CA2042560C - Paper composition and uses therefor - Google Patents
Paper composition and uses therefor Download PDFInfo
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- CA2042560C CA2042560C CA002042560A CA2042560A CA2042560C CA 2042560 C CA2042560 C CA 2042560C CA 002042560 A CA002042560 A CA 002042560A CA 2042560 A CA2042560 A CA 2042560A CA 2042560 C CA2042560 C CA 2042560C
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
- D21H5/14—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of cellulose fibres only
- D21H5/141—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of cellulose fibres only of fibrous cellulose derivatives
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/005—Microorganisms or enzymes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Paper (AREA)
- Pens And Brushes (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
A mixture of polymers derived from degradation of a polysaccharide derivative is used during the paper-making process as a means of strengthening the paper and as a dewatering agent.
Paper is either coated or impregnated with a mixture of the polymers.
Paper is either coated or impregnated with a mixture of the polymers.
Description
FIELD OF THE INVENTION
This invention pertains to the field of paper.
pulp and textile making and their chemistry.
BACKGROUND OF THE INVENTION
Of the many raw materials used by the paper industry, cellulose fibers have occupied the dominant position for nearly 2000 years. The techniques of paper, making are known worldwide and the basic principles have not changed. Despite great improvements in papermaking, however, procedures fo: strengthening cellulose fibers in the papermaking process are often e:cpensive, time consuming, and environmentally questionable.
204~~6~
The kraft or sulfate process is probably the most extensively employed method to produce strong cellulose fibers. The active ingredients in pulping wood to its fibrous state axe sodium hydroxide and sodium sulfide, in a strong alkaline solution. The process generates objectionable smells from the sodium sult:ide produced during the process. Kraft pulps are dark in color, difficult to bleach and very strong.
Nevertheless, cellulose fibers obtained from the pulping process are generally unsuited for paper making and muss first be refined. With given pulps, final,paper properties are largely controlled by the type and extent of refining action employed. r1 variety of additive materials can be introduced to the paper-making pulps, commonly called "furnish", during stock preparation. Fillers such as clays, or calcium carbonate are used for the control of sheet opacity and for other reasons. Dyes are used extensively for color control and other additives such as wet-strength agents, and defoamers are used as needed.
For the most part. however, operations designed to inerea-e tlae strength and/or other physical properties of paper take place subsequent to the paper making operation and are called "off-machine converting." These converting operations are highly complex and include embossing, coating, waxing, laminating, Impregnating, saturating, currogating, and printing. For example, food packaging has led to extensive paper utilization with the paper often being coated, waxed, resin-impregnated, or combined with other fcils and films. ~ relatively simple and inexpensive method of improving the paper making process and increasing the stiffness and ultimate strength of paper is needed.
SUMMARY OF T4E INVy'NTIQN
It is an object of the invention to provide materials that improve the properties of paper, pulp and textile products.
It is a further object of the invention to provide a simplified paper-making process by improving the dewatering and draining properties of paper pulp, It is yet another object of the present invention to provide degradation.products of polysaccharide derivatives which are useful as strengthening and dewatering agents for treating paper products or materials.
The invention discloses the manufacture of novel paper materials comprising treating paper wi;,h water soluble or water suspendable mixtures of relative:y low molecular weight polymers. The poly~r.ers are obtained by degrading polysaccharide derivatives, most preferably starch and cellulose derivatives.
The invention further pertains to a paper product treated with a composition comprising a mixture of polymers derived from degradation of a cellulose derivative, the derivative comprising one or more substituents, said mixture of polymers having an average degree of polymerization in the range of about 5 to about 500, and wherein a majority of the polymers has a degree of polymerization and molecular weight such that the polymer conforms to a rod-like configuration.
In accordance with the invention, there is provided a water soluble or water dispersable mixture of polymers derived from a degraded polysaccharide derivative, the mixture of polymers having an average degree of polymerization in the range of about 5 to about 500. The most preferred polysaccharide derivative comprises starch or cellulose. The polysaccharide derivative may be degraded by enzymatic, chemical, physical, or mechanical agents/mechanisms. In embodiments where an enzyme preparation is utilized to perform the degradation, the enzyme preparation is typically selected from the group of polysaccharide degrading enzymes. In the case of starch derivatives, enzymes such as amylases or pullulanases and mixtures thereof are suitable.
In embodiments where degradation of a polysaccharide derivative is to be effected by chemical or physical means, chemical hydrolysis, chemical oxidation and heat treatment are preferred mechanisms for achieving ~he desired polymeric mixtures according to the invention.
By conventional means, a polymer or an initially degraded polysacchride derivative mixture may be further separated into fractions of polymers of differing average chain lengths, e.g. using chromatographic techniques. The viscosity of the various fractions will vary with the degree of average chain length of the polymers contained within in a fraction. Depending on the particular paper product application, one or more fractions are selected from an initial polymeric mixture having a viscosity (average chain length) which is most appropriate for the particular application.
