JP2022538880A - Combination of Sugar Fatty Acid Ester Inorganic Particles - Google Patents

Abstract

The present disclosure describes methods of treating cellulosic materials with compositions that enable better retention of inorganic particles on cellulosic substrates. The disclosed method involves combining a sugar fatty acid ester (SFAE) with such inorganic particles and applying such a combination onto a cellulosic material as a retention aid for fillers in the papermaking process. or eliminating or reducing the use of binding agents. Compositions comprising such combinations of SFAE and inorganic particles are also disclosed.

Description

[Cross reference to related applications]
This application claims priority to U.S. Patent Application Publication No. 16/456,433 filed in the U.S. Patent and Trademark Office on June 28, 2019, which is incorporated herein by reference in its entirety. shall form a part.

The present invention relates generally to treating cellulosic-based materials, and specifically with sugar fatty acid esters (SFAEs) in combination with inorganic particles, such as compositions containing such combinations, to It is concerned with processing such materials.

Inorganic particles such as kaolin, talc, calcium carbonate, and _TiO2 are typically used as fillers in papermaking processes. For example, calcium carbonate is used as a filler material in the alkaline papermaking process of paper mills. Currently, calcium carbonate predominates over other papermaking filter materials (eg kaolin). The main reason for the preference for calcium carbonate is the demand for lighter, higher loft papers. There are significant advantages to using calcium carbonate in the alkaline papermaking process (e.g. calcium carbonate is inexpensive, has high brightness, creates a porous surface on the paper sheet, improves printability, and is a binder). can reduce the demand for , increase machine speed and productivity, improve drainage, improve machine runnability, are cost-effective in the papermaking process, can reduce fiber consumption, compared to other paper fillers to obtain high retention).

Calcium carbonate generally occurs in three natural forms, eg limestone, chalk, and marble. It occurs in a reaction between calcium salts and carbon dioxide. There are two types of calcium carbonate used in paper mills: ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC).

Ground calcium carbonate is produced by crushing limestone or marble and finds use because of its high brightness and purity. Generally, the particle shape of ground calcium carbonate is rhombohedral. This filler material is used in alkaline wood-free papermaking processes. GCC brightness is about 86-95%

The coarse grain shape and small amounts of quartz frequently found in GCC cause problems, which are highly abrasive and shorten the life of the paper machines forming the wire and press felts.

Precipitated calcium carbonate is a form of _CaCO3 , which is produced by a chemical reaction, a process known as the carbonation process. PCC ameliorate the deficiencies of GCC, which gives the paper excellent gloss and opacity properties. The structure of PCC is different from that of GCC. The crystal structure of PCC can be controlled and includes acicular, rhombohedral (cubic), scalenohedral (triangular) and prismatic structures. The brightness of PCC is about 90-97%. However, PCC formations involving paper sheets may be less satisfactory than GCC formations involving paper sheets.

In modern high-speed twin-wire paper machines, the turbulence required to obtain good formation often leads to poor filler retention. Also, both types of calcium carbonate do not adhere to cellulose by themselves and require a retention aid or binder to bind to the pulp. Typically, such retention aids or binders include papermaker's alum, synthetic polymers, polyacrylamides, microparticle systems, latex, starches, and polyvinyl alcohol (PvOH), which retain Enhancers or binders can add cost or optionally make the product less "green" (eg, synthetic polymers).

Calcium carbonate can be bound to obviate the use of retention aids or binders or to reduce the amount of retention aids or binders required to bind the inorganic particles to the cellulosic surface. Desired.

The present disclosure relates, inter alia, to methods of treating cellulosic materials with compositions that enhance retention of inorganic particles (ie, fillers). The disclosed method involves combining sugar fatty acid esters (SFAEs) with such fillers and applying such combinations onto cellulose to act as retention aids or binders for fillers in the papermaking process. and eliminating or reducing the use of agents. Compositions containing combinations of SFAE and inorganic particles are also disclosed.

In one embodiment, a composition comprising a sugar fatty acid ester (SFAE) and inorganic particles, wherein the SFAE is present in a concentration sufficient to cause the inorganic particles to be retained on the cellulose-based material, Compositions are disclosed wherein substrates comprising the compositions exhibit superior water and/or grease resistance compared to substrates comprising compositions comprising only inorganic particles or one or more SFAEs.

In one aspect, the SFAE comprises all unsaturated fatty acids, all saturated fatty acids, or a mixture of saturated and unsaturated fatty acids, optionally further comprising one or more binders selected from PvOH or starch. .

In another aspect, the SFAE is a mixture of two or more different SFAEs, the two or more different SFAEs comprising all saturated fatty acids.

In one aspect, the inorganic particles include clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof, wherein the inorganic particles comprise at least 1% of the composition on a dry basis (db) occupy

In another aspect, the SFAE comprises at least one sugar and at least one aliphatic group containing 8-30 carbons. In one aspect, the inorganic particles are calcium carbonate and the substrate exhibits water resistance. In a related aspect, the inorganic particles are clay and the substrate exhibits grease resistance.

In one aspect, cellulose-based substrates include paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon paperboard, diapers, Weed Blocking/Barrier Fabrics or Films, Mulching Films, Plant Pots, Packing Beads, Bubble Wrap, Oil Absorbent Materials, Laminates, Envelopes, Gift Cards, Credit Cards, Gloves, Raincoats, OGR Paper, Shopping Bags, Compostable Bags , release paper, tableware, hot or cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, non-carbonated liquid storage bottles, food wrap films, garbage disposal containers, Food handling utensils, cup lids, moldable paper cup lid screws, paper straws, fabric fibers, water storage and transportation equipment, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transportation equipment , casings, external screens for electronic products, internal or external components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, water conduits, pharmaceutical packaging, clothing, medical equipment, contraceptives, camping Included are tools, formed cellulosic fibrous materials, and combinations thereof.

In one embodiment, an article of manufacture comprising a coating comprising one or more sugar fatty acid esters (SFAEs), inorganic particles, a cellulose-based substrate, and optionally one or more binders An article of manufacture is disclosed wherein the inorganic particles are present in the coating at a concentration of at least 1% on a dry basis (db). In a related aspect, cellulose-based substrates include paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon paperboard, diapers. , weed blocking/barrier fabrics or films, mulching films, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compost Bags, release papers, tableware, hot and cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, still liquid storage bottles, food wrap films, garbage disposal containers , food handling utensils, cup lids, moldable paper cup lid screws, paper straws, fabric fibers, water storage and transportation equipment, paperboard for pharmaceutical applications, release paper, storage and transportation of alcoholic or non-alcoholic beverages Utensils, casings, external screens for electronic products, internal or external components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, conduits, pharmaceutical packaging, clothing, medical equipment, contraceptives, Included are camping equipment, formed cellulosic fibrous materials, and combinations thereof.

In one embodiment, a method of treating a cellulosic substrate, comprising: adding at least one sugar fatty acid ester (SFAE) to a composition comprising inorganic particles to form a mixture; and curing for a sufficient time to adhere the mixture to at least one surface, wherein the cured surface is coated with at least one SFAE or inorganic particles. Disclosed are methods that exhibit greater hydrophobicity and/or oleophobicity compared to surfaces treated with compositions containing only.

In one aspect, the treated cellulosic surface is hydrophobic. In another aspect, the treated cellulosic surface is oleophobic.

In one aspect, the SFAE contains all saturated fatty acids or a mixture of saturated and unsaturated fatty acids. In another aspect, the SFAE is a mixture of two or more different SFAEs.

In one aspect, the inorganic particles include clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof, wherein the inorganic particles are present at a concentration of at least about 1% on a dry basis (db) present in the mixture. In a related aspect, the composition further comprises polyvinyl alcohol or starch.

In one aspect, the inorganic particles comprise calcium carbonate, and the calcium carbonate comprises about 50% or more of the mixture on a dry basis (db).

In another aspect, cellulosic substrates include paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon paperboard, diapers, Weed Blocking/Barrier Fabrics or Films, Mulching Films, Plant Pots, Packing Beads, Bubble Wrap, Oil Absorbent Materials, Laminates, Envelopes, Gift Cards, Credit Cards, Gloves, Raincoats, OGR Paper, Shopping Bags, Compostable Bags , release paper, tableware, containers for holding hot or cold beverages, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, still liquid storage bottles, food wrap films, raw materials Garbage disposal containers, food handling equipment, lids for cups, screws for moldable paper cup lids, paper straws, fabric fibers, water storage and transport equipment, paperboard for medical applications, release paper, alcoholic or non-alcoholic beverages outer casings or screens for electrical appliances, inner or outer components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, conduits, pharmaceutical packaging, clothing, Medical devices, contraceptives, camping gear, formed cellulosic materials, and combinations thereof.

FIG. 2 shows a scanning electron micrograph (SEM) of an untreated porosity Whatman filter paper (magnification 58×). FIG. 13 shows an SEM (1070× magnification) of an untreated, void Whatman filter paper. FIG. 2 is a side-by-side SEM (27x magnification) comparison of paper made from recycled pulp before (left) and after (right) coating with microfibrillated cellulose (MFC). FIG. 2 is a side-by-side comparison of SEM (magnification 98) of paper made from recycled pulp before (left) and after (right) coating with MFC. Polyvinyl alcohol (PvOH), ◇; SEFOSE (registered trademark) + PvOH, 1:1 (v/v), □; Ethylex (starch), Δ; SEFOSE (registered trademark) + PvOH, 3:1 (v/v), × Figure 2 shows the penetration of water in paper treated with various coating formulations.

Before describing the compositions, methods, and methodologies of the present invention, this invention is not limited to the particular compositions, methods, and experimental conditions described, as such compositions, methods, and conditions may vary. It should be understood that you may The terminology used herein is intended to describe particular embodiments only and is not intended to be limiting, as the scope of the present invention is limited only by the appended claims It should also be understood.

In this specification and the appended claims, the singular forms "a," "an," and "the" include referents of plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a sugar fatty acid ester" includes one or more sugar fatty acid esters and/or compositions of the type described herein that would be apparent to one of ordinary skill in the art upon reading this disclosure and the like. .

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is to be understood that any methods and materials similar or equivalent to those described herein may be used in the practice or testing of the invention, so that modifications and variations are encompassed within the spirit and scope of this disclosure. Available.

As used herein, "about," "approximately," "substantially," and "substantially" are understood by those of skill in the art and vary to some extent depending on the context in which they are used. "About" and "approximately" mean plus or minus <10% of the specified term, and "substantially By"and"substantially"means plus or minus >10% of the specified term. "Comprising" and "consisting essentially of" have their customary meanings in the art.

All pigments must be retained evenly on the sheet to be effective. Paper can be made cheaper if fillers are used which are less expensive than fibers. However, the percentage of filler in the sheet is limited by the resulting loss in strength, bulk and sizing quality. Although there is a definite trend toward increasing filler content, barrier properties are significantly degraded when pigment concentrations exceed 10 or 20% in any barrier coating.

SFAE is not a polymer per se, but serves to retain fillers or inorganic particles such as PCC. Without being bound by any theory, SFAE may crosslink or provide a network with fines and fiber surfaces. The combination works well and allows for increased levels of adhesion without compromising product quality, including increased performance levels.

