Process for creating a foam utilizing an antimicrobial starch within a process for manufacturing a paper or board product

Abstract

The present invention relates to a new process for creating foam in a process for manufacturing a paper or board product. According to the present invention, certain types of antimicrobial starch is used in the creation of the foam.

Claims

1. A process for manufacturing a paper or board product, comprising the steps of a) providing an antimicrobial starch as a foam forming aid, wherein said starch has at least 1% by weight of a grafted polymer, said grafted polymer being an amino-containing polymer which has antimicrobial activity against E. coli and S. aureus of a minimum inhibitory concentration of 50 ppm or less; b) mixing the antimicrobial starch with water in the presence of air in an aqueous phase to obtain a foamed suspension; and, c) manufacturing a paper or board product with the foamed suspension obtained in step b) wherein an amount of antimicrobial starch in the foamed suspension is between 0.05 and 500 kg/ton of the paper or board product, and, wherein an amount of any additional foaming aid in the foamed suspension is less than 0.02 g/L.

2. The process according to claim 1, wherein the amino-containing polymer of the antimicrobial starch is a guanidine-based polymer.

3. The process according to claim 2, wherein the guanidine-based polymer is polyhexamethylene guanidine hydrochloride.

4. The process according to claim 1, wherein the foam is created in the absence of any additional foaming aid.

5. The process according to claim 1, wherein the foam is created in the presence of a foam stabilizer.

6. The process according to claim 1, comprising the addition of microfibrillated cellulose in the creation of the foam.

7. The process according to claim 1, wherein at least step b) is carried out in a wet end of a process for manufacturing a paper or board product.

8. The process according to claim 1, wherein the amount of antimicrobial starch in the foamed suspension is between 1 and 25 kg/ton of the paper or board product.

Description

DETAILED DESCRIPTION

(1) In one embodiment of the present invention, the process is carried out in a paper or board machine or in equipment arranged near or connected to a paper machine. The process can also be a wet laid technique or modified method thereof. The generated foam could also be deposited with a surface treatment unit or impregnation unit such as film press, size press, blade coating, curtain coating, spray, or a foam coating applicator/coater.

(2) In one embodiment of the present invention, the process is carried out in the wet end of a process for manufacturing a paper or board product.

(3) In one embodiment of the present invention, in foam coating, the amount of antimicrobial starch used is at least 0.25 g/m.sup.2.

(4) In one embodiment of the present invention, in foam forming, the amount of antimicrobial starch used is at least 0.05 kg/ton paper or board product, such as 0.05 to 500 kg/ton or 1 to 50 kg/ton or 1 to 25 kg/ton or 5 to 15 kg/ton paper or board product.

(5) The air content in step b) is typically in the range of from 30% to 70% by volume, such as in the range of from 35% to 65% by volume.

(6) The foam created in accordance with the present invention prevents fiber flocculation, thus giving improved formation. The foam generally disappears in/on the wire section as the solids increase and water is sucked from the web with vacuum or pressure or centrifugal forces. The foam helps create higher solids content from the wire section as well as increased bulk of the end product. The foam is also beneficial to enhance the mixing of long fibers.

(7) The foam obtained according to the present invention has a sufficiently even bubble size, i.e. the size distribution of the bubbles is narrow. The foam obtained according to the present invention is also controllable, i.e. when the amount of air is increased or decreased the bubbles remain of an even size, i.e. a narrow bubble size distribution is maintained. The foam obtained according to the present invention is also sufficiently stable, i.e. the foam is maintained for a sufficient period of time. These parameters, i.e. bubble size and foam stability, can be determined using methods known in the art.

(8) Sodium dodecyl sulphate (SDS) is typically required as a foaming aid. However, it generally causes problems when used in a paper or board machine. It typically prevents fiber-fiber bondings, thus causing weaker strength properties of the material produced. In addition, from a process efficiency point of view, the SDS ends up in the water and causes problems i.e. in the waste water treatment plant. However, by the use of certain types of modified starch as defined above in step a), the use of SDS can be avoided or significantly reduced. When antimicrobial starch is used in accordance with the present invention, a synergistic effect of the addition of tenside or surface active polymer can be observed on the strength and evenness of the foam. In one embodiment, the amount of tenside used is less than 0.2 g/l in the furnish, preferably less than 0.1 g/l or less than 0.05 g/l or less than 0.02 g/l. In one embodiment of the present invention, no tenside is used.

(9) In one embodiment of the present invention, the antimicrobial starch can be used in combination with other agents useful to create and/or stabilize foam, such as PVA, proteins (such as casein) and/or hydrophobic sizes. The foam may also contain other components such as natural fibers, such as cellulose fibers or microfibrillated cellulose (MFC).

(10) In one embodiment of the present invention, the foam is used in a foam coating process.