There is provided a method of increasing the strength of paper, comprising treating the paper with a mixture of polymers derived from a substituted cellulose derivative, said mixture having an average degree of polymerization in the range of about 5 to about 500.
The method of enhancing the dewatering properties of paper pulp comprises treating the pulp with a water soluble or water dispersable mixture of relatively low molecular weight polymers, which polymers are obtained by degrading polysaccharide derivatives, most preferably starch and cellulose.
There is also provided a method of paper manufacture having the steps of:
(a) pulping the fibers;
(b) refining the paper stock;
(c) forming the paper sheet; and (d) drying the paper sheet, wherein the improvement comprises the step of:
treating the paper with a mixture of polymers derived from a cellulose derivative, the derivative comprising one H
or more substituEmt:~, sa:iay riiyt~..ire ~~~~~..~~.~;c° an average degree of polymarirati.on cJ:' af;~cuz~. t:~o :zho at. '~Cn:), a,~.nd wl~arain a majority of tree x>c~~.~~~cners n,_~s ,:z s:lc~ 7i:~:~E ~ a ~:~u Lyrr;er~_z,:~~ i<>n and molecular weight saa,.:h t~:~~t ~.r~e ~~-.;.1..~,,m:,.r~ ~:~o;forms to a rcd-like configuration.
i f, ~~3~~ ~~~
_,_ BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a force-distance curve of Whatman No. 1 filter paper treated with carboxylmethyl cellulose hydrolyzate.
Figute 2 is a force-distance curve of Whatman No. 1 filter paper dipped in distilled water.
Figute 3 is a force-distance curve of untreated 'Ahatman No. 1 filter paper.
figure 4 shows results of drainage tests on furnish treated with carboxymethyl cellulose (CMC) hydrolyzate (~), carboxymethyl cellulose (o), carboxymethyl starch (CM starch) hydrolyzate (D), carboxymethyl starch (CM starch) (,1), and untreated furnish (O).
Figure 5 shows results of drainage tests on furnish/calcium carbonate mixtures treated with carboxymethyl cellulose (C?tC) hydrolyzate (.), carbo~.ymethyl cellulose (o), carboxyn,ethyl starch (CM starch) hydrolyzate (p), and carboxymethyl starch (CM starch) (p), -DETAILc.D DESCRIP:ION OF THE I.WENT_IO_N
:his invention describes paper materials trea:ed with the c:egradation product of a polysaccharide derivative and :r,ethods therefor. ~,'he term "polysaccharide' refers to a polymeric carbohydra~e having a plurality of repeating units comprised of ~d~42a~~
simple sugars. The term "polymeric" or "polymer" is meant to include both oligmeric and polymeric units and, specifically, those polysaccharides having more than four repeating monomeric simple sugar units.
The C-O-C linkage formed between two joined simple sugar units in a polysaccharide chain is called a glycosidic linkage, and continued condensation of monosaccharide units will result in polysaccharides. The most common polysaccharides are amylase and cellulose, both made up of glucose monomers. ~mylose is a major constituent of starch and glycogen. Cellulose is the major structural component of plants. Other polysaccharides useful in this invention have a straight chain or branched polymer backbone including one or more sugar monomers. These polysaccharides include those having sugar monomers such as glucose, galactose.
arabinose, mannose. Fructose, rahmnose, and xylose.
Preferred polysaccharides useful in the article and methods of this invention are cellulose and starch. Nevertheless, examples of other such polysaccharides with branched or straight backLones are carragenan, pullulan. pustulan, laminarin.
sclercglucan, alginate, guar gum, gum arabic, inulin, pectin, whelan, rhamsan, gellan, :canthan, zooglan, met:~ylan, chitin, cyclodextrin and chitosan, The term "derivative" is meant to define ~~4~
_ g _ polysaccharides according to this invention that are substituted. Preferably, the polysaccharide derivative starting material has a degree of derivatization or substitution of between about 0.1 and about 3Ø "Degree of substitution" refers to the number of derivative groups (e. g. carboxymethyl, hydroxypropyl) per monomer unit in the polysaccharide backbons (branch or straight chain backbone). A degree of substitution of 0.2 means, for example that there is about one derivative substituent for every Eive monomer,units in the polysaccharide backbone. ~ degree of substitution of three would mean there are three derivative substituents per every monomer unit in a polysaccharide chain. Typical substituents comprise one or more of sulfate, carboxylic acid (found in carragenan, alginate, pectin), carboxylic ester, pyruvic acid .(found in pectin, xanthan gum, zooglan, and methylan), carboxymethyl, hydroxypropyl, methyl, methylethyl, hydroxyethyl, hydroxyethylmethyl and the like.
Specifically, carboxymethyl starch can be degraded enzymatically to produce correspondii:g carboxymethyl starch hydrolyzates. Ot'~er typical suitable starch derivatives include hydroxypropyl, methylethyl and hydroxyethyl starct:es. :he substituents are typically bonded to a starch 1 ::~
glucose monomer un.. t ,~t, t.h~~ ?, 3 a~~d 6 posit.i.or:,s. Most typically a starcl-: startirr.g materi...;1 ~.~~~;rnpr.ises between about 1~ to 85-'amyl~:~se and <ab~asr:t 1~~'. t~:7 '~~~" amyl_opE-ct.in.
