTRATHENE and VYNATHENE EVA
copolymers, avaîlable from U.S. Industries Chemical Company.
More commonly, EVA copolymer based blends are used by the hot melt industry. Such blends generally include additional thermoplastic polymers, such as polypropylene or . . .

20~5442 polyethylene or a block copolymer such as styrene-isoprene- ¦
styrene block copolymers or styrene-butadiene-styrene block copolymers; tackifier resins, lubricants, waxes, fillers and the like.
The EVA copolymer, per se, or a blend of the copolymer with other additives is sold in a solid form, such as a block, a rod or small chips or flakes.
The copolymer is heated to above its melting point and then applied as desired through a nozzle. Typical hot melt application equipment contain a melt tank which has a heater to melt the copolymer and maintain it in a molten state. Additionally, the equipment generally has a pump for supplying molten hot melts to a delivery point, such as a valve actuated nozzle. In some equipment, the pump also circulates unused hot melts back to the tank for storage.
Another option is a foaming means for the hot melt.
Another typical form of equipment for hot melt applications is an extruder. The estruder is preferably used in coating materials with hot melts or in making sheet materials from hot melts.
Typically, the equipment heats and maintains the EVA
based hot melts at temperatures from about 93C (200F) to about 232C (450F).
The stabilizing system of the present invention is ,.
comprised of at least one fatty acid amide, or an eposidized soya oil or a blend or mixture of at least one fatty acid amide and an epoxidized soya oil.
One or more fatty acid amides may be used in the present stabilizing system, alone or in combination with an e~oxidized ya oil.

.
.
' ., 202~442 Examples of suitable fatty acid amides that are useful in the present invention include but are not limited to 13-docosenamide (erucamide), octadecanamide, 9-octadecenamide (oleamide), 9,12-octadecadienamide, eicosanamide (arachidamide), docosanamide (behenamide), formamide, acetamide, prionamide, n-butyramide, stearamide, valeramide, caproamide, caprylamide, capramide, lauramide, myristamide, oleyl palmitamide, stearyl stearamide, erucyl stearamide, N,N'-ethylenebisstearamide, N,N'-ethylenebisoleamide and mixtures thereof. Other fatty acid amides and mixtures thereof may also be used in the present invention.
The amount of fatty acid amide used in the hot melt should be sufficient to stabilize the hot melt and inhibit or reduce the generation of acetic acid. Preferably, the amount of fatty acid amides should be from about 1 to about 10 parts per 100 parts of EVA copolymer. Additional amounts may be used, if necessary to achieve the desired level of stabilization. - ~-More preferably, about 5 to about 9 parts per 100 parts of EvA copolymer of one or more fatty acid amides are used as a stabilizer in the present invention.
A preferred fatty acid amide stabilizer is a blend of three amides comprised of the following amides in the~
following percentages: 6% of octadecanamide, 91% of 9-octadecenamide and 3% of 9, 12-octadecadienamide. The total amount of the blend used as a stabilizer should be the same as for any of the other fatty acid amide stabilizers, which amounts ar et forth above.

1~
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202~2 In applications that are used with food, such as gaskets for food and beverage containers, the amount of fatty acid amides should be close to but not exceed the FDA
regulated amount of amide allowed in such hot melt systems.
It is preferred that the one or more fatty acid amide stabilizers be used in combination with one or more epoxidized soya oils.
It has been determined that combination of the fatty acid amide stabilizer with the epo~idized soya oil stabilizer provides excellent stabilization and reduced acid production without substantially effecting the other characteristics of the EVA copolymer hot melt.
An epoxidized soya oil either by itself or preferably in combination with one or more fatty acid amides, may be used as a stabilizer in the present invention. Soya oil is also ~nown as soya bean oil or soy bean oil. While the term soya oil is used in the present invention, it is meant to include any such oil derived from the soy bean.
The epoxidized soya oil may be used, alone or in combination with other stabilizers of the present invention, ¦ in an amount of from about 1 part to about 15 parts per 100 parts of EVA copolymer. Preferably, the amount used is i sufficient to reduce the amount of acetic acid generation without effecting other properties of the EVA copolymer such as adhesiveness. More preferably, about 10 parts of epoxidized soya oil per 100 parts of EVA copolymer are used when the epoxidized soya oil is the sole stabilizer in the hot melt.
When the epoxidized soya oil is used in combination with one or more fatty acid amide stabilizers, it is preferred that the amount of epoxidized soya oil be about 5 parts per lOO parts o VA copolymer.

