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Publication numberUS3053677 A
Publication typeGrant
Publication dateSep 11, 1962
Filing dateNov 12, 1959
Priority dateNov 12, 1959
Publication numberUS 3053677 A, US 3053677A, US-A-3053677, US3053677 A, US3053677A
InventorsTouey George P
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Petroleum wax for paper coatings
US 3053677 A
Abstract  available in
Images(3)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Ofltice 3,053,677 PETRQLEUM WAX F012 PAPER COATINGS George P. Touey, Kingsport, Tenn, assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Nov. 12, 1959, Ser. No. 852,225 7 Claims. (Cl. 1ll6162) This invention concerns an improved type of petroleum wax for use in wax coating compositions, more particularly petroleum wax modified with an aliphatic acid ester of a sugar.

Petroleum waxes are well known in the paper coating field used for making waxed paper of various types. Waxed papers of this type are cheap and highly eflicient in producing water-proof paper containers such as milk cartons, paper cups and the like for various types of beverages. These Waxed papers are also used for wrapping various food items to protect them from dirt, dehydration, moisture and the like.

Not only are wax coatings inexpensive but they have the desirable features of being free flowing liquids in the melted state, frequently melting under 100 C. permitting paper to be coated by simply dipping or passing the paper through a hot melt of the material.

Although petroleum wax coatings are used extensively to water-proof paper, they have several shortcomings which have not been previously resolved successfully. For instance, they have poor scuff-resistance and poor resistance to impact. This means that the coatings are often scraped off of the paper in normal usage or are easily shattered by a heavy blow. Another disadvantage is that the coatings, being extremely non-polar in character, often do not bond sufiiciently to the paper to permit folding of the paper without having the wax coating flake off.

As a means of avoiding these disadvantages, it has been suggested that plasticizers be added to the wax formulations to reduce their tendency to flake and to make them adhere more firmly to paper. However, the common plasticizers are not compatible with petroleum wax. Usually the pl-asticizer is not sufliciently soluble in the wax or in the event that it is soluble, it gradually exudes to the surface of the coating producing a sticky or glossy film.

We have discovered a more compatible plasticizer for petroleum wax which not only is compatible with petroleum wax but also provides a better adherence to the paper surface and reduces flaking when the paper is bent or folded.

One object of this invention is to disclose a new type of additive for petroleum waxes designed for coating operations. Another object is to disclose a new type of additive which is highly soluble in the wax and which will not exude to form a glossy or tacky surface. A third object is to disclose a new type of Wax formulation which will bond more firmly to the paper than the petroleum wax alone. A fourth object is to disclose a new and more compatible plasticizer for petroleum wax. These objects are accomplished by blending certain types of sugar esters with the Wax before it is used as a paper coating. The esters are substantially completely esterified aliphatic acid esters of glycose, sucrose, sorbitol and the lower alkyl glycosides such as methyl alpha-D-glycoside and ethyl alpha-D-glucoside.

The amount of sugar ester required depends on the type of ester and the amount of plasticizing and enhanced bonding action of the wax desired. Thus for som-epaper surfaces only as little as 2% of the sugar acid additive is all that is required, whereas in other applications the concentration of the sugar additive may be as high as 25%. Normally, however, a concentration of 3-15 parts sugar ester to 97-85 parts of petroleum wax is sufficient. Higher concentration of sugar esters, althoughsuitable for certain specialized operations usually tend to make a tacky wax coating. The preferred concentra tion for general use in paper coatings is 3-10 parts sugar ester and 97-90 parts petroleum wax.

The sugar esters which function as plasticizers and bonding agents for the petroleum waxes are the substantially completely esterified aliphatic acid esters (containing 3-8 carbon atoms in their acyl substituents) of glucose, sucrose, sorbitol, methyl a-D-glucoside. Thus, the propionic, butyric, isobutyric, valeric, isovaleric, hexanoic, isohexanoic, heptanoic, octanoic, and 2-ethylhexanoic acid esters of these sugars may be employed. Also the aliphatic acids can be unsubstituted as in the case of crotonic, methacrylic, and the like.

Sugar esters with aliphatic acyl groups containing more than '8 carbon atoms such as, for example, sucrose octapalmitate or octaoleate are undesirable. These are not sufiiciently compatible with the wax and gradually exude to the surface of the wax after standing several weeks. The aromatic acid esters are undesirable for similar reasons. In addition, aromatic acid esters of sugars in general are considered more toxic than the aliphatic acid esters.

The preferred sugar esters are the isobutyrate esters of glycose, sucrose, sorbitol and methyl (or ethyl) alpha- D-glucoside. They can be made by inexpensive procedures, impart no objectionable odor to the Wax, and they have a sufiicient number (4) of carbon atoms on their acyl substituents to provide the proper amount of solubility in the wax. Also, they are completely waterinsoluble and are quite stable to heat. The glucose and per 1 sugar molecule since the presence of a substantial.

amount of unesterified hydroxyl groups in the product tends to make it less compatible with the wax.