Cellulose der.i~~.:~ti°;re~~ ar~F: c-ommerv~~a.l~,~ a~;railab.ie.
Sucr exemplary products as metriui.c.~~l:Lul,.ac= ,;MC,Methocel* MC.', 64630, I-'luka C~erro~e AG, ..-~~:i'7i.::=~c~-r>, Swi.t~~~rland) , hydroxypropylmetr~nylc~allulc-se ~,~-'fMc';, C-___c~ ~t>~ , S;_gmG Chem.
Co. , St. Louis, M01 and c:~arl::».~ycne:t:C-i.~, 1. ~~~e L~u_i.o::,e (CPfIC
~MF'L?, BlanOSa*, HarC~ll~:~~~ yrle'r"1. l~f'~, , '~~_, ~''>~.~~/ rxl2E~l. ~.-M~~1'rr'Lal;iGn C:adar, Frances all have a ~lef~.~ ~-~E: <af: w ~>:r: i ~.~t:i..c:~r~ k:>etween 0. 1.
and 3. Hydroxypropyl ce:, lu:Lc,t;e:~~ Ar.e K_ L ~,~~~ ,:c_>,znr~i:~~ c::;i<~ l.ly a~~~ai.l.abl.e anc:~ suitable for use~~.
As descri.bec~ nn:pre f~~_ril.~~ )... ~t..E,ir~, s ac~r~ p;olysac:~charide derivatives may k:~w decCradc~d tc~ ;~c:.~i yrrw ~ z. ~. mi;~t.u:res of average degree o.f_ pc~lymc~rizt~t ion ;I'~F! L~~:tween abou-t. 5 and about 500 by en:~~~rn::3ti.c-, <:h~:,rr,icv=x_~, ~.sl,~;»3~~r3 cr mec:hanical agents,~means . The pc: i_yme r ic.~ cra :~;tu t:e:a <r-~ ~~:rwrs:~ll.y :referred to as a ~~hydrolyzate". ~'he t:.errn "dectrade~." refers to the procedure whereby y:olysa~~cha.~:z~:~<~ ~1<e:.i~a-:.tines are broken down into smaller oc.i vrn~ ric: l.:n;i_ts .
Exem~:.lary en<:y:n:es _e:.L a.~c. i.r._ cy ac,~:i.ng ~_~ert.ain of the above de;~:::ribed ~,~; y.,,ac ..,i.lax ~_c:lt: dez:uvatives * trademarks are pectinases, lyases, lysozymes, xanthanases.
chitinases and laminarases. Exemplary enzymes which are suitable for degrading cellulose derivatives are various cellulases. They can be produced from a multitude of different microorganisms such as strains of Trichoderma. Asperqillus, Penicillium.
etc. A selected microorganism strain is gro=.m by conventional means in a suitable medium such that the cellulases are produced, the microorganism is separated from the medium, the medium is collected and typically concentrated and dried. Cellulase preparations suitable Eor use herein are, e.g. the commercially available cellulase preparations designated as the Econase series as produced by Alko Ltd., Helsinki, Finland.
A polysaccharide derivative mad be hydrolyzed by treating a polysaccharide derivative with a solution of acid. ~Pypical acid treatment solutions might contain acids such as sulphuric acid, hydrochloric acid, phosphoric acid, or mixtures of the foregoing. The concentration of the acid in the treatment solution and the treatment time and temperature may vary depending on the degree of dagradation of the polysaccharide derivative which is desired. In any event where an acid hydro:hsis treatment is u~ilized, the acid concentration and the treatment time and temperature is selected to ~(~~~~~~
produce a mixture of polymers having an average pp of between S-5oo.
A selected polysaccharide (e.g, starch or cellulose) derivative may be degraded by oxidation with such a,ients as chlorine,t~oxygen or hydrogen peroxide. Such oxidative treatments and reaction conditions are well known in the art. It may also be possible to use physical methods like heat or mechanical shear treatment or sonication when cleaving the chain backbone of polysaccharide derivatives.
Whatever conventional chemical ('hydrolytic, oxidative or otherwise) or physical treatments are employed, the conditions and the degree o~ treatment are selected such that the poly",eric mixture resulting from the initial treatment has an aveCage Dp of between about 5 and about 500.
Enzymes which may be Used with res pect to paper products prepared or coated with degraded starch derivatives, are various amylolytic enzyme preparations. They can be produced from a multitude of different microorganisms such as strains of Bacillus, K~Siella, Clostridium, ~illus, ----------_ as oe r RSizo us. Typical commercially -available enzyme preparations suitable for use herein are amylolytic preparations (such as alpha and beta amylases), pulluianases; and cyclodextrin glycosyltransEer ses ~~~~r~~~
(CGTase).