(11) In a foam coating process, the created foam prevents coating color or surface size starch penetration into the structure of the paper or board being manufactured. More specifically, air bubbles in the foam prevent penetration of the coating color or surface sizing starch into the structure of the paper or board being produced. By use of the foam, the surface produced becomes less porous, thereby having improved optical properties or improved physical properties for printing. The foam also makes it possible to increase the solid content. In addition to improve the optical or physical performance of the coated substrate, the said foam coating can be used to make dispersion coating in order to provide barrier properties, such as in the manufacture of grease resistance paper which may optionally contain MFC.

(12) In one embodiment of the present invention, a foam generator is used to create the foam. In one embodiment of the present invention, the created foam is dosed to a size press. The foam coating may be carried out in the wet end of a papermachine, as a curtain coating of the wet-web. One benefit of using foam coating is this context is that with the use of foam, the solids have an improved tendency to stay on the surface of the base web.

(13) The foam obtained according to the present invention can also be used in cast coating or blade coating.

(14) In one embodiment of the present invention, high-pressure air is used when creating the foam.

(15) The antimicrobial starch used in accordance with the present invention can be prepared as described in US2014/0303322 A1. The minimum inhibitory concentration can be determined using methods known in the art.

(16) The antimicrobial starch is prepared by grafting a reactive amino-containing polymer (ACP) onto starch using ceric ammonium nitrate [Ce(NH.sub.4).sub.2(NO.sub.3).sub.6] as an initiator in the graft copolymerization. A person of ordinary skill in the art would understand that other initiators could be used, such as potassium persulfate or ammonium persulfate. In one embodiment, the amino-containing polymer is a guanidine-based polymer. In one embodiment, the amino-containing polymer is polyhexamethylene guanidine hydrochloride. In one embodiment, a coupling agent is added when preparing the antimicrobial starch. In one embodiment, the coupling agent is selected from the group consisting of glycerol diglycidyl ether and epichlorohydrin.

(17) The foam may also contain pulp prepared using methods known in the art. Examples of such pulp include Kraft pulp, mechanical, chemical and/or thermomechanical pulps, dissolving pulp, TMP or CTMP, PGW etc. In one embodiment of the present invention, microfibrillated cellulose is used for stabilization of the foam created in accordance with the present invention.

(18) The foam according to the present invention may also contain microcrystalline cellulose and/or nanocrystalline cellulose.

(19) The foam and and/or the paper or board product manufactured may also comprise other bioactive agents, such as other antimicrobial agents or chemicals, such as antimicrobial agents that are approved for direct or indirect contact with food.

(20) Microfibrillated cellulose (MFC) shall in the context of the patent application mean a nano scale cellulose particle fiber or fibril with at least one dimension less than 100 nm. MFC comprises partly or totally fibrillated cellulose or lignocellulose fibers. The liberated fibrils have a diameter less than 100 nm, whereas the actual fibril diameter or particle size distribution and/or aspect ratio (length/width) depends on the source and the manufacturing methods.

(21) The smallest fibril is called elementary fibril and has a diameter of approximately 2-4 nm (see e.g. Chinga-Carrasco, G., Cellulose fibres, nanofibrils and microfibrils,: The morphological sequence of MFC components from a plant physiology and fibre technology point of view, Nanoscale research letters 2011, 6:417), while it is common that the aggregated form of the elementary fibrils, also defined as microfibril (Fengel, D., Ultrastructural behavior of cell wall polysaccharides, Tappi J., March 1970, Vol 53, No. 3.), is the main product that is obtained when making MFC e.g. by using an extended refining process or pressure-drop disintegration process. Depending on the source and the manufacturing process, the length of the fibrils can vary from around 1 to more than 10 micrometers. A coarse MFC grade might contain a substantial fraction of fibrillated fibers, i.e. protruding fibrils from the tracheid (cellulose fiber), and with a certain amount of fibrils liberated from the tracheid (cellulose fiber).

(22) There are different acronyms for MFC such as cellulose microfibrils, fibrillated cellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulose fibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers, cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulose microfibril aggregates. MFC can also be characterized by various physical or physical-chemical properties such as large surface area or its ability to form a gel-like material at low solids (1-5 wt %) when dispersed in water. The cellulose fiber is preferably fibrillated to such an extent that the final specific surface area of the formed MFC is from about 1 to about 300 m.sup.2/g, such as from 1 to 200 m.sup.2/g or more preferably 50-200 m.sup.2/g when determined for a freeze-dried material with the BET method.

(23) Various methods exist to make MFC, such as single or multiple pass refining, pre-hydrolysis followed by refining or high shear disintegration or liberation of fibrils. One or several pre-treatment step is usually required in order to make MFC manufacturing both energy efficient and sustainable. The cellulose fibers of the pulp to be supplied may thus be pre-treated enzymatically or chemically, for example to reduce the quantity of hemicellulose or lignin. The cellulose fibers may be chemically modified before fibrillation, wherein the cellulose molecules contain functional groups other (or more) than found in the original cellulose. Such groups include, among others, carboxymethyl (CM), aldehyde and/or carboxyl groups (cellulose obtained by N-oxyl mediated oxydation, for example “TEMPO”), or quaternary ammonium (cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC or nanofibrillar size fibrils.

