Starch-Containing Compositions for Use in Imparting Oil or Grease Resistance to Paper

(54) Title: COMPOSITION OF STARCH AND PRODUCT (57) Summary: PAPER (30) Unionist Priority: 12/26/2007 us 11 / 964,144,

02/13/2007 US 60 / 889,612 (66) Internal Priority: 860446 (73) Holder (s): tate & lyle ingredients americas, inc (72) Inventor (s): patrícia, tippit (74) Attorney (s): Antonio Maurício Pedras Arnaud (86) International Order: pct US2OO8O51875 from

24/01/2008 (87) International Publication: wo 2008 / i00688de 21/08/2008

COMPOSITION OF STARCH AND PAPER PRODUCT.

Background of the invention

The present invention relates to the fields of starch compositions. More particularly, it concerns compositions that impose resistance to oil or grease when coated on paper products.

Fluorochemicals have been used to impose resistance to oil or grease on paper or cardboard used to pack oily or fatty foods, such as pet food, microwave popcorn, pizza, chips, fried vegetables, confectionery, chocolate bars , or foods containing oil-based sauces. However, there are several concerns regarding possible negative impacts of fluoro chemicals on human health or the environment, and at least one major supplier of fluoro chemicals has left the market for these reasons.

There is a need for alternative materials to impose oil resistance on paper or cardboard.

Summary of the invention

In one embodiment, the present invention relates to a composition containing a refined starch having from about 0.1% by weight to about 10% by weight of substitutions with a hydrophobic substituent where, after cooking about 15% of solids to about 30% solids, the composition has a viscosity of about 1,000 cps at 35 ° C.

In another embodiment, the present invention relates to a paper product containing a substrate containing paper or cardboard and having a first surface and a second surface and a coating applied to at least substantially the entire first surface of the substrate, the coating being contains a refined starch having from about 0.1% by weight to about 10% by weight of substitutions with a hydrophobic substituent where, after cooking about 15% solids to about 30% solids, the coating has a viscosity of about 1,000 cps at 35 ° C, with the paper product containing from about 5 pounds of starch to about 500 pounds of starch per ton of substrate. Description of illustrative configurations

In one embodiment, the present invention relates to a composition containing a refined starch having from about 0.1% by weight to about 10% by weight of substitutions with a hydrophobic substituent where, after cooking about 15% solids up to about 30% solids, the composition has a viscosity of about 1000 cps at 35 ° C.

Starch, as used here, encompasses materials known as starches or flours that can come from one or more of a variety of sources, such as corn, oats, peas, potatoes, rice, tapioca and others known in the industry. In one embodiment, the starch has an amylopectin content of at least about 60% by weight. In an additional configuration, fatty starches, having an amylopectin content of at least about 95% by weight can be used. High amylose starches (having less than about 60% amylopectin by weight) can also be used. Chemically modified starches can be used, as well as amylase resistant starches. It should be understood that a combination of two or more types of starches can be used.

In one configuration the starch is waxy corn starch.

The starch for use in the composition is replaced with from about 0.1% by weight to about 10% by weight with a hydrophobic substituent. Replaced with a hydrophobic substituent here refers to the esterification of the starch with one or more hydrophobic substituents, which introduces hydrophobic portions in the starch. In one embodiment, the starch has from about 2% by weight to about 4% by weight of substitutions with a hydrophobic substituent.

In one embodiment, the hydrophobic substituent is alkenyl succinate. In some embodiments, the alkenyl group of the starch one of the succinate invention, alkenyl has from about 2 to about 12 carbon atoms. In an additional configuration, the alkenyl group of the alkenyl succinate starch has from about 6 to about 12 carbon atoms. Octenyl succinate shy is a suitable example. Such starches are commercially available, for example 661 STACAP® starch and 662 Mira-Mist® starch, both available from Tate & Lyle (Decatur, Illinois). With respect to these exemplary starches, STA-CAP 661 has a maximum non-waxy starch content of 7%, a linked octenyl succinate content of 1.7-2.4%, a free octenyl succinate content of less than 0 , 3%, and a total content of octenyl succinate less than 3%. Mira-Mist 662 has a maximum non-waxy starch content of 7%. Other starches can be used. In some embodiments of the invention, alkenyl succinate starch having a relatively high viscosity is preferred.