The petroleum waxes of this invention are those hydrocar'bon fractions which have a melting point range of from above about 40 C. to about 96 C. The main two waxes in this classification are the paraffin waxes (melting point 4366 C.) and the microcrystalline' waxes (melting point 63-94 C.). These are the pe troleum waxes used by the paper coating industry. is understood, however, that these waxes can contain a minor proportion of the various polyolefin waxes. polyolefin waxes may be used in concentrations up to 1 part polyolefin wax to 9 parts petroleum wax without any eifect on the compatibility of the sugar esters with the petroleum wax.

EXAMPLE 1 This example illustrates the compatibility of the sugar esters of this invention with a standard grade of paraffin wax (M.P. 55 C.). 1

Ten grams of the sugar ester (Table I) was mixed with g. of the melted paraflin wax at a temperatureof C. When thoroughly mixed, the hot solution was rated for its clarity. A clear solution indicated thatthe sugar derivative had dissolved completely in the wax,

whereas a hazy solution or a two-layer system den0ted'- incompatibility.

Patented Sept. 11, 1962 However, this amount:

The

After the compatibility test was performed, the melted wax was then poured into a shallow dish, whereupon it solidified. The solidified product was stored for one week at 78 F. and 55% relative humidity. Any exudation of the sugar ester was noted after this storage period.

Table I Compatibility Observation of Sugar Ester Rating at 100 C. Exudation Glucose pentaacetate Insoluble Crystals of sugar ester on surface.

Glucose pentapropionate Partly soluble..- A trace of sugar ester crystals on the surface.

Glucose pentabutyrate No exudation.

Glucose pentaisobutyrate..- Do.

Glucose pentavalerate. Do.

Glucose pentadecanoate- Slightly greasy surface.

Glucose pentaolcate Ggeasy liquid on sura Insoluble Partly solublece. Sucrose octaacetate Crystals of sugar ester on surface. A trace of sugar ester crystals on surface.

No exudation.

Sucrose octapropionate Sucrose octabutyratc Sucrose octaisobutyrate Do. Sucrose octavalerateu Do. Sucrose octa-Z-ethyl-h Do.

anoate. Sucrose octadecauoate Slightly greasy surface, Sucrose octastearate- Greasy solid particles.

Sorbitol hexaacetate Crystals of sugar ester on surface.

Sorbitolhexapropionatenne A trace of sugar ester crystals on the surface.

Sorbitol hexabutyrate No exudation.

Sorbitol hexaisobutyrate D0.

Sorbitol hexavalerate Do.

Sorbitol hexa-Q-ethyl-hexa- Do.

noate. Sorbitol hexaoctadecanoate. Slightly greasy surface.

Sorbitol hexapalmitate Methyl a-D-glucoside tetraacetate.

Methyl a-D-glucoside tetraproplonate. Methyl a-Dglucoside tetra- Greasy solid particles on surface.

Crystals of sugar ester on surface.

No exudation.

Do. butyrate. Methyl a-D-glucoside tetra- Do.

isobutyrate. Methyl a-D-glucoside tetra- Do.

valerate. Methyl a-D-glucoside tetra Slightly greasy surface.

2-ethyl-hexanoate. Methyl a-D-glucoside tetra- Do.

octadecauoatc.

Greasy surface.

The compatibility tests show that the sugar esters with acyl constituents containing more than 8 carbon atoms are compatible with the melted wax but gradually exude to the surface of the wax when it solidifies. This is probably because they are not sufficiently soluble in the wax at room temperature. The sugar acetates and some of the propionates were either insoluble in the melted wax or insoluble in it when it returned to room temperature. The tests also show that those esters with acyl carbon numbers between 3 and 8 were considerably more soluble in the wax and had little or no tendency to exude to the surface of the solidified wax.

EXAMPLE 2 This example illustrates how the wax coatings containing the wax-compatible sugar esters did not flake off when the coatings were bent.

An uncoated milk-carton grade of heavy paper was cut into strips of 2" x 6". A strip of this paper was submerged in each of the hot melts shown on Table II for minutes. The temperature of the melts was maintained between 95 and 100 C. during this operation. After the strips were thoroughly wetted with the liquid wax, they were removed and allowed to come to room temperature. They were then stored for 24 hours at 78 F. and 55% relative humidity before they were tested.

The coated strips were bent to an angle of 180 and the degree of flaking of the wax along the crease was observed. This operation was repeated until flaking of the wax in all cases was finally observed.

N umber oi Folds Required to Cause the Wax to Flake oil the Paper at the Crease Sugar Ester in the Wax Coating 1 1 Except for the control coating, all of the waxes consisted of parts paratfin wax and 10 parts sugar ester.