Also, organic particles such as uncooked starch, wood particles, oat hulls, etc. may be added to provide much-needed bulk and thickness in some products, while minerals increase density. Furthermore, for hydrophobic polymers, including wood resins, hot melt waxes, bioplastics, etc., which may produce undesirable particles and/or sticky lumps or deposits, the use of SPAE-inorganic particle combinations Such undesirable aggregation can be overcome.

Additionally, the addition of compositions containing mixtures of inorganic particles and SFAEs provides improved fine tuning of various properties of the sheet. For example, such sheets may contain wood fibers and include a combination of bioplastic fibers and SFAEs to waterproof such sheets. The envisaged combination allows the use of cheaper, more common materials such as mechanical or recycled pulp, which is a large percentage of the mass of the sheet. In such cases, the addition of, for example, a calcium carbonate-SFAE mixture provides an improvement that allows control of the density of the sheet.

In one embodiment, the present disclosure demonstrates that by treating a cellulosic material with a combination of inorganic particles and sugar fatty acid esters, the resulting material can be made, inter alia, strongly hydrophobic and/or oleophobic. Moreover, these sugar fatty acid esters are themselves readily digested when removed by, for example, bacterial enzymes. The derivatized surface exhibits very high thermal resistance, can withstand temperatures as high as 250° C., and can be more impermeable to gases than the underlying base substrate. The material is therefore an ideal solution to the problem of derivatizing the hydrophilic surface of cellulose in any one embodiment in which cellulosic materials may be used.

Advantages of the products and methods disclosed herein include that the coating composition is made from renewable agricultural sources - sugars and vegetable oils; Suitable for contact; even with high levels of water resistance, can be tailored to lower the coefficient of friction of the paper/board surface (i.e., making the paper less slippery for downstream processing or end use may or may not be used with special emulsifying equipment or emulsifiers; be compatible with conventional paper recycling programs; and do not have an adverse effect on In addition, the increased use of minerals, such as PCC, provides advantages of the inherent properties of fillers (eg, low abrasiveness).

As used herein, "bio-based" means materials intentionally made from substances derived from living (or formerly living) organisms. In a related aspect, materials containing at least about 50% of such substances are considered biobased.

As used herein, "bind," including grammatical variations thereof, means to adhere or bring together essentially as a single mass.

As used herein, "cellulosic" refers to a natural, synthetic or semi-synthetic material that can be molded or extruded into objects (e.g., bags, sheets) or films or filaments, wherein such objects or films or It means a natural, synthetic or semi-synthetic material that can be used to make filaments and is structurally and functionally similar to cellulose, eg coatings and adhesives (eg carboxymethyl cellulose). In another example, complex carbohydrates (C ₆ H ₁₆ O ₅ ) _n composed of glucose units, cellulose, which forms the major component of cell walls in most plants, are cellulosic.

As used herein, "coating weight" is the weight of material (wet or dry) applied to a substrate. Expressed in pounds per specified ream or grams per square meter.

As used herein, "compostable" means that these solid products are biodegradable in soil.

As used herein, "dry basis" is a measure of the mass of all constituents (eg, solids) except water.

As used herein, "edge wicking" in paper construction is, but is not limited to, capillary penetration of pores between fibers, diffusion through fibers and bonds, and surface diffusion of fibers. It means the absorption of water at the outer limit of said structure by one or more mechanisms, including these. In a related aspect, coatings containing the sugar fatty acid esters described herein prevent edge wicking in treated products. In one aspect, there is a similar problem of grease/oil getting into creases that may be present in paper or paper products. The "grease creasing effect" produced by folding, pressing or crushing the paper structure can be defined as the absorption of grease in the paper structure.

As used herein, "effect," including grammatical variations thereof, means imparting a specific property to a particular material.

As used herein, "hydrophobic substance" means a substance that does not attract water. For example, waxes, rosins, resins, sugar fatty acid esters, diketene, shellac, vinyl acetate, PLA, PEI, oils, fats, lipids, other water repellent chemicals, or combinations thereof are hydrophobic materials.

As used herein, "hydrophobic" means the property of being water-repellent, tending to repel and not absorb water.

As used herein, "lipid-resistant" or "oleophobic" means the property of being lipophobic and tending to repel and not absorb lipids, greases, fats, and the like. In a related aspect, grease resistance can be measured by the "3M kit" test or the TAPPI T559 kit test.

As used herein, "cellulose-containing material" or "cellulose-based material" means a composition consisting essentially of cellulose. Such materials include, for example, paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon paperboard, diapers, weed blocks/barriers. Fabrics or films, mulching films, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compostable bags, release paper, Tableware, containers for holding hot or cold beverages, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, non-carbonated liquid storage bottles, food wrap films, garbage disposal containers, Food handling utensils, lids for cups, paper straws, fabric fibers, water storage and transport equipment, paperboard for pharmaceutical applications, release paper, storage and transport equipment for alcoholic or non-alcoholic beverages, outer casings for electrical appliances or screens, internal or external components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping gear, molded cellulose system materials, as well as combinations thereof, but are not limited to these.

As used herein, "release paper" means a paper sheet used to prevent a tacky surface from prematurely adhering to an adhesive or mastic. In one aspect, the coatings disclosed herein can be used to replace or reduce the use of silicon or other coatings to produce materials with low surface energies.表面エネルギーの決定は、接触角の測定（例えば、Ｏｐｔｉｃａｌ Ｔｅｎｓｉｏｍｅｔｅｒ ａｎｄ／ｏｒ Ｈｉｇｈ Ｐｒｅｓｓｕｒｅ Ｃｈａｍｂｅｒ、Ｄｙｎｅ Ｔｅｓｔｉｎｇ、Ｓｔａｆｆｏｒｄｓｈｉｒｅ、Ｕｎｉｔｅｄ Ｋｉｎｇｄｏｍ）またはＳｕｒｆａｃｅ Ｅｎｅｒｇｙ Ｔｅｓｔ Ｐｅｎｓ ｏｒ Ｉｎｋｓの使用（例えば、Ｄｙｎｅ Ｔｅｓｔｉｎｇ、Ｓｔａｆｆｏｒｄｓｈｉｒｅ、Ｕｎｉｔｅｄ Ｋｉｎｇｄｏｍをsee ).

As used herein, "removable" in the context of SFAE means that the SFAE coating, once applied, can be removed from the cellulose-based material (e.g., by manipulating physical properties removable). As used herein, "non-peelable" in the context of SFAE means that the SFAE coating once applied substantially irreversibly bonds to the cellulose-based material (e.g., is removable by chemical means). means

As used herein, "fiber in solution" or "pulp" means a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops or waste paper. . In a related aspect in which the cellulose fibers are treated by the methods disclosed herein, the cellulose fibers themselves contain the bound sugar fatty acid esters as isolated entities and the bound cellulose fibers are free fibers. (eg, pulp or cellulose fibers or nanocellulose or microfibrillated cellulose-sugar fatty acid ester bonded materials do not form hydrogen bonds between fibers as readily as unbonded fibers).

As used herein, "repulpable" means making a paper or paperboard product suitable for crushing into a loose, soft mass for reuse in the manufacture of paper or paperboard. do.

As used herein, "adjustable," including grammatical variations thereof, means adjusting or adapting a method to achieve a specified result.

As used herein, "water contact angle" means the angle, measured through a liquid, at which the liquid/vapor interface meets a solid surface. It quantifies the wettability of solid surfaces by liquids. Contact angles reflect the strength with which liquid and solid molecules interact relative to the strength with which each interacts with its own species. On many highly hydrophilic surfaces, water droplets exhibit contact angles between 0° and 30°. Generally, a solid surface is considered hydrophobic if the water contact angle is greater than 90°. Water contact angles may be readily obtained using an optical tensiometer (see, eg, Dyne Testing, Staffordshire, United Kingdom).

As used herein, "water vapor permeability" means breathability, or the ability of a textile to transport moisture. There are at least two different measurement methods. One of them, the MVTR (Moisture Vapor Transmission Rate) test according to ISO 15496, indicates the moisture vapor permeability (WVP) of a fabric and thus the extent of sweat transport to the outside air. The measurement determines how many grams of moisture (water vapor) pass through a square meter of fabric in 24 hours (the higher the level, the more breathable).

In one aspect, the TAPPI T 530 Hercules size test (ie, paper size test by ink resistance) may be used to determine water resistance. Ink resistance by the Hercules method is best classified as a direct measurement test of the degree of penetration. Others classify it as a rate of penetration test. No single test "measures sizing" is the best. Test selection will depend on the end use and need for mill control. This method is particularly suitable for use as a mill-controlled sizing test that accurately detects changes in sizing levels. It provides reproducible results, reduced test time, and the sensitivity of the ink float test while automatically determining the endpoint.

Sizing, measured by the resistance to permeation of aqueous liquids through the paper or absorption of aqueous liquids into the paper, is an important characteristic of many papers. Typical of these are bags, containerboard, meat wrap, writing and some printing grades.

This method may be used to monitor the production of paper or paperboard for a particular end use. provided that an acceptable correlation has been established between the test values and the end-use performance of the paper. Due to the nature of the test and permeant, it is not sufficiently correlated to be applicable to all end-use requirements. This method measures sizing by permeability. Other methods measure sizing by surface contact, surface penetration, or absorption. A size test is selected based on its ability to simulate the means of water contact or absorption in the end use. This method can also be used to optimize sizing chemical usage costs.

As used herein, "oxygen permeability" means the degree to which a polymer allows the passage of gases or fluids. The oxygen permeability (Dk) of a material is a function of its diffusivity (D) (i.e., the speed at which oxygen molecules traverse the material) and solubility (k) (or absorption of oxygen molecules per volume of material). be. Oxygen permeability (Dk) values typically fall within the range of 10-150×10 ⁻¹¹ (cm ² ml O ₂ )/(s ml mmHg). A semi-logarithmic relationship was shown between hydrogel water content and oxygen permeability (in units: Barrer units). The International Organization for Standardization (ISO) has designated permeability using the SI unit of hectopascals (hPa) for pressure. Therefore Dk=10 ⁻¹¹ (cm ² ml O ₂ )/(s ml hPa). Barrer units can be converted to hPa units by multiplying it by the constant 0.75.

As used herein, "biodegradable", including its grammatical variations, means capable of being broken down by the action of living organisms (eg, by microorganisms) into particularly harmless products.

As used herein, "recyclable", including grammatical variations thereof, can be processed or (for used and/or scrap) processed to make said material suitable for reuse. means a material that can

As used herein, "filler" means finely divided white minerals (or pigments) added to the papermaking furnish to improve the optical and physical properties of the sheet. The particles fill the spaces and interstices between the fibers, thus producing sheets with increased brightness, opacity, smoothness, gloss, and printability, but generally reduced bond and tear strength. do the work Commonly encountered papermaking fillers include clays (kaolin, bentonite), calcium carbonate (both GCC and PCC), talc (magnesium silicate), and titanium dioxide.

As used herein, "Gurley second" or "Gurley number" means that 100 cubic centimeters (deciliter) of air passes through 1.0 square inch of a given material with a water pressure difference of 4.0. A unit that indicates the number of seconds required to pass through 88 inches (0.176 psi) (ISO 5636-5:2003) (porosity). Further, with respect to stiffness, the "Gurley number" is a unit of a piece of material that measures the force required to deflect the material held vertically by a given amount (1 milligram of force). Such values can be measured with equipment from Gurley Precision Instruments (Troy, New York).

The Hydrophilic-Lipophilic Balance (HLB) of a surfactant is a measure of how hydrophilic or lipophilic it is, determined by calculating the values of different regions of its molecule.