~.. ~ .. -. .... . , - .
- 2~2~42 ~

Epo~idized soya oil is commercially available. One such commercially available product is known as Vikofles 7170 by Viking Chemicals.
EXAMPLES
The following compositions were prepared by heating oil, wax and tackifier resin to appro~imately 325F and melt mixing the EVA copolymer into the heated ingredients.
Antioxidants, the stabilizinq system and the surfactant were then melt mixed into the above composition. These compositions solidified when cooled to room temperature.
Samples were then put in a sealed chamber and heated to 216C
(420F) for two hours while the head space gases were evacuated. These gases were then analyzed for acid content by bubbling through a standardized NaOH solution and titrating.
Table I shows the results obtained.

~ 202~44 :.
,.
TA~LE I
EXAMPLE A B C D E F
Escorene UL 7740 from Exxon 100 100 100 100 100 100 Parafin Wax (M P 175F) 26.32 26.32 26.32 17.95 17.95 Picolastic A75 from Hercules 16.7 16.7 16.7 16.7 16.7 350 USP White Mineral Oil 17.54 17.54 17.54 12.54 12.54 Dilauryl 3,3-Thiodipropionate 0.88 0.88 0.88 0.88 0.88 (antioxidant~
Irganox 1010 1.67 1.67 1.67 1.67 1.67 antioxidant from Ciba Geigy Polyguard antioxidant 1.67 1.67 1.67 1.67 1.67 from Uniroyal Chemical Witconate K
Flake (WITCO) 3 3 3 3 - 3 Armid-O Flake 8.83 8.37 ~Armor Chemical) Adogen 58 8.37 Epo~idized Soya Oil, Vikoflex, 10 5 5 7170 from Viking Chemical % Acetic Acid* 0.3 0.7 0.015 0.17 0.034 0.007 ~ wt Aceti cid/wt EVA after two hours at 216C

:::

' ' ~02~4~2 As can be seen from the results, hot melt compositions containing either only an EVA copolymer (E~ample A) or an EVA copolymer and other hot melt additives, (Example B) had signi~icantly greater acetic acid generation than any of the Examples (C-F) which contained a stabilizing system of the present invention. The best stabilizing system of the Examples was found to be Example F which contained 8.37 parts per 100 parts of EVA copolymer of a fatty acid amide and 5 ; parts of an epoxidized soya oil. The acid generated by ` Example F is one~one hundredth of the acid generated by the hot melt composition of Example B and about one/fiftieth the amount of acid of the EVA copolymer of Example A.
Stabilizing systems of the present invention are useful in EVA copolymers, per se, or in EVA copolymer based hot melts. Such hot melts are used as adhesives, book bindings, coatings, films and gaskets for container closures.
By stabilizing the hot melt and inhibiting its decomposition with the corresponding generation of acetic acid, one is able to extend the life of the hot melt equipment and also to prevent any deleterious effects that the decomposition of the i hot melt may have on the finished product.
~i While the present invention has been described in relation to its preferred embodiments, other variations and modifications would be obvious to those skilled in the art and it is intended in the appended claims to cover such variations, modifications and equivalents as fall within the true spirit and scope of this invention.