The viscosity of about 1,000 cps as used here is measured at about 35 ° C using an RVA viscometer at 160 rpm (corresponding to a shear rate of about 75 s'¹) .

The concentration of starch required to provide a cooked paste of about 1,000 cps at 35 ° C can be modified, before or after replacement with a hydrophobic substituent, by techniques known in the art, such as acid thinning, among others. The concentration required to provide a cooked paste of 1,000 cps at 35 ° C can be from about 15% solids to about 30% solids. (The percentage of solids is by weight). In one embodiment, the concentration required to provide a cooked paste of 1,000 cps at 35 ° C can be from about 18% to about 28% solids. In an additional configuration, the concentration required to provide a cooked paste of 1,000 cps at 35 ° C can be from about 20% to about 25% solids. It will be apparent to the skilled technician that, whatever the solids concentration that provides a cooked paste of 1,000 cps at 35 ° C, other concentrations of solids often within any of the declared ranges can provide cooked pastes with higher or lower viscosities at 35 ° C.

The viscosity test indirectly measures the weighted average molecular weights of starch. The finer the starch, that is, the greater the reduction in the lengths of the polymeric chains in the starch as a result of the thinning technique, the higher the concentration of solids that will be required to reach about 1,000 cps of viscosity.

In the handling of starch, the starch is pJSSSGnlLS θΓΠ UlUâ IUÍStUI'cl UO1LL ctyuct. Cylinder under conditions and techniques known in the art to hydrate and swell or gel starch. Typical starch cooking conditions include a temperature of about 80 ° C to about 200 ° C for a duration of about 5 min to about 60 min. Appliances that can be used for cooking starch include open pans or high pressure jet cookers.

In addition to the hydrophobic substituted starch, the composition may contain other materials. In a composition it also contains water. A solid or semi-solid containing primarily water and starch can be called an aqueous paste. In one embodiment, the composition can be an aqueous slurry having from about 5% by weight to about 30% by weight of dry solids and a viscosity of about 25 cps to about 300 cps at a temperature of about 50 ° At about 60 ° C. In an additional configuration, the aqueous slurry can have from about 8% by weight to about 15% by weight of dry solids and a viscosity of about 50 cps to about 150 cps at a temperature of about 50 ° C at about 60 ° C. In these configurations, the viscosity of the aqueous slurry at about 50 ° C to about 60 ° C is measured by a Brookfield viscometer at 100 rpm.

The composition may contain one or more water-soluble gums, such as caragenan, locust bean gum, xanthan, configuration, non-gelanic composition, Agar, alginate, guar, gum arabic, or pectin.

The composition may contain particles of organic or inorganic charge or pigments, such as clay, calcium carbonate, titanium dioxide, or synthetic organic pigments.

In one embodiment, the composition contains no added protein, sugars, or low molecular weight polyols. Protein refers to any longer pentapeptide or peptide. Sugar refers to any mono-, di- or oligosaccharide having a molecular weight less than about 2 kDa. Low molecular weight polyols refer to QU3 _L Cfíl © T? Orgánicu compound LtJílÚU UU ± Ô Ou. May ÇxüpvS hydroxyl and a molecular weight less than about 2 kDa. In an additional configuration, the substantially protein-free, low molecular weight. Substantially free in this context means that the composition has less than typical baseline levels of materials in typical starches, 0.5% by weight of each protein, sugar composition, can be and polyols such as about sugars, and low weight polyols molecular.

In another embodiment, the present invention relates to a paper product containing a substrate containing paper or cardboard and having a first surface and a second surface and a coating applied to at least substantially the entire first surface of the substrate, the coating containing a refined starch having from about 0.1% by weight to about 10% by weight substitution with a hydrophobic substituent where, after cooking about 15% solids to about 30% solids, the coating has a viscosity of about 1,000 cps at 35 ° C, with the paper product containing from about 5 pounds of starch to about 500 pounds of starch per ton of substrate.