Griffin's method for nonionic surfactants described in a 1954 study is HLB=20*M _h /M
[where M _h is the molecular weight of the hydrophilic portion of the molecule and M is the molecular weight of the entire molecule. ] and the results are expressed on a scale of 0-20. An HLB value of 0 corresponds to a completely lipophilic/hydrophobic molecule and a value of 20 corresponds to a completely hydrophilic/lipophobic molecule.

HLB values can be used to predict surfactant properties of molecules.
<10: Fat-soluble (water-insoluble)
>10: water soluble (non-lipid)
1.5 ~ 3: Defoamer 3 ~ 6: W / O (water-in-oil type) emulsifier 7 ~ 9: Wetting spreading agent 13 ~ 15: Cleaning agent 12 ~ 16: O / W (oil-in-water type) emulsifier 15 ~18: solubilizer or hydrotrope

In some embodiments, HLB values for sugar fatty acid esters (or compositions comprising said esters) disclosed herein may be in the lower range. In other embodiments, HLB values for sugar fatty acid esters (or compositions comprising said esters) disclosed herein may be in the medium to high range. In one embodiment, mixing SFAEs with different HLB values may be used.

As used herein, "SEFOSE®" is the name for sucrose fatty acid esters containing one or more unsaturated fatty acids made from soybean oil (soybean oil fatty acid esters) and is available from Procter & Gamble Chemicals. (Cincinnati, OH) under the trade name SEFOSE® 1618U (see polysoybean oil fatty acid sucrose below). As used herein, "OLEAN®" is the name for sucrose fatty acid esters having the formula Cn+ _{12H2n + 22O13} , where all fatty acids are saturated, available from Procter & Gamble Chemicals. be. Additionally, SFAE can be purchased from Mitsubishi Chemical Foods Co., Ltd. (Tokyo, Japan), which offers a variety of such SFAEs.

As used herein, "soybean oil fatty acid ester" means a mixture of salts of fatty acids derived from soybean oil.

As used herein, "oilseed fatty acid" means soybean, peanut, canola, barley, canola, sesame seed, cottonseed, palm kernel, grapeseed, olive, safflower, sunflower, copra, corn, coconut, linseed, hazelnut means plant-derived fatty acids including, but not limited to, wheat, rice, potato, cassava, legumes, camelina seed, mustard seed, and combinations thereof.

As used herein, "wet strength" means a measure of how well the web of fibers holding the paper together can resist breaking forces when the paper is wet. Wet strength can be measured using a Finch Wet Strength Device manufactured by Thwing-Albert Instrument Company (West Berlin, NJ). In this case, wet strength is typically provided by wet strength additives such as cymene, cationic glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, including Contains epoxide resins. In one embodiment, the SFAE-coated cellulose-based materials disclosed herein achieve such wet strength in the absence of such additives.

As used herein, "wet" means covered or saturated with water or another liquid.

In one embodiment, the process disclosed herein comprises mixing a sugar fatty acid ester with inorganic particles (e.g., clay, talc, calcium carbonate), applying the mixture to a cellulosic material, and to the cellulosic material, the process comprising: contacting the cellulosic-based material with a combination; exposing the contacted cellulosic-based material to heat, radiation, a catalyst, or a combination thereof for a sufficient time exposing to bind the combination to the cellulose-based material. In a related aspect, such radiation can include, but is not limited to UV, IR, visible light, or combinations thereof. In another related aspect, the reaction may be carried out at room temperature (ie, 25°C) to about 150°C, from about 50°C to about 100°C, or from about 60°C to about 80°C.

Additionally, the binding reaction between the mixture and the cellulosic material may be carried out with or substantially reduced from retention aids (ie, binders such as PvOH or starch). In one aspect, the mixture may comprise a mixture of mono-, di-, tri-, tetra-, penta-, hexa-, hepta- or octaesters. In another aspect, the mixture includes, but is not limited to, milk proteins (e.g., casein, whey protein, etc.), wheat gluten, gelatin, prolamins (e.g., corn zein), soy protein isolates, starch, processed Proteins, polysaccharides and lipids may also be included, including starches, acetylated polysaccharides, alginates, carrageenan, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof.

In one embodiment, the cellulosic material may be made oleophobic by adding polyvinyl alcohol (PvOH) and/or prolamines. In one aspect, prolamines include zein, gliadin, hordein, secalin, catillin and avenin. In a related aspect, the prolamin is zein.

In one embodiment, catalysts and organic supports (e.g., volatile organic compounds) are not required to carry out the binding reaction, for which lamination of materials using the disclosed methods is contemplated. It includes what is not done. In a related aspect, the reaction time is substantially instantaneous (ie, less than 1 second). Furthermore, the material obtained exhibits low blocking.

As used herein, all sugar fatty acid esters, including mono-, di- and trisaccharides, are adaptable for use in connection with this aspect of the invention. In a related aspect, the sugar fatty acid ester may be a mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octaester, and combinations thereof, wherein the fatty acid moiety may be saturated, unsaturated or a combination thereof.

Without wishing to be bound by any theory, the interaction between the sugar fatty acid ester and the cellulose-based material may be through ionic, hydrophobic, van der Waals interactions, or covalent bonds, or combinations thereof. There may be. In a related aspect, the sugar fatty acid ester binding to the cellulose-based material may be substantially irreversible (eg, using SFAFs containing a combination of saturated and unsaturated fatty acids).

Furthermore, the binding of sugar fatty acid esters alone in sufficient concentration is sufficient to render cellulose-based materials hydrophobic, i. This is achieved without the addition of PEI, oils, other water repellent chemicals or combinations thereof (i.e. a second hydrophobe), which includes other properties such as reinforcement of cellulose-based materials, among others. , stiffening, and bulking are achieved solely by sugar fatty acid ester linkages.

An advantage of the present invention is that multiple fatty acid chains are reactive with cellulose and two sugar molecules within the structure, e.g., the disclosed sucrose fatty acid esters give rise to tight crosslinked networks and and that the strength of fibrous webs such as textiles is improved, thus overcoming the potential undesirable effects of some fillers, such as calcium carbonate and reduced bond and tear strength. This is not typically found in other sizing or hydrophobic treatment chemistries. The sugar fatty acid esters disclosed herein also provide/increase wet strength, a property not present when using many other water resistant chemistries.

Another advantage is that the disclosed sugar fatty acid esters soften fibers and increase the space between them, thus increasing bulk without substantially increasing weight. Additionally, the processed fibers and cellulose-based materials disclosed herein may be repulped. Further, for example, water cannot easily "push" through the low surface energy barrier and enter the sheet.

Saturated SFAEs are typically solids at nominal processing temperatures, and unsaturated SFAEs are typically liquids. This allows the formation of uniform, stable dispersions of saturated SFAEs in aqueous coatings without significant interaction or incompatibility with other typically hydrophilic coating components. In addition, the dispersion prepares high concentrations of saturated SFAEs without adversely affecting coating rheology, uniform coating application, or coating performance properties. If the particles of saturated SFAE melted and spread out during heating, drying and solidification of the coating layer, the coating surface would become hydrophobic. In one embodiment, a method of producing a bulky fibrous structure that retains strength even when exposed to water is disclosed. Generally dried fiber slurries form dense structures that readily degrade when exposed to water. Shaped textile products made using the disclosed methods include paper plates, drink holders (e.g., cups), lids that are lightweight, strong, and resistant to exposure to water and other liquids. , food trays and packaging.

In one embodiment, sugar fatty acid esters can be mixed with polyvinyl alcohol (PvOH) to produce a size for water resistant coatings. As disclosed herein, a synergistic relationship between sugar fatty acid esters and PvOH was demonstrated, including the ability to reduce the amount of PvOH in the case of inorganic mixtures. PvOH is a good film former by itself and is known in the art to form strong hydrogen bonds with cellulose, but it is not very resistant to water, especially hot water. In embodiments, the use of PvOH helps emulsify sugar fatty acid esters into waterborne coatings. In one aspect, PvOH provides sugar fatty acid esters with a rich source of OH groups for cross-linking along the fiber, and paper strength, especially wet strength, and water resistance, is possible with PvOH alone. increase beyond. For saturated sugar fatty acid esters with free hydroxyls on the sugar, cross-linking agents such as dialdehydes (eg, glyoxal, glutaraldehyde, etc.) can also be used.

In one embodiment, the sugar fatty acid ester comprises or consists essentially of sucrose esters of fatty acids. Many methods are known and available for making or providing the sugar fatty acid esters of the present invention, and all such methods are available for use within the broad scope of the present invention. it is conceivable that. For example, in certain embodiments, the fatty acid ester is one derived from sugars and oilseeds including, but not limited to, soybean oil, sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof. or synthesized by esterification with multiple fatty acid moieties.

［式中、「Ａ」は、水素または以下の構造１

In one embodiment, sugar fatty acid esters comprise sugar moieties including, but not limited to, sucrose moieties in which one or more of the hydroxyl hydrogens have been replaced by an ester moiety. In a related aspect, the disaccharide ester has the structure of formula I

[wherein "A" is hydrogen or structure 1 below

(wherein "R" is a linear, branched, or cyclic, saturated or unsaturated, aliphatic or aromatic moiety of about 8 to about 40 carbon atoms), and at least 1 If the two "A's" are at least one, at least two, at least three, at least four, at least five, at least six, at least seven, and all eight, then the "A" portion of the formula is , according to structure 1. ]
Also in a related aspect, the sugar fatty acid esters described herein are mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters, and combinations thereof. and the aliphatic groups may be all saturated, contain saturated and/or unsaturated groups, or a combination thereof.

Suitable "R" groups include any form of aliphatic moiety, including those containing one or more substituents, which may occur on any carbon in the moiety. good too. Also included are aliphatic moieties containing functional groups within the aliphatic moiety, such as ether, ester, thio, amino, phospho, and the like. Also included are oligomeric and polymeric aliphatic moieties such as sorbitan, polysorbitan and polyalcohol moieties. Examples of functional groups that can be added to an aliphatic (or aromatic) moiety containing an "R" group include, but are not limited to, halogen, alkoxy, hydroxy, amino, ether and ester functionalities. In one aspect, the moieties may have crosslinkable functional groups. In another aspect, SFAE (eg, activated clay/pigment particles) may be crosslinked to the surface. In another aspect, the double bonds present on SFAE may be used to facilitate reactions to other surfaces.

Suitable disaccharides include raffinose, maltodextrose, galactose, sucrose, glucose combinations, fructose combinations, maltose, lactose, mannose combinations, erythrose combinations, isomaltose, isomaltulose, trehalose, trehalulose, cellobiose, lamina Includes ribiose, chitobiose, and combinations thereof.

In one embodiment, the substrate for adding fatty acids can include starch, hemicellulose, lignin, or combinations thereof.

In one embodiment, the composition comprises a starch fatty acid ester, wherein the starch is dent corn starch, waxy corn starch, potato starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum starch, sweet potato starch, and mixtures thereof. may be derived from any suitable source such as

More specifically, the starch can be raw starch or starch that has been modified by chemical, physical or enzymatic processing.