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ll~363P ~9~ ~;

11 ~
'' ~

Claims (24)

1. A hot melt composition comprising:
a) one or more ethylene vinyl acetate copolymers;
b) one or more lubricants, tackifier resins and fillers; and c) one or more copolymer stabilizers selected from the group consisting of fatty acid amides, epoxidized soya oils and mixtures thereof.
2. The hot melt composition of Claim 1 wherein the acetate content of the copolymers is from about 2% to about 55%.
3. The hot melt gasket composition of Claim 1 wherein the stabilizers based upon the fatty acid amides are selected from the group consisting of 13-docosenamide (erucamide), octadecanamide, 9-octadecenamide (oleamide), 9,12-octadecadienamide, eicosanamide (arachidamide), docosanamide (behenamide), formamide, acetamide, prionamide, n-butyramide, stearamide, valeramide, caproamide, caprylamide, capramide, lauramide, myristamide, oleyl palmitamide, stearyl stearamide, erucyl stearamide, N,N'-ethylenebisstearamide, N,N'-ethylenebisoleamide and mistures thereof.
4. The hot melt composition of Claim 1 wherein the stabilizer is a blend of one or more fatty acid amides and an epoxidized soya oil.
5. The hot melt composition of Claim 4 wherein stabilizer is formed of a blend of about 8.37 parts per 100 parts copolymer of one or more fatty acid amides, and about 5 parts per 100 parts of copolymer of an epoxidized soya oil.
6. The hot melt composition of Claim 5 wherein the one or more fatty acid amides comprise 6% octadecanamide, 91%
9-octadecenamide and 3% 9-12 octadecadienamide.
7. A hot melt composition comprising a copolymer of ethylene and vinyl acetate and a copolymer stabilizer selected from the group consisting of fatty acid amides, epoxidized soya oils and blends thereof.
8. The hot melt gasket composition of Claim 7 wherein the stabilizers based upon the fatty acid amides are selected from the group consisting of 13-docosenamide (erucamide), octadecanamide, 9-octadecenamide (oleamide),
9,12-octadecadienamide, eicosanamide (arachidamide), docosanamide (behenamide), formamide, acetamide, prionamide, n-butyramide, stearamide, valeramide, caproamide, caprylamide, capramide, lauramide, myristamide, oleyl palmitamide, stearyl stearamide, erucyl stearamide, N,N'-ethylenebisstearamide, N,N'-ethylenebisoleamide and mixtures thereof.
9. The hot melt composition of Claim 7 wherein the stabilizer is a blend of one or more fatty acid amides and an epoxidized soya oil.
10. The hot melt composition of Claim 9 wherein stabilizer is formed of a blend of 8.37 parts per 100 parts copolymer of one or more fatty acid amides, and 5 parts per hundred parts of copolymer of an epoxidized soya oil.
11. The hot melt composition of Claim 10 wherein the one or more fatty acid amides comprise a blend of 6% of octadecanamide, 91% of 9-octadecenamide and 3% of 9,12-octadecadienamide.
12. A hot melt composition comprising 100 parts of an ethylene vinyl acetate copolymer, 8.37 parts per hundred parts of copolymer of one or more fatty acid amides, and 5 parts per hundred parts of copolymer of an epoxidized soya oil.
13. The hot melt composition of Claim 12 wherein the one or more fatty acid amides are a blend of at least two fatty acid amides.
14. The hot melt composition of Claim 12 wherein the one or more fatty acid amides are selected from the group consisting of octadecanamide, 9-octadecenamide, 9,12-octadecadienamide, 13-docosenamide, eicosanamide, docosanamide and blends thereof.
15. The hot melt composition of Claim 14 wherein the one or more fatty acid amides are a blend of octadecanamide, 9-octadecenamide and 9,12-octadecadienamide.
16. The hot melt composition of Claim 15 wherein the blend of fatty acid amides comprises 6% of octadecanamide, 91%
of octadecenamide and 3% of 9,12-octadecadienamide.
17. The hot melt composition of Claim 12 wherein the one or more fatty acid amides is 13-docosenamide.
18. A copolymer stabilizing system for EVA hot melt compositions comprising one or more copolymer stabilizers selected from the group consisting of fatty acid amides, epoxidized soya oils and blends thereof.
19. The copolymer stabilizing system of Claim 18 wherein the stabilizers comprise from about 1 part to about 10 parts per 100 parts of copolymer of at least one fatty acid amide and from about 1 part to about 10 parts per 100 parts of copolymer of an epoxidized soya oil.
20. The copolymer stabilizing system of Claim 18 wherein the fatty acid amides are selected from the group consisting of 13-docosenamide (erucamide), octadecanamide, 9-octadecenamide (oleamide), 9,12-octadecadienamide eicosanamide (arachidamide), docosanamide (behenamide), formamide, acetamide, prionamids, n-butyramide, stearamide, valeramide, caproamide, caprylamide, capramide, lauramide, myristamide, oleyl palmitamide, stearyl stearamide, erucyl stearamide, N,N'-ethylenebisstearamide, N,N'-ethylenebisoleamide and mixtures thereof.
21. The copolymer stabilizing system of Claim 20 wherein the fatty amides are a blend of octadecanamide, 9-octadecenamide and 9,12-octadecadienamide.
22. The copolymers stabilizing system of Claim 18 wherein the stabilizer is from about 1 part to about 15 parts per 100 parts of EVA copolymer of an epoxidized soya oil.
23. The copolymer stabilizing system of Claim 22 wherein the stabilizer is about 5 parts per 100 parts of EVA
copolymer of an epoxidized soya oil.
24. The copolymer stabilizing system of Claim 18 wherein the stabilizer is from about 1 part to about 10 parts per 100 parts of EVA copolymer of one or more fatty acid amides.
CA002025442A 1989-09-29 1990-09-14 Stabilizing system for eva hot melt compositions and eva hot melt compositions containing them Abandoned CA2025442A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41499289A 1989-09-29 1989-09-29
US414,992 1989-09-29