The polymers described above are used in the method of the invention to improve the properties of paper products and to strengthen paper produc t . In its broadest embodiment, the method comprises preparing a polymeric mixture of substituted polysaccharides having an average degree of po~ymerization (DP) in the range of 5-500. Next.
the mixture is then contacted with paper for a period of time sufficient to treat the paper with the polymer mixture.
This invention relates more specifically to a paper or paper product treated with water soluble or dispensable mixture of polymers derived from a polysaccharide derivative. The polymeric mixtures are characterized by having an average degree of polymerization (DP) in the range of about 5-500.
Preferably, the DP range is between 7-200.
The terms "paper" and "pulp products" are intended to include a variety of products made from cellulose, synthetic or other fibers, such p:oducts being recognized by those skilled in the art as paper, boards, construction paper, in addition, these terms refer to ar;.icles prepared frcm cellulose, synthetic, or other fibers or filamenatous materials such as those used in the textile industry. Specific examples include :eited or matted sheets of cellulose Fibers, fcrmed on a Fine wire sc:een from a dilute water suspension, and bonded together as the water is removed ar:d the sheet is dried. These terms may also include sheet materials produced from other types of fibers, particularly mineral or synthetic'fibers, formed and bonded by other means. These terms also include liquified or semi-solid mixtures of pulped fibers, commonly called "furnish", to which i,s added various materials such as fillers (clays, calcium carbonate), dyes, wet-strength agents and the like during the typical paper-making process.
Methods of paper manufacture include the basic steps of pulping fibers. refining the pulp by addition of various materials, as described below.
forming the paper on mesh screens, and drying the matted fibers.
The polymer mixtures can be applied after the paper is made, in the so-called "off-machine converting" procedures. The mixtures can be applied using methods well known in the art suet. as dipping, spraying, and rolling.
Not wishing to be bound by any theory, it is believed that the polysaccharide derivative mixture thus prepared coats the surface of the paper and becomes fixed thereon by attraction between the polysaccharide mixture and ~he polysaccharide .
components o: the paper including by physical :orces such as hydrogen binding, Van der Waals Forces and the like. The low molecular weight Folyzners cf the invention are aligned along the cellulose, or other fibers. As a result, the intermolecular attraction per unit length increases, facilitating the quality of the final product and improving the p:ocessability of the paper or pulp product.
The polymeric mixtures can also be incorporated into the papar furnish during pulp refining procedures. In this embodiment, the mixture of degraded polysaccharides can be incorporated into the pulp furnish along with other dyes, colorants.
wet-strength agents (agents capable of increasing the strength of wet or suspended materials), defoamers, and the like. In this procedure, the polysaccharides will become impregnated into the matri:c of the paper fibers, The term "treated" or "treatment" are intended to include means or methods for contacting paper products with the polymeric mixtures so that at least one effect of such contact is to strengthen the paper, coat or impregnate the paper, improve the paper or pulp handling properties during manufacturing, improve the paper or pulp handling properties during manufacture, and/or increase the dewatering capacity of the paper pulp. Examples cf a methods of treatment include the two methods of inr.roducing the polymer derivatives of the invention to the paper or paper products,described above.
Paper produced according to the method of this invention may be stronger than non-treated papec.
rloreover, treated paper may less water spreading than untreated paper. Furnish treated with the polymers of the invention show an increased rate of dewatering during the early stages of draining.
This invention will now be more particularly described using the following examples.
Example 1: Pretiaration of a S
Nydrolyzate . -------- tarc=rec=
Starch derivative hydrolyzates may be prepared from starch derivatives as defined above.by an enzymatic hydrolysis utilizing an amylolytic preparation having a-amylase as the main active hydrolytic agent such that only insignificant amounts of mono- arid disaccharides are produced.
The hydrolysis procedure is generally carried out by dissolving the starch derivative in water, adjusting the pft and the temperature to tt:e value suitable for the enzyme activity, adding the enzyme to the solution and allowing the enzyme to react for a suitable time. After the enzyme reaction, enzyme is inac~ivated by heating the solution up to about loo°C and the hydrolyzate product is concentrated and dried. The average degree of poly;r,erization (DP) of the products formed by such a ~. f l hydrolysis is less tharu ':~00 as ~_~eter:r'i.na:a by the reducing end group measureme.,..it, ~c..cc'rd.i.ry t<::- ;~~on,~>~~~~%i, M. ~~. Bial.
Chem. 19'J, 19-33, ( : 9'.p:~. . '~r:e s peci.i.i c: c ondit.ions :_aui table for and the spec:.fic t.in;c-~ :~m~ticient to sec~.~re the desirab:Le hydrolysis-: may bc:~ ra~ac:.i.l. ~ '.:letr=rrniried f~::or each selected s parch aF~rz~r at :i.v~> «nd ~:=-'~h se_iected enzyme preparation.
Similarly, what~a c~ar~r ~.l~ti-~;rv; i ' a~rr.ia:~ o~.zt:: l.rsing chemical or physical meain~., .Lv~!:: ~c~ ~x-~~~1~.,: I >' a~;:f. ~:he~
c:o.l.icTomer~s is less than 500.