Chemical processing includes any treatment of starch with chemicals that results in modified starch (eg, plastarch material). Chemical processing includes within the scope of starch depolymerization, starch oxidation, starch reduction, starch etherification, starch esterification, starch nitrification, starch defatting, starch hydrophobization, etc. is not limited to Chemically modified starch may also be prepared by using any combination of chemical treatments. Examples of chemically modified starches include the reaction of alkenylsuccinic anhydrides, especially octenylsuccinic anhydride, with starch to produce hydrophobic esterified starches; 2,3-epoxypropyltrimethyl to produce cationic starches. reaction of ammonium chloride with starch; reaction of ethylene oxide with starch to produce hydroxyethyl starch; reaction of hypochlorite with starch to produce oxidized starch; reaction of starch with acid; defatting of starch with solvents such as methanol, ethanol, propanol, methylene chloride, chloroform, carbon tetrachloride, etc. to produce defatted starch.

Physically modified starch is starch that has been physically treated in a manner to provide physically modified starch. Physical processing includes heat treatment of starch in the presence of water, heat treatment of starch in the absence of water, crushing of starch granules by any mechanical means, pressure treatment of starch to form starch granules. and the like, but are not limited to these. Physically modified starch can also be prepared by using a combination of any of the physical treatments. Examples of physically modified starches include heat treatment of starch in an aqueous environment to swell starch granules without granule breakage; heat treatment of anhydrous starch granules to cause polymer rearrangement; fragmentation of starch granules by mechanical degradation; and pressure treatment of the starch granules through an extruder to cause the starch granules to melt.

An enzymatically modified starch is any starch that has been treated with an enzyme in any way that provides an enzymatically modified starch. Enzymatic processing includes, but is not limited to, α-amylase and starch reactions, protease and starch reactions, lipase and starch reactions, phosphorylase and starch reactions, oxidase and starch reactions, and the like. Enzymatically modified starch can be prepared by using any combination of enzymatic treatments. Examples of enzymatic processing of starch include reaction of alpha-amylase enzyme with starch to produce depolymerized starch; reaction of alpha-amylase debranching enzyme with starch to produce debranched starch; Reaction of protease enzyme with starch to produce starch with reduced protein content; reaction of lipase enzyme with starch to produce starch with reduced lipid content; reaction of phosphorylase enzyme with starch. and reacting an oxidase enzyme with starch to produce enzymatically oxidized starch.

Disaccharide fatty acid esters have the formula I [wherein the "R" group is aliphatic, linear or branched, saturated or unsaturated, and has between about 8 and about 40 carbon atoms. ] may be a sucrose fatty acid ester.

As used herein, the terms "sugar fatty acid ester" and "sucrose fatty acid ester" include compositions having different purities, as well as mixtures of compounds of any purity level. For example, the sugar fatty acid ester compound can be a substantially pure material, i.e., having a predetermined number of "A" groups substituted by only one of the structure 1 moieties (i.e., all "R groups are the same and all of the sucrose moieties are substituted to an equal extent). It also includes compositions comprising blends of two or more sugar fatty acid ester compounds having different degrees of substitution, but all of the substituents having the same "R" group structure. It also includes compositions in which the "A" groups have different degrees of substitution and the substituent moieties of the "R" groups are independently mixtures of compounds selected from two or more "R" groups of Structure 1. In a related aspect, the "R" groups can be the same or different, including that the sugar fatty acid esters in the composition can be the same or different (ie mixtures of different sugar fatty acid esters).

In the composition according to the invention, the composition may consist of a sugar fatty acid ester compound with a high degree of substitution. In one embodiment, the sugar fatty acid ester is sucrose polysoybean oil.

ポリダイズ油脂肪酸スクロース(SEFOSE(登録商標)1618U)

Sucrose polysoybean oil fatty acid (SEFOSE® 1618U)

Sugar fatty acid esters may be made by esterification with substantially pure fatty acids by known esterification processes. They can also be prepared by transesterification using sugars with fatty acid esters in the form of fatty acid glycerides, e.g., derived from natural sources, e.g., oils extracted from oilseeds, e.g., those found in soybean oil. Transesterification reactions using fatty acid glycerides to provide sucrose fatty acid esters are described, for example, in U.S. Pat. Nos. 3,963,699; 4,517,360; 4,518,772; 5767257; 6504003; 6121440; and 6995232; shall form part of this specification.

In addition to making hydrophobic sucrose esters via transesterification, similar hydrophobic properties have been demonstrated in fibrous cellulosic articles by directly reacting acid chlorides with polyols containing ring structures similar to sucrose. may be achieved by

As noted above, sucrose fatty acid esters can be prepared by transesterification of sucrose from methyl ester feedstocks prepared from glycerides derived from natural sources (e.g., hereby incorporated by reference in its entirety). See US Pat. No. 6,995,232). As a result of the source of fatty acids, the feedstocks used to prepare sucrose fatty acid esters contain a variety of saturated and unsaturated fatty acid methyl esters with fatty acid moieties containing 12-40 carbon atoms. This is reflected in the products made from such sources, sucrose fatty acid esters, because the sucrose moieties comprising the products contain a mixture of ester moiety substituents, described above. Referring to Structure 1 of , the "R" group is a mixture having 12-26 carbon atoms in a ratio that reflects the feedstock used to prepare the sucrose ester. To further illustrate this point, sucrose esters derived from soybean oil contain oleic acid (H ₃ C—CH ₂ ] ₇ —CH═CH—[CH ₂ ] ₇ —C(O _{) OH ) triglycerides , 49 wt} . , 11% by weight of the triglyceride of linolenic acid (H ₃ C-[--CH ₂ -CH=CH-] ₃ -[--CH ₂ -] ₇ -C(O)OH), and 14% by weight of Seventh Ed. It is a mixture of species with an "R" group structure reflecting the inclusion of various saturated fatty acid triglycerides as described in the Of the Merck Index. All of these fatty acid moieties are representative of the substituent "R" groups of the product sucrose fatty acid esters. Thus, when referring to sucrose fatty acid esters herein as the product of a reaction employing a fatty acid feedstock derived from a natural source, such as soybean oil fatty acid sucrose, the term is used as a result of the source from which the sucrose fatty acid esters are prepared. It is intended to include all of the various components typically found. In a related aspect, the disclosed sugar fatty acid esters may exhibit low viscosity (eg, about 10-2000 centipoise at room temperature or normal atmospheric pressure). In another aspect, unsaturated fatty acids may have 1, 2, 3 or more double bonds.

In one embodiment of the invention, the sugar fatty acid ester, in aspect the disaccharide ester, has an average of greater than about 6 carbon atoms, about 8 to 16 carbon atoms, about 8 to about 18 carbon atoms. , about 14 to about 18 carbon atoms, about 16 to about 18 carbon atoms, about 16 to about 20 carbon atoms, about 20 to about 40 carbon atoms.

In one embodiment, the sugar fatty acid ester may be present at different concentrations to achieve hydrophobicity/oleophobicity depending on the morphology of the cellulose-based material. In one aspect, when the sugar fatty acid ester (SFAE) is attached to the cellulose-based material as a coating, the SFAE is applied to the surface of the cellulose-based material from at least about 0.1 g/m ² to about 1.0 g/m 2 . ² , present at a coating weight of from about 1.0 g/m ² to about 2.0 g/m ² , from about 2 g/m ² to about 3 g/m ² . In related aspects, it is from about 3 g/m ² to about 4 g/m ² , from about 4 g/m ² to about 5 g/m ² , from about 5 g/m ² to about 10 g/m ² , from about 10 g/m ² About 20 g/m ² can be present. In another aspect, when the cellulose-based material is a solution containing cellulose fibers, the SFAE is present at a concentration of at least about 0.025% (wt/wt) of all fibers present. In a related aspect, it comprises from about 0.05% (wt/wt) to about 0.1% (wt/wt), from about 0.1% (wt/wt) to about 0 .5% (wt/wt), from about 0.5% (wt/wt) to about 1.0% (wt/wt), from about 1.0% (wt/wt) to about 2.0% (wt/ wt), about 2.0% (wt/wt) to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0% (wt/wt). 0% (wt/wt) to about 5.0% (wt/wt), about 5.0% (wt/wt) to about 10% (wt/wt), about 10% (wt/wt) to about 50 % (wt/wt). In another related aspect, the amount of SFAE may equal the amount of fiber present. In some embodiments, the SFAE can coat the entire outer surface of the cellulose-based material (eg, coat the entire piece of paper or cellulose-containing article).

In other embodiments, the coating comprises, by weight of the coating, from about 0.9% to about 1.0% (wt/wt), from about 1.0% to about 5.0% (wt/wt), about 5.0 to about 10% (wt/wt), about 10% to about 20% (wt/wt), about 20% to about 30% (wt/wt), about 40% to about 50% (wt/ wt) sugar fatty acid esters. In a related aspect, the coating can contain from about 25% to about 35% sugar fatty acid ester by weight of the coating (wt/wt).

In one embodiment, cellulose-based materials include paper, paperboard, paper sheets, paper pulp, cups, boxes, trays, lids, release paper/liners, compostable bags, shopping bags, shipping bags, bacon paperboard. , tea bags, insulating materials, coffee or tea containers, pipes and aqueducts, food grade disposable cutlery, dishes and bottles, screens for TVs and portable devices, clothing (e.g. cotton or cotton blends), bandages, pressure sensitive Labels, pressure-sensitive tapes, feminine products, and medical devices used on or in the body such as contraceptives, drug delivery devices, containers of pharmaceutical materials (e.g., pills, tablets, suppositories, gels, etc.), etc. include, but are not limited to. The disclosed coating techniques can also be used on furniture and upholstery, outdoor camping gear, and the like.

In one aspect, the coatings described herein are tolerant to pHs ranging from about 3 to about 9. In related aspects, the pH can be from about 3 to about 4, from about 4 to about 5, from about 5 to about 7, from about 7 to about 9.

In one embodiment, an alkanoic acid derivative is mixed with a sugar fatty acid ester to form an emulsion, and the emulsion is used to treat cellulose-based materials.

In one embodiment, the sugar fatty acid ester can be an emulsifier and is a mixture of one or more mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, or octa-esters. can include In another aspect, the fatty acid portion of the sugar fatty acid ester may contain saturated groups, unsaturated groups, or combinations thereof. In one aspect, the sugar fatty acid ester-containing emulsion contains milk protein (e.g., casein, whey protein, etc.), wheat gluten, gelatin, prolamins (e.g., corn zein), soy protein isolate, starch, acetylated polysaccharides. , alginate, carrageenan, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof, including but not limited to proteins, polysaccharides and/or lipids.

In one embodiment, the sugar fatty acid esters disclosed herein include, but are not limited to, agalites, esters, diesters, ethers, ketones, amides, nitriles, aromatic compounds (e.g., xylene, toluene), acid halogens. compound, anhydride, alkylketene dimer (AKD), alabaster gypsum, alganic acid, alum, alvarin, glue, barium carbonate, barium sulfate, chlorine dioxide, dolomite, diethylenetriamine pentaacetate, EDTA, enzymes, form Amidine sulfate, guar gum, gypsum, lime, magnesium bisulfate, milk of lime, milk of magnesia, polyvinyl alcohol (PvOH), rosin, rosin soap, satin, soap/fatty acid, sodium bisulfate, soda ash, titania, surfactant, starch. , modified starches, hydrocarbon resins, polymers, waxes, polysaccharides, proteins, latexes, and other chemicals used for papermaking, including combinations thereof, may be used in the coating. In one embodiment, the disclosed mixture comprises one or more SFAEs and the following inorganic particles: clay (kaolin, bentonite), calcium carbonate (both GGC and PCC), talc (magnesium silicate), and titanium dioxide. In a related aspect, the inorganic particles are present in the coating composition from about 1% to about 2%, from about 2% to about 5%, from about 5% to about 10%, from about 10% to about 20%, from about 20%. % to about 30%, about 30% to about 40%, about 40% to about 50%, about 50% to about 60%, or about 60% to about 70%. In a further related aspect, the SFAE may be present in the same, higher or lower proportion compared to the amount of inorganic particles in the coating. In one aspect, a coating comprising one or more SFAEs comprises all saturated fatty acids.