Paper and cardboard are known materials. Typical paper known for use in food packaging weighs from about 15 pounds per 3,000 square feet to about 190 pounds / 3000 square feet, and typical cardboard has a caliber of 0.012 inches or greater. The starch component of the coating can be as described above. The coating can be applied to at least substantially the entire first surface of the substrate by any known technique. Exemplary techniques include, but are not limited to, the use of a cooking press, a vat, a portal cylinder, a spray applicator, a calender stack ironer, a blade coater, or a rod coater, among others. The coating can also be applied to part or substantially the entire surface of the substrate, if desired.

In one configuration, the paper product may be in the form of a package that contains an oily or greasy food, the coating being between the oily or greasy food and the substrate. Such an arrangement can allow the paper product to resist penetration by oil or fat packed in it. In one configuration, oily or greasy food is selected from the group consisting of pet food, microwave popcorn, pizza, chips, fried vegetables, confectionery, chocolate bars, and foods containing an oil-based sauce ( for example, a cream based sauce, vegetable oil, butter, or lard, among other materials).

In one embodiment, the coating imposes at least 4 grease resistance on the paper product in the 3M Test Kit known in the art and discussed in more detail in the examples below. In an additional configuration, the coating imposes at least 5 grease resistance on the paper product in the 3M Test Kit. In yet an additional configuration, the coating imposes at least 6 grease resistance on the paper product in the 3M Test Kit.

The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those skilled in the art that the techniques disclosed in the examples that follow represent techniques discovered by the inventor to work well in the practice of the invention, and therefore can be considered to constitute preferred modes for their practice. However, those experienced in the art, in the light of the present disclosure, must appreciate that many changes can be made in the specific configurations that are disclosed and still obtain an equal or similar result without deviating from the spirit and scope of the invention.

Examples

Experimental methods

Used shy

The starches used were Sta Mist 7415 (Tate & Lyle, Decatur, IL), waxy corn starch refined with acid substituted with 2% octenyl succinate; potato starch tuned with acid, 5% hydroxypropylated; Ethylex

<td> 2065</td><td>(Tate</td><td>&amp; Lyle,</td><td>Decatur,</td><td>IL),</td><td>starch</td><td>of corn</td><td>in tune</td>

<td>with</td><td>acid,</td><td colspan="2">hydroxyethylated</td><td> 2%,</td><td>more</td><td>fructose;</td><td>Ethylex</td>

<td> 2025</td><td>(Tate</td><td>&amp; Lyle,</td><td>Decatur,</td><td>IL),</td><td>starch</td><td>of corn</td><td>in tune</td>

<td>with</td><td>acid,</td><td colspan="2">hydroxyethylated</td><td> 2%,</td><td colspan="3">more fructose; Koldex 50</td>

(Tate &amp; Lyle, Decatur, IL), dextrin; and Electra 7458 (Tate &amp; Lyle, Decatur, IL), acid-cationic waxy corn starch.

Starch concentration for viscosity procedure of

1,000 cps

The starches were cooked in various concentrations of solids. The cooking profile specified an initial maintenance at 35 ° C for 1 minute, heating from 35 ° C to 95 ° C over the course of 4 minutes, maintenance at 35 ° C during the

95 ° C per stroke for minutes, minutes, cooling churn and churning

2

35 ° C for an additional 7 minutes. The agitator at 160 rpm constant (corresponding to a shear rate of about 75 s ”¹ as measured by a Rapid Visco Analyzer (Newport Scientific, Jessup. MD)) throughout and viscosity measured throughout the test. The reported viscosity was at the end of the test (35 ° C).

The solids were selected to provide a viscosity between 500 and 1,000 cps and a viscosity between 1,000 and 1,500 cps. We interpolate this data, to estimate the solids that should be needed to get around 1,000 cps. This estimate of solids was confirmed with subsequent cooking.

Cooking procedure

The starches were cooked to known solid levels. For each starch the levels of solids were selected to provide a Brookfield viscosity of no more than 150 cps at 140 ° F, 100 rpm. The starches were cooked in a multiple stirrer of boiling water for 50 minutes. At the end of 60 minutes, the temperature of the multiple stirrer was adjusted to 155 ° F. The starch pastes were removed from the multiple shaker, one at a time. The water lost during cooking was added to each starch solution. The beaker containing the starch solution was placed in a 10 ° C water bath and the starch was stirred manually with a thermometer until the starch temperature was 140 ° F. The Brookfield viscosity of the starch was measured at 140 ° F, 100 rpm. The lowest Brookfield stem number that would provide a reading between 15-85% of the full scale was chosen, generally a # 2 stem. Shaking procedure