60 g of= carbox.,~methy~L =~i,:;~:rt:::kz (C"1~1 :>t,irvc~hu; deri_~red. from potato starch (F.rimojel ~; ~-lve~r~E:, ~~~;0! ~>',T' FoxTuc>l, The Netherlands) was mi~~'::;d il~ 12i)~:~ rr::l. ~~:~ uaat'.er. Tne ter~~tlerature of the mixture was raisec::i t..o ~a~>''C: :3ri'~.i t rve suspens ion was mixed cont.inuous:iy. About 1.. '~: m1 ~~f arr;y_Ta:,e (l3an* 120h, Novo, Industri A!S, Nova ??~ lc~, ~8~~:~ Bags>vaerd, t:?enmark) diluted 1i50 by volu:rne was a,adecx t:o f.t:e si.x~,pension rrx.ixt.ure.
After, hydrolysis c_w.f= ahout ~i~ m:i r...~ t:es r.~ie ersz~;~me was inactivated by he~~ti..ng ;:i..;n0''C, l_ia ro':ii~.. '.1'l:e huvci~:olyzate waa then Breeze-dri..e'::k.
Tha hydrc:>lyzat i~' s vra 1 ~aF: c:~f e::cTUCi. cug s~.zgar_ s was 0.:'T3o. Tha v_i.scot;a;:y c:_~f a ~,:°a! i~~y ~ra.:.lic.;~ht~
susp~~n~:;-ion of the hydrolyzate, :r~easu:r°E~ra .~,~.i.r~ng E-Taake--Rc:~toviscc RV 12 viscometer w~~itf's. seru:ac.:.t~ sy:.~i_c~~rns T~~J; iF~Ca~ lsruhe, "..G . ~7 Federal Republic: ~f Garm,:;:.~"~i ~:~:. .... . wa~> > mPa.s us:i._ng the sr~e,:~r r :~t=.a sir Yy 7 ~',.. t~.:- vis~c~=.,i.ty ~~f * trademark ~~~~~6~
- la -the unhydrolysed raw C~1 starch material was 106 mPa.s (25°C, 692 1/s).
Example 2: Preparation of a Cellulose Precursor ~drolyzate ----Cellulose derivative hydrolyzates may be prepared :rom soluble cellulose derivatives as discussed above by an enzymatic hydrolysis utilizing a cellulase preparation having endo- i, 4-beta-glucanase as the sole active hydroly.~_ie agent.
The average degree of polymerisation (DP) of the polymers formed by such a hydrolysis is less than about SoO, and thus the viscosity of solutions of the hydrolyzate is reduced significantly compa:ed to the viscosity of solutions of the unhydrolysed cellulose derivatives. The specific conditions suitable for and the specific time sufficient to secure the desired hydrolysis may be readily determined for each selected cellulose derivative and each selected enzyme preparation.
Similar?y in other embodiments of the invention where degradation is carried out using chemical or physical means, the average DP of the polymers is less than 500 and the viscosity of the resulting mixture is significantly reduced.
_ 19 -Example 3: Preparation of Specific Cellulose Derivative Enzyme Hydrolyzates a. Methylcellulose hydrolyzate 30 g of methylcellulose (14C, hlethocel MC, 64630, Fluka Chemie AG, CH-9470 Buchs, Switzerland) was mixed in 3 1 of watt;r and the pH of the solution was adjusted to 5.5 with 15% phosphoric acid and the temperature ways raised to 40°C. 0.3 ml of the enzyme preparation having a total endo-1, 4 beta-glucanase activity of 1680 nkat from which the beta-g111CO51dase activity was removed chromatcgraphically (as described above) was added to the solution. After hydrolysis for 24 hours the enzyme was inactivated by heating (90°C. 15 min.). The hydrolyzate solution was subsequently cooled and freeze-dried.
The hydrolyzate product contained less than 0.5°a by weight of glucose and cellobiose.
b. H~drox rwlmeth ly cellulose h~drol.yz~tP
20 g of hydroxypropylmethylcellulose (HPP1C, H-9262, Sigma Chemical Company, St. Louis, DtO, U.S..1. ) was ;ni:ced in 1 1 of water and the pH of the solution was adjusted to 5.5 with 15~ phosphoric acid and the temperature was raised to ~;o° C.
0.24 m: of tha enzyme preparation haviag a tctal Pndo-1. 4 beta-glucanase activity of 1340 ni:at Erom ~~~~~6~
which the beta-glucosidase activity was removed chCOitIatographically (as described above) was added to the solution. After two hours another tog of hydroxyprOpylmethylcellulose was added to the solution. After th a hydrolysis of 22 hours the enzyme was inactivated by heating (90°C, is min.). Finally the hydrolyzate solution was cooled and freeze-dried.