In one embodiment, the cellulose-containing material produced by the methods disclosed herein exhibits increased hydrophobicity or water resistance compared to cellulose-containing material without treatment. In a related aspect, the treated cellulose-containing material exhibits increased oleophobicity or grease resistance as compared to cellulose-containing material without treatment. In another related aspect, the treated cellulose-containing material can be biodegradable, compostable, and/or recyclable. In one aspect, the treated cellulose-containing material is hydrophobic (water resistant) and oleophobic (grease resistant).

In one embodiment, the treated cellulose-containing material may have improved mechanical properties compared to the same untreated material. For example, paper bags treated with the methods disclosed herein exhibit increased burst strength, Gurley number, tensile strength and/or maximum load energy. In one aspect, the burst strength is increased by about 0.5-1.0 fold, about 1.0-1.1 fold, about 1.1-1.3 fold, about 1.3-1.5 fold. ing. In another aspect, the Gurley number increased about 3-4 fold, about 4-5 fold, about 5-6 fold, and about 6-7 fold. In yet another aspect, the tensile strain is about 0.5-1.0 times, about 1.0-1.1 times, about 1.1-1.2 times, and about 1.2-1.3 times doubled. In yet another aspect, the maximum load energy is about 1.0-1.1 times, about 1.1-1.2 times, about 1.2-1.3 times, and about 1.3-1. increased fourfold.

In one embodiment, the cellulose-containing material is microfibrillated cellulose, for example, as described in US Patent Application Publication No. 2015/0167243, all of which is incorporated herein by reference. (MFC) or cellulose nanofibers (CNF), wherein the MFC or CNF is added during the forming and papermaking processes and/or is added to the preforming layer as a coating or second layer to form said base paper reduce the porosity of In a related aspect, the base paper is contacted with the sugar fatty acid esters described above. In a further related aspect, the contacted base paper is further contacted with polyvinyl alcohol (PvOH). In one embodiment, the resulting contacted base paper is controllably water- and grease-resistant. In a related aspect, the resulting base paper has a Gurley value of at least about 10 to 15 (i.e., Gurley air resistance (sec/100 cc, 20 ounce cylinder)), or at least about 100, at least about 200 to about 350. may indicate In one aspect, the sugar fatty acid ester coating may be a laminate with respect to one or more layers, or may provide one or more layers as a laminate, or a coating of one or more layers. may be decreased to achieve the same performance benefits (eg, water resistance, grease resistance, etc.). In a related aspect, the laminate may include a biodegradable and/or composable heat seal or adhesive.

In one embodiment, the sugar fatty acid ester may be formulated as an emulsion, and the choice of emulsifier and amount used is dictated by the properties of the composition and the ability of the emulsifier to facilitate dispersion of the sugar fatty acid ester. In one aspect, emulsifiers include water, buffers, polyvinyl alcohol (PvOH), carboxymethylcellulose (CMC), latex, milk proteins, wheat gluten, gelatin, prolamines, soy protein isolate, starch, acetylated polysaccharides, alginates. , carrageenan, chitosan, inulin, long chain fatty acids, waxes, agar, alginates, glycerol, gums, lecithin, poloxamers, monoglycerol, diglycerol, monosodium phosphate, monostearate, propylene glycol, detergents, cetyl alcohol, and Combinations of these may include, but are not limited to. In another aspect, the sugar ester:emulsifier ratio is about 0.1:99.9, about 1:99, about 10:90, about 20:80, about 35:65, about 40:60, and about It can be 50:50. Those skilled in the art will appreciate that the ratio may vary depending on the desired properties of the final product.

In one embodiment, sugar fatty acid esters are combined with binders (e.g. starch, soy protein, polymer emulsions, PvOH, latex) and additives (e.g. glyoxal, glyoxalated resins, zirconium salts, calcium stearate, lecithin oleates, polyethylene emulsions, carboxymethylcellulose, acrylic polymers, alginates, polyacrylate gums, polyacrylates, microbicides, oil-based defoamers, silicone-based defoamers, stilbenes, direct dyes and acid dyes) can be combined with one or more coating ingredients (alone or in combination) for internal and surface sizing, including but not limited to: In a related aspect, such ingredients build a microporous structure, provide a light scattering surface, improve ink receptivity, improve gloss, bind pigment particles, coat the paper, base Bonds to sheet reinforcement, fills pores in pigment structure, reduces water sensitivity, resists wet picking in offset printing, prevents blade scratching, improves gloss in supercalendering, reduces dusting adjust coating viscosity, provide water retention, disperse pigments, maintain coating dispersion, prevent coating/coating colorant degradation, control foaming, reduce entrained air and coating craters, One or more properties can be provided, including but not limited to controlling color and tint, increasing whiteness and brightness. It will be apparent to those skilled in the art that the combinations may vary depending on the properties desired in the final product.

In one embodiment, the method employing the sugar fatty acid ester is applied to primary/secondary coatings (e.g., silicone-based layers, starch-based layers, clay-based layers, PLA layers, Bio-PBS, PEI layers, etc.). ) to provide a layer of material exhibiting the desired properties (e.g., water resistance, low surface energy, etc.), thereby providing the necessary properties to achieve those same properties. The amount of primary/secondary layers is reduced. In one aspect, a material (eg, a heat-sealable agent) can be coated onto the SFAE layer. In one embodiment, the composition is fluorocarbon and silicone free.

In one embodiment, the composition enhances both mechanical and thermal stability of the processed product. In one aspect, the surface treatment is heat stable at temperatures from about -100°C to about 300°C. In another related aspect, the surface of the cellulose-based material exhibits a water contact angle of about 60° to about 120°. In another related aspect, the surface treatment is chemically stable at temperatures from about 200°C to about 300°C.

The substrate may be dried (eg, at about 80-150° C.) prior to application, but may be treated with the modifying composition, such as by dipping and allowing the surface to be exposed to the composition for less than 1 second. can be done. The substrate can be heated to dry the surface, after which the modified material is ready for use. In one aspect, according to the methods disclosed herein, the substrate may be treated with any suitable coating/sizing method typically practiced in a paper mill (e.g., all of which are herein incorporated by reference). Smook, G., Surface Treatments, Handbook for Pulp & Paper Technologists, (2016), 4th Ed., ^Cpt.18 , pp. 293-309, TAPPI Press, Peachtree , GA USA).

Although in some applications the material may be dried prior to processing, no special preparation of the material is required in practicing the present invention. In one embodiment, the disclosed method can be used on any cellulose-based surface including, but not limited to, films, rigid containers, fibers, pulps, fabrics, and the like. In one aspect, the sugar fatty acid ester or coating agent is applied to a conventional size press (vertical, tilted, horizontal), gate roll size press, metering size press, calender size application, tube sizing, on-machine, off-machine, single-side coater, It can be applied by double-sided coater, short dwell, simultaneous double-sided coater, blade or rod coater, gravure coater, gravure printing, flexographic printing, ink jet printing, laser printing, supercalendering, and combinations thereof.

Depending on the source, cellulose can be paper, paperboard, pulp, softwood fibers, hardwood fibers, or combinations thereof, nanocellulose, cellulose nanofibers, whiskers or microfibrils, microfibrillated cotton or cotton blends, other It can be non-wood fibers (such as sisal, jute or hemp, flax and straw), cellulose nanocrystals, or nanofibrillated cellulose.

In one embodiment, the amount of sugar fatty acid ester coating applied is sufficient to completely coat at least one surface of the cellulose-containing material. For example, in one embodiment, the sugar fatty acid ester coating may be applied to the complete exterior surface of the container, the complete interior surface of the container, or a combination thereof, or to one or both sides of the base paper. In other embodiments, the complete top surface of the film may be coated with a sugar fatty acid ester coating, or the complete bottom surface of the film may be coated with a sugar fatty acid ester coating, or a combination thereof. Sometimes. In some embodiments, the bore of the instrument/instrument may be covered by a coating, or the exterior surface of the instrument/instrument may be covered by a sugar fatty acid ester coating, or a combination thereof. In one embodiment, the amount of sugar fatty acid ester coating applied is sufficient to partially coat at least one surface of the cellulose-containing material. For example, only surfaces exposed to the ambient atmosphere are coated with the sugar ester coating, or only surfaces not exposed to the ambient atmosphere are coated with the sugar ester coating (eg, masking). As will be apparent to those skilled in the art, the amount of sugar fatty acid ester coating applied may depend on the use of the material being coated. In one aspect, one surface may be coated with a sugar fatty acid ester coating and the opposite surface is coated with protein, wheat gluten, gelatin, prolamin, soy protein isolate, starch, modified starch, acetylated polysaccharide. , alginate, carrageenan, chitosan, inulin, long chain fatty acids, waxes, and combinations thereof. In a related aspect, SFAE can be added to the furnish and the resulting material on the web may be provided with an additional coating of SFAE.

Any suitable coating method may be used to deliver any of the various sugar fatty acid ester coatings and/or emulsions applied during the course of practicing this aspect of the method. In one embodiment, the sugar fatty acid ester coating method comprises dipping, spraying, painting, printing, and any combination of any of these methods alone or in performing the disclosed methods. Including with other coating methods as applicable.

For example, by increasing the concentration of sugar fatty acid esters, the compositions disclosed herein are able to react more extensively with the cellulose being treated, with the end result still being improved water/lipid resistance properties. is shown. However, higher coat weights do not necessarily increase water resistance. In one aspect, various catalysts allow for faster "curing" to precisely tune the quality of sugar fatty acid esters to meet specific applications.

The choice of cellulose to be treated, the sugar fatty acid ester, the reaction temperature, and the exposure time are process parameters that may be optimized by routine experimentation to suit any particular application of the final product. will be clear to those skilled in the art.

A derivatized material has altered physical properties that can be defined and measured using appropriate tests known in the art. For hydrophobicity, analytical protocols can include, but are not limited to, contact angle measurements and moisture absorption. Other properties include stiffness, WVTR, porosity, tensile strength, lack of substrate degradation, burst and tear properties. A specific standardized protocol to be followed is defined by the American Society for Testing and Materials (protocol ASTM D7334-08).

The permeability of the surface to various gases such as water vapor and oxygen may also be modified by the sugar fatty acid ester coating method so as to enhance the barrier function of the material. The standard unit for measuring permeability is the Barrer, and protocols for measuring these parameters are also available in the public domain (ASTM Standard F2476-05 for water vapor and ASTM Standard F2622-8 for oxygen).

In one embodiment, materials treated according to the procedures of the present disclosure exhibit complete biodegradability as measured by degradation in an environment under microbial attack.

Various methods are available to define and test biodegradability, including the shake-flask method (ASTM E1279-89 (2008)) and the Zahn-Wellens test (OECD TG 302 B).

Various methods are available to define and test compostability, including but not limited to ASTM D6400.