After measuring the viscosity, the starch solutions were immediately poured into a Pyrex glass pan, approximately 10 inches x 6 inches. Sheets of paper (International Paper, Camden, AR) that had been cut to 5.5 inches by 4.25 conditioned overnight at 25 ° C, 50% were submerged in the After 60 seconds the moisture, paper solution was relative and pre-weighed, starch for 60 seconds.

placed in the wedge of a two-hand crank punch to remove excess starch. The starched sheets were stacked between paper towels until all the sheets were starched.

Drying procedure

The wet sheets of paper were dried in a rotary dryer (manual sheet dryer) that had first been heated to 235 ° F. The dried leaves were again conditioned overnight at 25 ° C, 50% relative humidity before re-weighing. Starch capture was calculated using the following equation:

peso_er.gomodotg) - peso_sem_ gom_The(g} ^ θθθ _{= cap},_ura __in __amidodbs , ,_O„Weight _ without _ gum (g)

3M Test Kit Procedure

Each sheet of paper to be tested was placed on a clean, flat surface, being careful not to touch the area to be tested. In the eastern area, a drop of the test solution was dropped from a height of about 2.5 cm with a disposable pipette from an intermediate Kit Number bottle. A timer was started when the drop was applied. After 15 seconds, the excess fluid was removed with a clean absorbent paper towel and the moistened area was examined. The failure was evidenced by pronounced darkening of the specimen caused by penetration, even in a small area, under the drop. The procedure was repeated as required, making sure that the drops from the following Kit Number bottles fell on untouched areas. The results were reported as the Kit Classification, which is the highest numbered solution (1-12) that stayed on the specimen surface for 15 seconds without causing failure. The fractional values ​​represent the measure of multiple tests.

Oil penetration test RP2

Test specimens were placed on a sheet of grease resistant test paper, printed with a test grid containing 100 squares. Test sand was placed on the coated paper. A small amount of oil was applied to the sand. The specimens were placed in an oven at 140 ° F. Periodically the test specimens were carefully lifted from the corners to assess the underside of the grease-resistant test paper for failure, as evidenced by staining. The number of stained squares is equal to the failure in%. The performances of the leaves were evaluated by the percentage failure of the coating to insulate, from 0 to

100. The papers were tested both flat (Table 2) and corrugated (Table 3).

Results

Table 1 shows that waxy starch OS (substituted with octenyl succinate) provides the value of the Test Kit

3M much better than other similar viscosity and capture chemicals.

rabeia i

<td>Starch</td><td>% in solids gives folder</td><td>Mistletoe sity gives folder cps</td><td>Catch in starch at the paper lb / t</td><td>Kit test 3M</td>

<td>Sta Mist 7415, 2% octenyl succinate in fine waxy corn starch</td><td> 10</td><td> 21</td><td> 170</td><td> 5, 5</td>

<td> \\</td><td> 17</td><td> 42</td><td> 275</td><td> 8</td>

<td>w</td><td> 22</td><td> 65</td><td> 308</td><td> 11</td>

<td>w</td><td> 25</td><td> 82</td><td> 389</td><td> 12</td>

<td>Potato starch refined with acid, 5% hydroxypropyl</td><td> 10</td><td> 38</td><td> 163</td><td> 1</td>

<td>Ethylex 2065, corn starch tuned with acid, 2% hydroxyethyl + fructose</td><td> 10</td><td> 40</td><td> 172</td><td> 1,5</td>

<td>Ethylex 2025, corn starch tuned with acid, 2% hydroxyethyl + fructose</td><td> 15</td><td> 49</td><td> 228</td><td> 0</td>

<td>Dextrin Koldex 5</td><td> 18</td><td> 50</td><td> 335</td><td> 4</td>

<td>Electra 6458, waxy corn starch tuned with acid</td><td> 15</td><td> 57</td><td> 223</td><td> 2</td>

Additional experiments show that higher molecular weight of starch, for the same level of OS substitution, improves grease insulation. Tables 2 and 3 show the performance of waxy starches Os of three molecular weights, applied in various captures, in the RP2 test for oil penetration. The starches used here had 3.0% OS substitution. Untreated leaf, without starch.

starch composition with viscosity

Highly tuned, about 1,000 cps Moderately tuned viscosity of about solids. Slightly tuned to the composition fence

1,000 cps composition

25% solids.

starch with about 21% starch with about 18% viscosity of about 1,000 solid cps.