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0611087A2 (en) * 1993-02-11 1994-08-17 Owens-Illinois Closure Inc., Plastic closure with compression molded sealing liner
US6201066B1 (en) * 1995-01-12 2001-03-13 Showa Denko K.K. Adhesive of polyolefin and polyepoxide for extrusion lamination
FR2807443A1 (en) * 2000-04-06 2001-10-12 Kurt Sorg Paraffin-free ethylene/vinyl acetate copolymer adhesives include erucic acid monoamide or silicone oil as lubricant
FR2807442A1 (en) * 2000-04-06 2001-10-12 Kurt Sorg Paraffin-free ethylene/vinyl acetate copolymer adhesives include erucic acid monoamide or silicone oil as lubricant
EP1674547A1 (en) * 2004-12-23 2006-06-28 Muylle-Facon N.V. Glue for cold glueing of construction materials

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969364A (en) * 1973-10-19 1976-07-13 Ciba-Geigy Ag Aminonaphthoselenazole
CA1202135A (en) * 1981-05-26 1986-03-18 Malcolm S. Smith Tack- and block-free pellets of ethylene co- and terpolmymers

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0611087A2 (en) * 1993-02-11 1994-08-17 Owens-Illinois Closure Inc., Plastic closure with compression molded sealing liner
EP0611087A3 (en) * 1993-02-11 1994-11-02 Owens Illinois Closure Inc Plastic closure with compression molded sealing liner.
US6201066B1 (en) * 1995-01-12 2001-03-13 Showa Denko K.K. Adhesive of polyolefin and polyepoxide for extrusion lamination
US6482530B2 (en) 1995-01-12 2002-11-19 Showa Denko K.K. Extrusion laminate with polyolefin-polyepoxide adhesive
FR2807443A1 (en) * 2000-04-06 2001-10-12 Kurt Sorg Paraffin-free ethylene/vinyl acetate copolymer adhesives include erucic acid monoamide or silicone oil as lubricant
FR2807442A1 (en) * 2000-04-06 2001-10-12 Kurt Sorg Paraffin-free ethylene/vinyl acetate copolymer adhesives include erucic acid monoamide or silicone oil as lubricant
EP1674547A1 (en) * 2004-12-23 2006-06-28 Muylle-Facon N.V. Glue for cold glueing of construction materials
BE1016393A5 (en) * 2004-12-23 2006-10-03 Muylle Facon N V ADHESIVE FOR COLD BONDING OF BUILDING MATERIALS.

Also Published As

Publication number Publication date
AU626721B2 (en) 1992-08-06
AU6239990A (en) 1991-04-11
JPH03124747A (en) 1991-05-28

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