Materials suitable for treatment by the method according to the invention include cotton fibres, plant fibres, such as flax, wood fibres, regenerated cellulose (rayon and cellophane), part Various forms of cellulose are included, such as alkylated cellulose (cellulose ethers), partially esterified cellulose (acetate rayon), and other modified cellulose materials. As noted above, the term "cellulose" includes all of these materials, as well as others with similar polysaccharide structures and similar properties. Among these are the relatively newer materials microfibrillated cellulose (cellulose nanofibers) (e.g., U.S. Pat. No. 4,374,702, U.S. Patent Application Publication, all of which are hereby incorporated by reference). See 2015/0167243 and 2009/0221812) are particularly suitable for this application. In other embodiments, the cellulose includes cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose (cellulose nitrate), cellulose sulfate, celluloid, methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, Non-limiting examples include hydroxypropylcellulose, cellulose nanocrystals, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, and combinations thereof.

The modification of cellulose disclosed herein, in addition to increasing its hydrophobicity, also increases its tensile strength, flexibility and stiffness, which may further broaden its range of uses. All biodegradable and partially biodegradable products made from or by using the modified cellulose disclosed herein, including recyclable and compostable products, are within the scope of the present disclosure. .

Among the available uses of coating technology, such items include paper, paperboard, paper pulp, cups, lids, boxes, trays, release paper/liners, compostable bags, such as containers for any purpose. , shopping bags, pipes and aqueducts, disposable cutlery for food, plates and bottles, screens for TVs and portable devices, clothing (e.g. cotton or cotton blends), bandages, pressure sensitive labels, pressure sensitive tapes, feminine products, as well as medical devices for use on or within the body such as contraceptives, drug delivery devices, and the like. The disclosed coating techniques can also be used on furniture and upholstery, outdoor camping equipment, and the like.

The following examples are intended to illustrate but not limit the invention.

[Example 1]
<Sugar fatty acid ester formulation>
SEFOSE® is liquid at room temperature and all coatings/emulsions containing this material were applied at room temperature using a benchtop drawdown apparatus. Rod types and sizes were varied to produce different coat weights.

<Formulation 1>
50 ml of SEFOSE® was added to a solution containing 195 ml of water and 5 grams of carboxymethylcellulose (FINNFIX® 10; CP Kelco, Atlanta, Ga.). The formulation was mixed for 1 minute using a Silverson homogenizer set at 5000 rpm. This emulsion was coated onto a 50 gram base sheet made of bleached hardwood pulp and an 80 gram sheet composed of unbleached softwood. Both papers were dried in an oven (105° C.) for 15 minutes. After removal from the oven, the sheets were placed on the lab bench and 10 drops of water (room temperature) were added by pipette to each sheet. The base sheet selected for this test immediately absorbs a droplet of water, while the level of water resistance increases with increasing coat weight for sheets coated with various amounts of SEFOSE®. (See Table 1).

It was observed that the heavier sheets lacked water resistance and that water resistance was not achieved unless the sheet was dry.

<Formulation 2>
Addition of SEFOSE® to cupstock: (Note this is a single ply stock without MFC treatment. 110 grams of paperboard made with eucalyptus pulp). 50 grams of SEFOSE® was added to 200 grams of 5% cooked ethylated starch (Ethylex 2025) and stirred for 30 seconds using a benchtop Kadi mill. Paper samples were coated and placed in an oven at 105°C for 15 minutes. Ten to fifteen test droplets were placed on the coated side of the paperboard and the water holdout time was measured and recorded in the table below. Water penetration of the untreated paperboard control was instantaneous (see Table 2).

<Formulation 3>
Pure SEFOSE® was warmed to 45° C. and placed in a spray bottle. A uniform spray was applied to the paper stock listed in the previous examples, as well as a piece of fiberboard and a quantity of cotton cloth. When a drop of water was placed on the sample, penetration into the substrate occurred within 30 seconds, but after drying in an oven at 105°C for 15 minutes, the drop evaporated before being absorbed into the substrate.

Continuing research has concerned whether SEFOSE® may be compatible with compounds used in oil and grease resistant coatings. SEFOSE® is useful for water resistance and stiffness improvement. 240 g of paperboard stock was used to conduct the stiffness test. The results are shown in Table 3 below. These data were obtained at a single coat weight of 5 grams/square meter and are reported as an average of 5 samples. The results are Taber Stiffness Units recorded using our V-5 Taber Stiffness Tester Model 150-E.

[Example 2]
<Binding of Sugar Ester to Cellulosic Substrate>
To determine whether SEFOSE® is reversibly binding to cellulosic materials, pure SEFOSE® and pure cellulose were mixed in a 50:50 ratio. The SEFOSE® was allowed to react at 300° F. for 15 minutes and the mixture was extracted with methylene chloride (a non-polar solvent) or distilled water. The samples were refluxed for 6 hours and gravimetric analysis of the samples was performed.

[Example 3]
<Investigation of cellulosic surface>
Scanning electron microscopy images of base papers with and without MFC show that a less porous base can potentially require much less waterproofing agent to react to the surface. Figures 1-2 show an untreated, void Whatman filter paper. Figures 1 and 2 show that there is a relatively large exposed surface area with which the derivatizing agent can react. On the other hand, it has also been shown that highly porous sheets have sufficient places for water to escape. Figures 3 and 4 show a side-by-side comparison of paper made from recycled pulp before and after coating with MFC (these are two magnification views of the same sample, left side of image). clearly does not contain MCF). Tests show that derivatization of sheets with much less porosity shows higher promise for long-term water/vapor barrier performance. The last two images are a close-up taken of the average "pores" of one piece of filter paper and a close-up taken of the CNF-coated paper at similar magnification for comparison.

From the above data, it became clear that the addition of more material, which is the critical point, resulted in a corresponding improvement in performance. Without wishing to be bound by any theory, the reaction appears to be faster on unbleached paper, suggesting that the presence of lignin may accelerate the reaction.

In fact, products like SEFOSE® are liquids and can be easily emulsified, suggesting that they can be easily adapted to work in the coating equipment commonly used in paper mills. .

[Example 4]
"Phluphi"
Liquid SEFOSE® was mixed and reacted with bleached hardwood fibers to produce a variety of forms that produced waterproof handsheets. It was found that when the sucrose esters were mixed with the pulp prior to sheet formation, most of them were retained with the fibers. Sufficient heating and drying resulted in the formation of a brittle, fluffy, yet highly hydrophobic handsheet. In this example, 0.25 grams of SEFOSE® was mixed with 4.0 grams of bleached hardwood fibers in 6 liters of water. The mixture was hand-stirred and the water was poured into a standard handsheet mold. The resulting fiber mat was removed and dried at 325°F for 15 minutes. The resulting sheets exhibited significant hydrophobicity and greatly reduced hydrogen bonding between the fibers themselves. (Water contact angles greater than 100 degrees were observed). Emulsifiers could be added. The SEFOSE® to fiber could be about 1:100 to 2:1.

Subsequent testing showed that talc was the only spectator in this and was dropped from further testing.

[Example 5]
<Environmental Effects on SEFOSE® Coating Properties>
In an attempt to better understand the reaction mechanism of sucrose esters and fibers, a low viscosity coating was applied to a bleached kraft sheet with added wet strength resin but no water resistance (no sizing). All coatings measured less than 250 cps using a Brookfield viscometer at 100 rpm.

SEFOSE® was emulsified with Ethylex 2025 (starch) and applied to paper via gravure roll. For comparison, SEFOSE® was also emulsified with Westcote 9050 PvOH. As shown in Figure 5, the oxidation of the double bond of SEFOSE® was enhanced by the presence of heat and an additional chemical environment that enhanced the oxidative chemistry (see also Table 5). ).

[Example 6]
<Effect of unsaturated fatty acid chain versus saturated fatty acid chain>
SEFOSE® was reacted with bleached softwood pulp and dried to form a sheet. Subsequent extractions with CH ₂ Cl ₂ , toluene and water determined the extent of reaction with the pulp. Extracted for at least 6 hours using Soxhlet extraction glassware. The results of the extraction are shown in Table 6 below.

The data showed that essentially all of the SEFOSE® remained on the sheet. To further verify this, the same procedure was performed with the pulp alone and the results showed that about 0.01 g was obtained per 10 g of pulp. Without wishing to be bound by any theory, this can easily be explained as residual pulping chemicals that have not been completely removed or more likely extractables.

Experiments were repeated using pure fibers of cellulose (eg, α-cellulose from Sigma Aldrich (St. Louis, Mo.)). As long as the SEFOSE® loading level remains below about 20% of the fiber mass, more than 95% of the SEFOSE® mass is retained with the fiber and extracted with either polar or non-polar solvents. I didn't. Without being bound by any theory, optimizing the baking time and temperature may further enhance the sucrose esters remaining with the fiber.

As indicated by the data, it was generally found that SEFOSE® could not be extracted from the material after drying. On the other hand, if a fatty acid containing all saturated fatty acid chains (e.g., OLEAN® available from Procter & Gamble Chemicals, Cincinnati, OH) is used instead of SEFOSE® (70° C. or higher ) hot water could be used to extract nearly 100% of the OLEAN® in the material. OLEAN® is identical to SEFOSE® with the only change being that instead of having unsaturated fatty acids attached (SEFOSE®), saturated fatty acids are attached (OLEAN® registered trademark)) point.

Another notable aspect is that multiple fatty acid chains exhibit reactivity with cellulose and two sugar molecules in the structure, SEFOSE® resulting in a tight crosslinked network, paper, paperboard, airlaid and wet-laid nonwovens. , as well as lead to improved strength of fibrous webs such as textiles.

[Example 7]
<Addition of SEFOSE® to achieve water resistance>
Both hardwood and softwood kraft pulps were used to make 2 gram and 3 gram handsheets. When SEFOSE® was added to a 1% pulp slurry at levels of 0.1% or higher, the water was drained off, and handsheets were formed, SEFOSE® was retained with the fibers and imparted water resistance. At 0.1% to 0.4% SEFOSE®, water beaded on the surface for less than a few seconds. Above 0.4% SEFOSE® loading, the time of water resistance increased rapidly to minutes and then hours towards loading levels higher than 1.5%.

[Example 8]
<Production of bulky fiber material>
Adding SEFOSE® to the pulp softened the fibers, increased the space between them and acted to make them loftier. For example, a 3% slurry of hardwood pulp containing 125 grams (dry) of pulp was found to drain and dry to occupy a volume of 18.2 cubic centimeters. 12.5 g of SEFOSE® was added to the same 3% hardwood pulp slurry containing an equal amount of 125 g of dry fiber. When drained and dried, the resulting mat occupied 45.2 cubic centimeters.

30 g of standard bleached hardwood kraft pulp (manufactured by Old Town Fuel and Fiber, LLC, Old Town, Me.) was sprayed with SEFOSE® that had been warmed to 60°C. 4.3 cm ³ of this was placed in a disintegrator at 10,000 rpm and essentially repulped. The mixture was poured through a handsheet mold and dried at 105°C. The resulting hydrophobic pulp occupied a volume of 8.1 ^cm3 . This material was cut into 2 inch squares and placed in a hydraulic press and 50 tons pressure was applied for 30 seconds. Although the squares have greatly reduced volume, they still occupy 50% more volume than the same 2-inch squares cut for the no-pressure control.