'The F:.oduct contained less than 0.05 by weight of glucose and cellobiose.
c. Carboxvmethylcellulose hvdrolyzate (i) E~dralYsis with Trichoderma reesei dPr,vo,y enZYme prepar=
20 'cg of carboxymethylcellulose (CbSC 7MFD-type, a cellulose gum, also designated by the tradename Hlanose and available from Hercules Chemical Company, 9250, Rueil-Malmaison Ceder, France; 7:~tFp designates a medium viscosity, food grade carboxymethylcellulose having 7 out of 10 glucose units substituted with carbo:cymethyl) was mixed in 320 1 Of water and the pH of the solution was adjus:ed to 5.5 with 15~ phosphoric acid and the temperature was raised to ~IOOC. about 0.27 1 of the' e::zy~ne preparation having a total endo-l, 4 beta-glucanase activity of 1,700,000 n kat from which the beta-glucosidase activity was removed J:1 chromatographic:aily (yaw c~es~:x-~i~;~4-i:I ~:~I_~c~t~~r:a saa.s adcleci t:a the CMC salut~ior~. Afi_~r onr~ ~icn_~i ,~ru,7t-t-,e:'~_:' i .~ ~>:f: c~'MC.:
w<::~s added to the solution. After rnyd~ ;:Lye=~i:-,, hours t_hf::r enzyme L ~_, was inactivated by heating '~j0e,, J=a m: r~. i . Final ly, the hydrolysis solut:ior. wa; c=~tn~:e~t:r.~i:ed try ror,vf~ntional evaporating and spray-d-ryi.ng.
The product c~~r~:ta:irned ~'~e~;s tharu _ weigr:t of glucose _ and cellobiose. WhE.tn t. icy ,~~<ctclc~~ :~ wa.s c.arr.ied lcydr~ l.y,z out with tha origin<:~ i ~:FS : Ii.a 1 mt:>~~ t_:~raparat i.or~
c:: -~yrna o.f Trichoderma reesei-vung~.r,~, t:.he ~~mo~_zr~tF-x~odut~.eci glucose a' and cellobiose was <<bave ~~ ~ k:-y we=l.gl-~r_ , (ii) Hydroid:-s _wi;'rr .~~er ill.us and ~~enicillium derived enzyme pre~:~at_~or:s The enzyrrue l:~rF::~par~.~to..cui~! : ~.l.er_wcere c,:mn::~r<:iall.y t.::~::1 availab:la ~w~al:1 u?..a~;c-~ F~~=~" ::~ (~lrn<arc:~rrr~a~c~:~~at:.~
Fl~ c:a:t L C:o. , Ltd. , Nagoya, ~Ja~>~:an) prc:dv,.n....c_--~d~~n ,~l:~p~~rgillas - ~::..a ng strain and Cellulas~} CP c;St~.srgt> Enzymes,North Yo~~kshire, England) produced using a ~;-eni cillium strain.
Carboxymethylcell_ulc~3e hyc,~is c;iy at.e=; .re orepal.~ed as we described it I,;xam,plE', c ( i.;~ ~ F ~c~ c::~i CMC.-'fMF'D
< ~.~',I t_ t.r~,~t,. ~ was asad in 1 1 of wat.arr ,:~~ar:l th~.- ~.ur~.:~~.~r~t-'n:~~,~rnes ~:~dc:Cacl . ,~f war.a 0.0?8 g of Ce:L.lul_aso APB ~ yreav:~nc~ az ,v,~~ endo~-~.., t;at ~ beta.-gl~_~canase activity of i.~5~) ;~ka~t:) t .nd ,;.048 g of * trademark ~~~~ ~~0 Cellulase CP (having a total endo-1, q beta-glucanase activity of 1350 nkat). The viscosities anti molecular weight distributions of the hydrolyzates produced by either cellulase were similar to the hydrolyzate produced with enzymes derived from Trichoderm~epsei.
The viscosities of the various cellulose derivatives and their hydroly:;ates as described above we:e measured using a Haake-Rotovisco viscometer with sensor systems h1V (Karlsruhe, Federal Republic of Germany) (Table 1). The viscosities were measured in water solutions at 25oC. Table 1 sets forth the concentrations (by weight) of a variety of solutions all having the same viscosity.
Concentrations of cellulose derivatives and their respective hydrolyzates in solution all having a viscosity °f 20 mPa.s (milli-Pascals-second) at 25oC.
Cellulose_Derivative--------------====concentration (by a~ei h~
___________ _ __ 9 ..) Methylcellulose -------2%
Methylcellulose hydrolyzate 5%
Hydroxypropylmethylcellulose 3%
t-tydroxyprcpylmethylcellulose10'1 hydroiyzat e Carbcxymethylcellulose 2'1 Carbo:cymethylcellulose 20%
hydroiyzate As the data in Table 1 a_ndic:~ak:~::, l:r:e toydrolyzate of a cellulose derivatiwk? k~a,> a -,,~.zi~~~ar~.:::c.~l._y l.owe:~:, vi.scosity than an equal amaur~ :. b~ ,~c.sca-?~ k: ~ n ,.... ~ ~~.V c~ a : ol. ui::
ic~ru of the cellulose deri~ratioTtwe it pelt: .