This nonfiaking characteristic of the wax is caused by a two-fold effect. The first is the more polar nature of the ester in comparison with the wax. This tends to give a stronger bond to the paper. The other is the plasticizing action which the ester has on the wax.

The polyolefin waxes which can be admixed with the petroleum-sugar ester combinations of this invention are chosen from those polyethylene and polypropylene waxes which are compatible with the petroleum waxes. Their molecular weights range from about 1000 to 10,000 and their melting points are within the limits of 70 C. and C.

I claim:

1. A wax coating composition consisting essentially of a petroleum wax consisting of those hydrocarbon fractions having a melting point range of from about 40 C. to about 96 C. and 040% of a polyolefin wax selected from the class consisting of polyethylene and polypropylene waxes having a molecular weight range of 1,000 to 10,000 and melting points within the range of 70 C. and 120 C., and 225%, based on the total weight of the composition, of a sugar ester, having an average of no more than one hydroxyl group per sugar molecule, selected from the class consisting of the esters of glucose, sucrose, sorbitol, and the lower alkyl glucosides obtained by reacting the sugar with an acid selected from the class consisting of propionic, butyric, isobutyric, valeric, isovaleric, hexanoic, isohexanoic, heptanoic, octanoic, 2-ethyl hexanoic, crotonic, and methacrylic acids.

2. A coating composition consisting essentially of a petroleum wax consisting of those hydrocarbon fractions having a melting point of 40-96 C. and 225%, based on the weight of the coating composition of a substantially completely esterified isobutyrate sugar ester obtained from glucose.

3. A coating composition consisting essentially of a petroleum wax consisting of those hydrocarbon fractions having a melting point of 40-96 C. and 225%, based on the weight of the coating composition, of a substantially completely esterified isobutyrate sugar ester obtained from sucrose.

4. A coating composition consisting essentially of a petroleum wax consisting of those hydrocarbon fractions having a melting point of 40-96" C. and 2-25%, based on the weight of the coating composition, of a substantially completely esterified isobutyrate sugar ester obtained from sorbitol.

5. A coating composition consisting essentially of a petroleum wax consisting of those hydrocarbon fractions 5 having a melting point of 40-96 C. and 2-25 based on the weight of the coating composition, of a substantially completely esterified isobutyrate sugar ester obtained from methyl-u-D'glucoside.

6. A coating composition consisting essentially of a petroleum Wax consisting of those hydrocarbon fractions having a melting point of 40-96 C. and 2-25%, based on the weight of the coating composition, of a substantially completely esterified isobutyrate sugar ester obtained from ethyl-a-D-glucoside.

7. A Waxed paper comprising a paper substrate having thereon a coating composition consisting essentially of a petroleum wax consisting of those hydrocarbon fractions having a melting point range of from about 40 C. to about 96 C. and 010% of a polyolefin Wax selected from the class consisting of polyethylene and polypropylene Waxes having a molecular weight range or" 1,000 to 10,000 and melting points within the range of 70 C. and 120 C., and 225%, based on the total weight of the composition, of a sugar ester, having an average of no more than one hydroxyl group per sugar molecule, selected from the class consisting of the esters of glucose, sucrose, sorbitol, and the lower alkyl glucosides obtained by reacting the sugar with an acid selected from the class consisting of propionic, butyric, isobutyric, valeric, iso- Valeric, hexanoic, isohexanoic, heptanoic, octanoic, 2-ethyl hexanoic, crotonic, and methacrylic acids.

References Cited in the file of this patent UNITED STATES PATENTS 2,094,771 Charch Oct. 5, 1937 2,108,808 Finzel Feb. 22, 1938 2,322,198 Parsons June 15, 1943 2,700,022 Clayton Ian. 18, 1955 2,733,225 Smith Ian. 31, 1956 2,783,156 Oathont Feb. 26, 1957 2,791,510 Sproule May 7, 1957 2,893,990 Haas July 7, 1959 2,908,681 Anderson Oct. 13, 1959

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US6193841Nov 30, 1998Feb 27, 2001Eastman Chemical CompanyShaped, plastic articles comprising a cellulose fiber, a cellulose ester, and a non-ionic surfactant
US6228895Nov 30, 1998May 8, 2001Eastman Chemical CompanyMethod for plasticizing a composition comprised of cellulose fiber and a cellulose ester
US6268028Nov 30, 1998Jul 31, 2001Eastman Chemical CompanyComposition and paper comprising cellulose ester, alkylpolyglycosides, and cellulose
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Classifications
U.S. Classification106/217.8, 106/270
International ClassificationC07H13/06, C09D191/08, C07H13/04, C07H15/04, D21H19/18
Cooperative ClassificationC07H13/04, C09D191/08, C07H13/06, C07H15/04, D21H19/18
European ClassificationC07H13/04, C07H15/04, C07H13/06, D21H19/18, C09D191/08