Table

CM

<td rowspan="6">Failure% RP2 - plan</td><td rowspan="6">Time, min</td><td> 1440</td><td rowspan="12"></td><td> 100</td><td rowspan="12"></td><td> 100</td><td> 100</td><td> 100</td><td rowspan="12"></td><td> 70</td><td> 100</td><td> 40</td><td rowspan="12"></td><td> 32</td><td>&lt;N</td>

<td> 120</td><td>O</td><td> 20</td><td> 25</td><td>cn</td><td>QC</td><td>CO</td><td>1—1 O</td><td>LiQ O</td><td>QC</td>

<td> 90</td><td> 52</td><td> 19 1_</td><td> 21</td><td>co</td><td>OO</td><td>co</td><td>I-1 O</td><td>5-1 O</td><td>O</td>

<td> 09</td><td>⁴³</td><td> 10</td><td> 13</td><td>OQ</td><td>'tr</td><td></td><td> 0,1</td><td>5-1 O</td><td>O</td>

<td> 30</td><td> 35</td><td>CO</td><td>r-</td><td>LIQUID O</td><td>CN</td><td>CN</td><td> 0,1</td><td>5-1 O</td><td>O</td>

<td>O</td><td>CN</td><td>CN O</td><td>1—1 O</td><td>O</td><td>1-1 QC</td><td>O</td><td>O</td><td>O</td><td>O</td>

<td colspan="3">Catch in starch pound / t</td><td></td><td> 116</td><td> 170</td><td>j 200</td><td> 119</td><td> 167</td><td> 201</td><td> 119</td><td> 167</td>

<td colspan="3">Brookfield viscosity 100 rpm cps @ 140 ° F</td><td></td><td> 50</td><td> 73</td><td> 86</td><td> 122</td><td> 165</td><td> 288</td><td> 293</td><td> 430</td>

<td colspan="3">% solids starch</td><td></td><td>GO</td><td> 10</td><td> 13</td><td>OO</td><td> 10</td><td> 13</td><td>OO</td><td> 10</td>

<td colspan="3">% substit. with succinate in octenila</td><td></td><td>CN</td><td>Γ CN</td><td>r- ~ CN</td><td> 2,7</td><td>Γ CN</td><td>CN</td><td>θ'- CN</td><td> 2,7</td>

<td colspan="3">Thinning level</td><td></td><td>highly tuned</td><td>highly tuned</td><td>highly tuned</td><td>moderately in tune</td><td>moderately in tune</td><td>moderately in tune</td><td>slightly tuned</td><td>slightly tuned</td>

<td colspan="3">'3 m</td><td>untreated sheet</td><td>waxy</td><td>waxy</td><td>waxy</td><td>waxy</td><td>waxy</td><td>waxy</td><td>waxy</td><td>waxy</td>

Table

<img file="BRPI0807280A2_D0001.tif" />

Higher levels of OS substitution provide improved performance in the 3M Test Kit in comparable starch capture, as illustrated in Table 4 for Sta Mist 7415 and the low molecular weight starch discussed in Tables 2 and 3.

Table 4

<td>Starch</td><td>Starch capture on paper, lb / t</td><td>Kit test 3M</td>

<td>Waxy corn starch, acid-enhanced, 2.1% OS</td><td> 210</td><td> 2</td>

<td>Acid-tuned waxy corn starch, 3.0% OS (Highly tuned)</td><td> 205</td><td> 5</td>

All apparent and claimed arctic reactions and claims can be made here and can be produced and performed without undue experimentation in the light of the present disclosure. Although the compositions and methods of this invention have been described in terms of preferred configurations, it will be to those skilled in the art that variations applied to the compositions and articles described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents that are both chemically and physiologically related can be replaced by the agents described here although the same or similar results are achieved. All such similar substituents and modifications apparent to those skilled in the art are considered to be within the scope and concepts of the appended claims.

spirit, invention as defined by