Importantly, not only was an increase in bulk and softness observed, but the forced repulped mat upon draining resulted in a fibrous mat that retained all of its hydrophobicity. This quality is valuable in addition to the knowledge that water cannot easily "push" through the low surface energy barrier and enter the sheet. This property is not exhibited by the binding of single hydrophobic fatty acid chains.

Without wishing to be bound by any theory, this suggests that SEFOSE® has reacted with cellulose and the OH groups on the surface of the cellulose fibers are no longer available to participate in subsequent hydrogen bonding. represents additional evidence. Other hydrophobic materials interfere with initial hydrogen bonding, but upon repulp this effect is reversed and the cellulose OH groups are free to participate in hydrogen bonding upon redrying.

[Example 9]
<Bag paper test data>
The table below (Table 7) shows the properties imparted by coating a mixture of 5-7 g/m ² of SEFOSE® and polyvinyl alcohol (PvOH) onto unbleached kraft bag stock (control). Also included for reference are commercially available bags.

As shown in the table, tensile and burst increased when the control base paper was coated with SEFOSE® and PvOH.

[Example 10]
<Wet and dry tensile strength>
A 3 gram handsheet was made from the bleached pulp. The following compares the wet and dry tensile strength at different addition levels of SEFOSE®. Note that these handsheets SEFOSE® did not emulsify during any coating, they were simply mixed into the pulp and drained without adding any other chemicals (see Table 8). want to be.).

Note also that the 5% addition for wet strength does not significantly undermine the dry strength of the control.

[Example 11]
<Use of Esters Containing Less Than 8 Saturated Fatty Acids>
Some experiments were performed with sucrose esters produced with less than 8 fatty acids attached to the sucrose moiety. SP50, SP10, SP01 and F20W (Sisterna, The Netherlands) samples contained 50%, 10%, 1% and essentially 0% monoester, respectively. These commercial products are made by reacting sucrose with saturated fatty acids and are therefore not useful for further cross-linking or for similar chemistries but investigating emulsifying and water repellent properties. It was useful.

For example, 10 g of SP01 was mixed with 10 g of glyoxal in a 10% hot PvOH solution. The mixture was "heated" at 200° F. for 5 minutes and applied by draw down to a porous base paper made from bleached hardwood kraft. The result was a crosslinked wax-based coating on the surface of the paper that exhibited good hydrophobicity. When a minimum of 3 g/m ² was applied, the contact angle obtained was greater than 100°. Since glyoxal is a well-known crystallizer used in compounds with OH groups, this method allows the remaining alcohol groups on the sucrose rings to be combined with available alcohol groups on substrates or other coating materials. is a promising means of attaching fairly unreactive sucrose esters to surfaces.

[Example 12]
<HST data and moisture absorption>
To demonstrate that waterproof properties are observed with SEFOSE® alone, porous Twins River (Matawaska, ME) base paper was emulsified with varying amounts of SEFOSE® (and Treated with plastered PvOH or Ethylex 2025) and assayed with the Hercules size test. The results are shown in Table 9 below.

As shown in Table 9, increasing the amount of SEFOSE® applied to the surface of the paper increased the water resistance (as indicated by the increase in HST (in seconds)).

This can also be seen using a coating of saturated sucrose ester product. As a specific example, the product F20W (available from Sisterna, The Netherlands) is described as having very low % monoesters for most molecules in the 4-8 substitution range. Note that when equal parts of each F20W product was used with PvOH to make a stable emulsion, the F20W product add-on was only 50% of the total coating. Thus, if the wet pickup is labeled "0.5 g/m ² ", the same wet pickup of PvOH is also present, yielding a total wet pickup of 1.0 g/m ² . The results are shown in Table 10 below.

As shown in Table 10, increasing F20W increased the water resistance of the porous sheet. Thus, the applied sucrose fatty acid ester itself renders the paper water resistant.

Since water resistance is not simply due to the presence of fatty acids that form ester bonds with cellulose, softwood handsheets (bleached softwood kraft) are loaded with SEFOSE® to form ester bonds with cellulose in the pulp. oleic acid was added directly to the pulp. The weight at time 0 represents the "bone dry" weight of the handsheet removed from the oven at 105°C. Samples were placed in a humidity controlled chamber maintained at 50% RH. Record the change in mass over time (in minutes). The results are shown in Tables 11 and 12 below.

Note the difference here when oleic acid is added directly to the pulp to form ester bonds, which greatly slows moisture absorption. In contrast, as little as 2% SEFOSE® slows moisture absorption and at higher concentrations SEFOSE® does not. Therefore, without being bound by any theory, the structure of the SEFOSE® binder material cannot be explained solely by structures formed by simple fatty acid esters and cellulose.

[Example 13]
<Saturated SFAE>
A class of saturated esters are waxy solids at room temperature, and because they are saturated, they are less likely to react with the sample matrix or themselves. When used at elevated temperatures (eg, at least 40°C, all tested above 65°C), these materials can be melted and applied as liquids, then cooled and solidified to form a hydrophobic coating. Alternatively, these materials can be emulsified in solid form and applied as an aqueous coating to impart hydrophobic character.

The data presented here represent HST (Hercules size test) readings obtained from paper coated with varying amounts of saturated SFAE.

A #45 bleached hardwood kraft sheet obtained from Turner Falls paper was used for the test coatings. Gurley porosity is measured at about 300 seconds and represents a fairly compact basesheet. S-370 obtained from Mitsubishi Foods (Japan) was emulsified with xanthan gum (up to 1% by weight of saturated SFAE formulation) prior to coating.

Coat weight (pounds per ton) of saturated SFAE formulation HST (average of 4 determinations per sample).

The experimental data obtained also confirm that limited amounts of saturated SFAE can enhance the water resistance of coatings designed for other purposes/applications. For example, when saturated SFAE was blended with Ethylex starch and polyvinyl alcohol based coatings, an increase in water resistance was observed in both cases.

The following examples were coated on a #50 bleached lyscycle base with a Gurley porosity of 18 seconds.

100 grams of Ethylex 2025 was heated to 10% solids (1 liter volume) and 10 grams of S-370 was added hot and mixed using a Silverson homogenizer. The resulting coating was applied using a common benchtop drawdown device and the paper dried under a heat lamp.

At a coat weight of 300#/ton, starch alone had an average HST of 480 seconds. A mixture of starch and saturated SFAE at the same coat weight increased the HST to 710 seconds.

Sufficient polyvinyl alcohol (Selvol 205S) was dissolved in hot water to form a 10% solution. This solution was coated onto the same #50 paper as above and had an average HST of 225 at a coat weight of 150 lbs/ton. Using this same solution and adding S-370 contains 90% PVOH/10% S-370 on a dry basis (i.e. 90 ml water, 9 grams PvOH, 1 gram S-370) A mixture was formed. Mean HST increased to 380 seconds.

Saturated SFAEs are compatible with prolamines (specifically zein; see US Pat. No. 7,737,200, all of which is incorporated herein by reference). Since one of the major barriers to commercial production of the subject matter of said patent is that the formulation is water soluble, the addition of saturated SFAE helps in this manner.

[Example 14]
<other saturated SFAE>
A size press evaluation of the saturated SFAE-based coating was performed on bleached lightweight sheet (approximately 35#) with no sizing and relatively poorly formed. All evaluations were performed using Exceval HR 3010 PvOH that was heated and emulsified with saturated SFAE. Sufficient saturated SFAE was added to account for 20% of total solids. The focus was on evaluating S-370 versus C-1800 samples (available from Mitsubishi Foods, Japan). Both of these esters performed better than the controls. Some of the important data are shown in Table 14 below.

Note that the saturating compound appears to provide an increase in Kit, both S-370 and C-1800 increase HST by approximately 100%.

[Example 15]
<Wet strength additive>
Laboratory testing has shown that the chemistry of sucrose esters can be adjusted to achieve various properties, including use as a wet strength additive. When sucrose esters are made by attaching a saturated group to each alcohol functional group of sucrose (or other polyols), the result is a hydrophobic waxy substance with low miscibility/solubility in water. be. These compounds can be added to cellulosic materials to impart water resistance either internally or as a coating, but since they do not chemically react with each other or with any part of the sample matrix, the solvent , susceptible to removal by heat and pressure.

Where water resistance and higher levels of water resistance are desired, unsaturated sucrose esters are used to achieve oxidation and/or cross-linking that help anchor the sucrose esters in the matrix and make it highly resistant to removal by physical means. Sucrose esters containing functional groups may be made and added to cellulosic materials. Controlling the number and size of the unsaturated groups of the sucrose ester provides a means of cross-linking with molecules that are not optimal to impart water resistance but to impart strength.

The data presented here are generated by adding SEFOSE® to bleached kraft sheet at various levels and obtaining wet tensile data. The percentages shown in the table below represent the sucrose ester (%) of the treated 70# bleached paper (see Table 15).

The data show that the addition of unsaturated sucrose esters to paper tends to increase wet strength as loading levels increase. Dry tensile refers to the maximum strength of the sheet as a reference point.

[Example 16]
<Method for Producing Sucrose Ester Using Acid Chloride>
In addition to making hydrophobic sucrose esters via transesterification, similar hydrophobicity can be achieved in textile articles by directly reacting acid chlorides with polyols containing ring structures similar to sucrose. did it.

For example, 200 grams of palmitoyl chloride (CAS 112-67-4) was mixed with 50 grams of sucrose and mixed at room temperature. After mixing, the mixture was brought to 100° F. and held at that temperature overnight (ambient pressure). The resulting material was washed with acetone and deionized water to remove any unreacted or hydrophilic material. Analysis of the remaining material using C-13 NMR showed that a significant amount of hydrophobic sucrose esters had been made.

Although it has been shown (BT3 and others) that the addition of fatty acid chlorides to cellulosic materials can impart hydrophobicity, the reaction itself does not allow the released by-product gaseous HCl to corrode surrounding materials. It is not desirable on site because it poses several problems in the field and is detrimental to workers and the surrounding environment. One additional problem posed by the generation of hydrochloric acid is that the fiber composition weakens as more is formed, ie as more polyol sites react. Palmitoyl chloride was reacted with increasing amounts of cellulose and cotton material. As the hydrophobicity increased, the strength of the article decreased.

The above reaction was repeated several times using 200 grams of R-CO-chloride reacted with 50 grams each of other similar polyols, including corn starch, birch-derived xylan, carboxymethylcellulose, glucose and extracted hemicellulose. repeated times.

[Example 17]
<Peeling test>
The peel test utilized a wheel between the two jaws of a tensile tester to measure the force required to remove the tape from the paper surface as a repeatable angle (ASTM D1876; For example, 100 Series Modular Peel Tester, Test Resources, Shakopee, Minn.).

A bleached kraft paper with a high Gurley (600 seconds) from Turners Falls, Mass. was used for this work. This #50 lb sheet represents a fairly tight but very absorbent sheet.

When #50 lb paper was coated with 15% Ethylex starch as a control, the average force required (of 5 samples) was 0.55 lb/inch. When treated with the same coating except that 25% of the Ethylex starch was replaced with SEFOSE® (so 25% add-on is SEFOSE® and 75% is still Ethylex). , the average force was reduced to 0.081 lb/inch. Substituting SEFOSE® for 50% of Ethylex reduced the required force to less than 0.03 pounds per inch.

Preparation of this paper followed TAPPI standard method 404 for determining tensile strength of paper.

Finally, the same paper was used with S-370 at a load factor of 750 pounds per ton. This effectively fills all the pores of the sheet and creates a complete physical barrier. Certainly this passes the TAPPI kit 12 on a plane. This short experiment showed that it is possible to obtain grease resistance using a saturated SFAE variant.