Example 4: Carbox~mE,?~~~sces? lulase-.:~herr;iua..1-?-I,ydrolys:i_s 2 gms of cark>oxym<>.thy:l.:~ell.l~lca~;e (J3:l.anase* n~~llulose Gum 7 LfD, Hercu i_u=~,.; i~W..r.;:i.c v:v L :c::~ . , , _~ ~~CnE' , Ruei.l_-Ma lma.it,on Y~ . ;e ~ ~ 4. 100 ml Cedar, France) w~:r~ ~uydn:~l. y ~~c t~~>~. ~.,. a:e.. hourm~
c.l 7.z:v n of 1M sulphuric ~~cid oluti.,.n at ai~c>.~t: 100c.";. After hydrolysis tha sc.~l~:t::~.c~ii c:;~~: ~I~~c:~ t:r.~ abot;it ~a,:as raom temperature, neutralized to airac~.~t ~-i ~~ ~ait.ti 25 ml of 25=a (w/w) of NaOH solw'~ ic.rl and f rs~eze~-d, ~~ec. ~t't~is hy:frolysi.s treatment prodvzcf~cl z ma..:~t.uYc~ p~~ mez s c:::oraaini-n.g c:~ _ es;
than about 4'~ by ~~;ez.~.~~~lt ~ I ,Y Ik ~r i r::le ~ ( ce.l.l.
~: ~ : c~,bi;.>s~ and glucose) . The vi~~::osit~~u~ ;ar~rcl ~~fc?~_~.=~c:e DE') ct this hydrolyzate is s_G.mi_a.ar to the v-..sc~<~:>i.r:i..es ;and a~,re~vage D
of the hydrolyzatt~s. pr~~c~iacec~ t.~~s:~ c~rr y~mruti.c~
b~~> tr~~. at:ments described above c.at ~.. izs.ng er~~:yc;~e-r.irre i i.r_c:>rv ~n~=s '1'ri~~:hoderrr~a.
re~asel.
C arboxymethy.l cvelii.zlos<~ ;i~Mt.) raydr..ta.~.yr.ates can be prepared by ~:~nz,ymt.a t.i.cv, ~:~1~~enn:i. ~ t:~ 1 c.~x~ >Ii ;r:~ ~.c:::a:l, rcnethods .
CMS:: hydrolyzates. u.>ed in ~;r_ sFit...~t irr ezitic:,n Eu~ave the average degree of pol~.;rneri_::~t i.:~_u a t:l-~r~ range of 5 * t:rademax:k to 500, based on the viscosity average molecular weight. The viscosity average molecular weights of the C:AC hydrolyzates were calculated using the Mark-Houwink equation:
( n 1 = Zcrt~
where (n) is intrinsic viscosity, My is the viscosity average molecular weight of the polymer and K and a are hydrodynamic constants caracteristic of the particular polymer-solvent system. The values of K and a for CMC, which were used in this study, were K = 0.043 in 0.2 M NaCl and a = 0.76 in 0.2 bS NaCl as described in Brown and Henley, Studies on Cellulose Derivatives Part IV. The Configuration of the Polyelectrolyte in Sodium Chloride Solutions.
Macromol. Chem " Vol. 79, 68-88 (1964). It is noted that a variety of methods for determining average molecular weights exist, and therefore the values of average molecular weights determined, as well as the average DP values calculated from them, depend upon the experimental method and the basis Eor calculation. CMC hydrolysates described in this invention have an intrinsic viscosity of between 50 ml. per gram to 3 ml, per gram, when determined in o.2M sodium chloride. The C;1C hydrolysates h..ve the viscosity value in the range oi' from S to l00 mPa.s, when measured in 20% (by weight) solutian at 25°C
with shear rate 584s 1 using a Haake Viscotester, _ 25 _ VI 500 with sensor system NV (Karlsruhe, Federal Republic of Germany).
Example S: Treatment of Paper with Polymers derived from Carboxymethyl cellulose (CMC) Ten percent of carboxylic cellulose hydrolyzate (intrinsic viscosity = 31.4 ml per gram) dispersion was prepared with deionized water by stirring overnight. The process was carried out by dipping Whatman No. 1 filter pager in the hydrolyzate dispersion in water for 5 minutes. After dipping, the papers were dried in an oven overnight. Three paper samples (hydrolyzate heated, water treated, and untreated papers) were tested for tensile strength, strain limit, modules. and water and oil spreading. For the tensile test, paper was cut to 50 x 2 mm and loaded in the grip of an Instron Universal Testing Machine (Model 1122, Canton PG1 02021).
Results After dipping into hydrolyzate solution, the treated paper was dried and tested. (Table 3).
Table 3. The Change in Properties" of Paper Treated with Carboxymethyl Cellulose Hydrolyzate (ChC) Sample Paper Maximum TensileTangentialStrain Strength Modulus Gimit (atm) (atm!%) (%) CT~SC Hydrolyzate286 168 3.6 C?1C Hydrolyzate385 184 4.2 b2 C;1C Hydrvlyzate297 211 3.0 Water 120 73 3.9 Untreated 160 , 90 2.7 Values are the average of 10 tests for each sample.