(24) The nanofibrillar cellulose may contain some hemicelluloses; the amount is dependent on the plant source. Mechanical disintegration of the pre-treated fibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer. Depending on the MFC manufacturing method, the product might also contain fines, or nanocrystalline cellulose or e.g. other chemicals present in wood fibers or in papermaking process. The product might also contain various amounts of micron size fiber particles that have not been efficiently fibrillated. MFC is produced from wood cellulose fibers, both from hardwood or softwood fibers. It can also be made from microbial sources, agricultural fibers such as wheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. It is preferably made from pulp including pulp from virgin fiber, e.g. mechanical, chemical and/or thermomechanical pulps. It can also be made from broke or recycled paper.

(25) The above described definition of MFC includes, but is not limited to, the new proposed TAPPI standard W13021 on cellulose nanofibril (CMF) defining a cellulose nanofiber material containing multiple elementary fibrils with both crystalline and amorphous regions.

EXAMPLES

Example 1. Foam Coating in Size Press

(26) Trials were conducted on a pilot paper machine. The production rate on pilot paper machine was 45 m/min and grammage of the base board 130 g/m.sup.2. In addition to CTMP pulp, cationic starch (6.0 kg/tn), alkyl succinic anhydride, ASA, (700 g/tn), alum (600 g/t), and two component retention system (100 g/tn cationic polyacryl amide, and 300 g/tn silica) were used in the furnish. The paper web was on-line surface sized with starch (Raisamyl 21221) or antimicrobial starch on a size press unit. The surface size uptake was 0.64 g/m.sup.2 and 0.95 g/m.sup.2 for the Raisamyl 21221 and antimicrobial starch, respectively. The paper was dried to 8% end moisture content, reeled and cut into sheets.

(27) As a reference sample, size press starch Raisamyl 21221, in solids 5% was used. In the reference sample, no foamed starch and no tensides were used. The surface energy (2 liquid method) top side was determined and was found to be 24.4 mJ/m.sup.2. When PE coated, it was found that the PE adhesion was very good, the plastic was totally bound and the fibers were splitting when PE was torn away.

(28) As a test sample, size press antimicrobial starch, solids 5% was used. The antimicrobial starch was foamed in the absence of tensides. The surface energy (2 liquid method) top side was determined and was found to be 24.3 mJ/m.sup.2. When PE coated, it was found that the PE adhesion was very good, the plastic was totally bound and the fibers were splitting when PE was torn away.

Example 2. Foaming

(29) The foaming tendency of antimicrobial starch was compared to traditional cationic wet-end starch (Raisamyl 50021). Both starches were cooked and diluted to 1% consistency, then mixed with a mixer with 6000 rpm propeller speed for 15 minutes. Amount of sample in the mixing was 300 ml.

(30) For antimicrobial starch the stability of the foam phase was studied as the content of foam turned into water as a function time. For this measurement 100 ml of foam was taken to a beaker and the content of the water phase was measured after several time intervals. Results for 3 parallel mixing batches of antimicrobial starch (ANTIMIC) and 1 mixing batch of traditional cationic wet-end starch (REF) are presented in Table 1.

(31) TABLE-US-00001 TABLE 1 CONTENT (ML) OF FOAM TURNED INTO WATER AS A FUNCTION TIME. Content of foam turned into water, Foam ml from 100 ml density 5 10 20 30 40 50 60 kg/m3 min min min min min min min ANTIMIC 1 202 11 16 18 20 20 20 20 ANTIMIC 2 285 25 27 28 28 28 29 29 ANTIMIC 3 240 18 21 22 23 23 23 23 REF No foam

(32) Furthermore, the antimicrobial starch and traditional cationic wet-end starch were compared as a foaming agent of chemi-thermomechanical pulp (CTMP). Consistency of CTMP slurry was 1.0%. Slurry was mixed with a mixer with 6000 rpm propeller speed for 15 minutes. Amount of sample in the mixing was 300 ml.

(33) For antimicrobial starch+CTMP the stability of the foam phase was studied as the content of foam turned into water as a function time. For this measurement 100 ml of foam was taken to a beaker and the content of the water phase was measured. Results for antimicrobial starch (ANTIMIC) and traditional cationic wet-end starch (REF) are presented in Table 2.

(34) TABLE-US-00002 TABLE 2 CONTENT (ML) OF FOAM TURNED INTO WATER AS A FUNCTION TIME. Content of foam turned into water, ml from 100 ml Density, 5 10 20 30 40 50 60 kg/m3 min min min min min min min ANTIMIC 337 11 16 18 20 20 20 20 REF No foam

(35) In view of the above detailed description of the present invention, other modifications and variations will become apparent to those skilled in the art. However, it should be apparent that such other modifications and variations may be effected without departing from the spirit and scope of the invention.