[Example 18]
<Saturated SFAE and Inorganic Particles (Fillers)>
Saturated sucrose fatty acid esters (SFAEs) range from hydrophilic to hydrophobic depending on the number (and chain length) of fatty acid chains attached to the sucrose molecule. These are not considered highly reactive compounds.

Various substituted SFAEs with side chains 16 or 18 carbons in length have been investigated. The test material was a waxy solid with a melting point below 150°C. When coated on paper, highly substituted esters provide significant levels of water resistance depending on coat weight and sheet porosity. For this example, the same paper of S-370 was used at a load factor of 750 pounds per ton which effectively filled all the pores of the sheet and created a complete physical barrier. The paper thus treated was found to have TAPPI Kit 12. This short-term experiment showed that grease resistance can be obtained using saturated SFAE variants.

<Observation results>
The more hydrophobic esters tend to agglomerate in aqueous emulsions/dispersions, thus making uniform coating on paper difficult. The low melting point of some of these molecules results in the "melting" of the coating into the sheet. When blending hydrophobic SFAEs with polymers to help stabilize the dispersion, these polymers (i.e., latex, starch, polyvinyl alcohol) surround these esters to weaken the desired hydrophobic properties. tend to

Mixing with calcium carbonate (eg, precipitated calcium carbonate) has an unexpected appeal. SFAE does not dissolve into paper under the same drying conditions. Calcium carbonate appears to help disperse the SFAE and the adherence is such that the SFAE acts as a binder to adhere the calcium carbonate particles to the surface of the coated paper. While not wishing to be bound by any theory, it is believed that such uniform dispersion enhances water resistance for a given amount of ester.

Table 16 below shows water resistance as measured by the Hercules Size Test (HST) and increases with formulations containing 50% calcium carbonate. Porous 40 pound sheets that did not fit were coated by manual drawdown. The coating weight was 7-10 g/m ² .

Advantages of the combination that have been demonstrated include reduced coating costs through the use of carbonates, as well as more efficient use of SFAE molecules as they are more evenly distributed over the paper substrate surface.

[Example 17]
<Saturated SFAE Blends and Inorganic Particles (Fillers and Clays)>
A. This example was designed to study the interaction between saturated sucrose fatty acid ester blends and calcium carbonate.

10% PVOH; 20% sucrose ester (SE-15/1803 blend, equal ratio of SFAE; SE-15 is available from Hangzhou Union Biotechnology Co., Ltd, Hangzhou China; C-1803 is from Itochu Chemicals America, Inc.; A paper coating was made having a composition (dry weight basis) of 70% precipitated calcium carbonate (available from OMYA Inc., Blue Ash, OH). This mixture was applied to 65# bleached kraft sheet at a coating weight of 8 g/ ^m2 . Calcium carbonate slurry itself does not exhibit water contact angle and HST when coated on paper. The results using the coating composition are shown in Table 17 below.

In this example, the ester-carbonate interaction is important enough that it serves to illustrate that the carbonate helps to keep the ester evenly distributed on the surface of the sheet and observes the maximum effect. I was able to Further, the data demonstrated that a bio-based material that can be used with _CaCO3 was identified that resulted in coating sheets exhibiting high contact angles when _CaCO3 was present as a major component of the composition. Without wishing to be bound by any theory, this effect is more pronounced when heavy coating weights with high pigment composition may be applied.

B: This example was designed to study the interaction between saturated sucrose fatty acid esters and pigments (eg, clay).

Kaolin-based materials have very different properties than calcium carbonate. Table 18 lists another SFAE blend, 80OE (available from Tensac, Sh., Tucuman, Argentina) and SE-15 in equal amounts and 80OE, SE-15 and Imerys CAPIM™ ( The results of using equal amounts of a kaolin-based material (available from Imerys Clay, Inc., Roswell, Ga.) to produce an OGR coating are shown. The following formulations were prepared at 10% solids and coated at 5 g/ ^m2 .

In any barrier coating, when the pigment is present above 10-20% using CAPIM™ only, the paper does not show kit, and when the pigment concentration exceeds 10 or 20% as described above, , typically the barrier properties are significantly reduced (eg, grease can find pores to penetrate). An important observation is that esters provide excellent grease resistance with low net esters in the formulation.

<Other uses>
It was observed that the cup-based stock was heavily treated with rosin to increase water resistance. However, the Gurley of this paperboard was found to be 50 seconds, indicating a very porous paperboard. The material is repulpable and softens with rapid steam penetration. Neat SEFOSE® was applied to the paperboard and dried in an oven at 100° C. overnight. The resulting material had a plastic-like feel and was completely waterproof. It was 50% (wt/wt) cellulose/50% (wt/wt) SEFOSE® by weight. Gurley was too high to measure. When the samples were submerged in water for 7 days, the material did not soften significantly, but greenhouse data suggests that it biodegrades in approximately 150 days. Common tapes and glues will not adhere to this composite material.

Experiments with saturated SFAE and zein were performed because zein has been shown to provide grease resistance to paper. Stable aqueous dispersions of zein (up to 25% in water) with 2-5% saturated SFAE were produced. Observations demonstrated that the saturated SFAE "locks" the zein onto the paper by imparting water resistance to the formulation (in addition to grease resistance).

A combination of SFAE, inorganic particles and bioplastics may be blended to produce moldable paper for designing biodegradable coffee cup lids. The use of wood fibers, and sufficient bioplastic fibers (e.g., polybutylene succinate (Bio-PBS) or polylactic acid (PLA)) with SFAE can render the resulting paper base water-resistant, making the article It has been shown that when the SFAE concentration is optimized to ensure water resistance and when cheap and common materials such as standard pulp are used, the mass percentage of the lid is increased. Thus, articles with relatively low mass (e.g., less than 10%) can be of other materials, such as biopolymers, to provide flexibility, improve tear or stretch properties, etc. It is possible to add other additives that may be used in

Addition of the calcium carbonate/SFAE mixture allowed control of lid density.

Although the invention has been described with reference to the above examples, it will be understood that modifications and variations are encompassed within the spirit and scope of the invention. Accordingly, the invention is limited only by the following claims. All references disclosed herein are hereby incorporated by reference.

Claims (20)

1. A composition comprising one or more sugar fatty acid esters (SFAEs) and inorganic particles, wherein said SFAE is present in a concentration sufficient to adhere said inorganic particles to a cellulose-based substrate; exhibits superior water and/or grease resistance compared to substrates comprising the inorganic particles or the composition comprising only one or more SFAEs. Claim 1, wherein the SFAE comprises all unsaturated fatty acids, all saturated fatty acids, or a mixture of saturated and unsaturated fatty acids, optionally further comprising one or more binders selected from PvOH or starch. The composition according to . 2. The composition of claim 1, wherein said SFAE is a mixture of two or more different SFAEs, said two or more different SFAEs comprising all saturated fatty acids. wherein said inorganic particles are selected from the group consisting of clay, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof, said inorganic particles comprising at least 1% of said composition on a dry basis (db) The composition of claim 1, comprising: The composition of claim 1, wherein said SFAE comprises at least one sugar and at least one aliphatic group containing 8-30 carbons. 5. The composition of claim 4, wherein the inorganic particles are calcium carbonate and the substrate exhibits water resistance. 5. The composition of claim 4, wherein said inorganic particles are clays and said substrate exhibits grease resistance. The cellulose-based substrate is paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon paperboard, diapers, weed block/barrier fabrics Or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compostable bags, release paper, tableware , Hot or Cold Beverage Containers, Cups, Paper Towels, Plates, Carbonated Liquid Storage Bottles, Insulating Materials, Still Liquid Storage Bottles, Food Wrapping Films, Garbage Disposal Containers, Food Handling Tools, Cups lids, moldable paper cup lid screws, paper straws, fabric fibers, water storage and transportation equipment, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transportation equipment, casings, electronic products exterior screens, interior or exterior components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic 2. The composition of claim 1 selected from the group consisting of fibrous materials, and combinations thereof. An article of manufacture comprising a coating comprising one or more sugar fatty acid esters (SFAEs), inorganic particles, a cellulose-based substrate, and optionally one or more binders, wherein said inorganic particles are An article of manufacture present in said coating at a concentration of at least 1% on basis (db). The cellulose-based substrate is paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon paperboard, diapers, weed block/barrier fabrics Or film, mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compostable bags, release paper, tableware , Hot or Cold Beverage Containers, Cups, Paper Towels, Plates, Carbonated Liquid Storage Bottles, Insulating Materials, Still Liquid Storage Bottles, Food Wrapping Films, Garbage Disposal Containers, Food Handling Tools, Cups lids, moldable paper cup lid screws, paper straws, fabric fibers, water storage and transportation equipment, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transportation equipment, casings, electronic products exterior screens, interior or exterior components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic 10. The article of manufacture of claim 9 selected from the group consisting of fibrous materials, and combinations thereof. A method of treating a cellulosic substrate, comprising:
a) adding at least one sugar fatty acid ester (SFAE) to a composition comprising inorganic particles to form a mixture;
b) applying the mixture to at least one surface of the cellulosic substrate;
c) curing for sufficient time to adhere said mixture to said at least one surface;
A method, wherein the cured surface exhibits higher hydrophobicity and/or oleophobicity compared to a surface treated with a composition comprising only at least one SFAE or said inorganic particles. 12. The method of claim 11, wherein the treated cellulosic surface is hydrophobic. 12. The method of claim 11, wherein the treated cellulosic surface is oleophobic. 12. The method of claim 11, wherein said SFAE comprises all saturated fatty acids or a mixture of saturated and unsaturated fatty acids. 12. The method of claim 11, wherein said SFAE is a mixture of two or more different SFAEs. wherein the inorganic particles are selected from the group consisting of clays, ground calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, and combinations thereof, and wherein the inorganic particles are added at a concentration of at least about 1% on a dry basis (db); 12. The method of claim 11, present in said mixture. 17. The method of claim 16, wherein said composition further comprises polyvinyl alcohol or starch. 12. The method of claim 11, wherein said inorganic particles comprise calcium carbonate, said calcium carbonate comprising about 50% or more of said mixture on a dry basis (db). 17. The method of claim 16, wherein said calcium carbonate is precipitated calcium carbonate. The cellulosic substrate is used in paper, paperboard, paper pulp, food storage cartons, food storage bags, shipping bags, coffee or tea containers, tea bags, bacon paperboard, diapers, weed block/barrier fabrics or films , mulching film, plant pots, packing beads, bubble wrap, oil absorbent materials, laminates, envelopes, gift cards, credit cards, gloves, raincoats, OGR paper, shopping bags, compostable bags, release paper, tableware, hot or cold beverage containers, cups, paper towels, plates, carbonated liquid storage bottles, insulating materials, still liquid storage bottles, food wrap films, garbage disposal containers, food handling tools, cup lids , mouldable paper cup lid screws, paper straws, fabric fibers, water storage and transport devices, paperboard for pharmaceutical applications, release paper, alcoholic or non-alcoholic beverage storage and transport devices, casings, exteriors of electronic products Screens, internal or external components of furniture, curtains, upholstery, films, boxes, sheets, trays, pipes, conduits, pharmaceutical packaging, clothing, medical devices, contraceptives, camping equipment, formed cellulosic fiber materials , and combinations thereof.

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