Force-elongation tests were performed with a cross-head speed of 5 mm min 1, a chart speed of 500 mm min 1, and a maximum load of 2000gf.
FIGS. 1. 2. 3 for hydrolyzate-treated, water-treated, and untreated papers, respectively.
The resultant values of the maximum tensile strength before rupturing of treated paper showed a 2 to fold increase over untreated or water treated papers when tt:e paper was ~reatetl with the hydrolyzate.
.\lso, the stain limit and mcdulus i7creased by dipping paper in hydrolyzate (Table 3). Dipoi:~g paper in water alor:e decreased t:~e Techanical ~~ ~~r~~
_ 27 strength and increased the strain limit (Table 3).
water and oil spreading on the papers were also tested (Table 4). Paper dipped in the water did not show any difference in water spreading compared to untreated paper, however, it showed more spreading of oil compared to untreated paper.
Hydrolyzate-dipped paper showed much less water spreading than untreated paper.
Table 4. Water and oil spreading on treated and untreated papers Sample Water spreadingl Oil spreading2 (diamqter, mm) (diameter, mm) Carboxymethyl cellulose hydrolyzate-treated 13 26 Water-treated 21 25 Untreated 20 23 Average of Triplicate (-~ s.e.) 1 Measured diameter 5 minutes after spotting 20u1 of water.
2 Measured diameter 30 minutes after spotting 20N1 of oil.
Example 6: Treatment of Paoer with Polymers derived from CarboxymethYl Starch (CMS) -Five percent carboxymethyl starch (C"1S) and carboxyme~hyl starch hydrolyzate (CMSH) dispersions were prepared with deionized water. Two sets of dispersions were made; one was mixed (l0 minutes) at room temperature and the other at' y0°C (to achieve gelatinization). :he coating process was carried out by dipping whatman No. 1 filter paper in each polymer dispersion for S minutes. After dipping, the papers were dried in an oven overnight. The paper samples were tested for tensile strength, strain limit and modules. For the tensile test, paper was cut to 50 x 2 mm and loaded in the grip of an Instron Universal Testing Machine (Model 1122, Canton, MA 02021).
In both sets of samples prepared at roam temperature and at 90°C, the paper treated with carboxymethyl starch hydrolyzate had highe: tensile strength and strain limit than the paper treated with carboxymethyl starch of higher molecular weight. (Table 5). This shows, that the mechanica:
properties of the paper can be improved core using carboxymethyl starch or icwer me?ecu:ar weight.
:,lso the modules was higher when the paper was treated with carboxy~nethyl starch !~ydrolyzates, suggesting an increase in the sti:fness of the paper (Table 5).
Table 5. The Change in Properties" of Paper Treated with Carboxymethyl Cellulose Hydrolyzate (i.?1C) Sample Paper Maximum Tensile Strain Tangential Strength Limit Plodulus (atm) (%) (atm/%) CM Starch 79 3.2 48 (room temp.) CM Starch (90°C) 80 4.9 A3 CM Starch 209 5.2 1'00 Hydrolyzate (CHSH) (room temp.) CM Starch 234 6.9 117 Hydrolyzate C:yISH
(90°C) Example 7: Hydrolyzed Polysaccharide Derivatives as Dewaterinq Aids Polysaccharide derivatives or their hydrolyzates were prepared and dissolved in water. After stirring Eor 10 minutes, the solution was added to Furnish. The Final mixture contained furnish (0.106% w/v solid) and 0.0053°s (w/v) polysaccharide derivatives or their hydrolyzates. The ni:cture was mixed for 10 minutes and pou:ed on basenent paper which serves ~s a screen. ;:~e amount o: water drained was recorded for ~he determination of dewatering rate and final water content was f.
measured. The furnish was dried in the oven and used in the tensile strength test.
Drainage tests Eor furnish treated with charged polysaccharides aad with their hydrolyzates showed initial drainage rates higher than that of furnish alone. (FIG, 4).
T:~e amount of drained water (i.e. an index of dewatering) and the water content of the furnish (i.e. an index of draining) treated with charged polysaccharide derivatives and their hydrolyzates are shown in Table 6, Table 6 Furnish Treatment amount of Water Weight of Retained Drained (ml) Water (g) (Final water Content) CrIC Hydrolyzate 95 5.3 CP1C 9 2 4 . 5 CM Starch Hydrolyzate 94 6.2 CM Starch 94 5.4 Control (Furnish) 93 5.0 :ensile strength ~ests showed that the Eurniah treated with charged polysaccharide hydrolyzates gave high er tensile strength and ;.angential modules than those tested with high molecular weight charged polysaccharides (Table 7), Table 7 Sample Furnish Maximum Tensile Strain Limit Modulus Treatment Strength (~) (atm ~) (atm) CMC Hydrolyzate 114.0 4.7 60 CMC 75.8 5.S 58 CM Starch Hydrolyzate100.0 4.7 CM Starch 85.7 4.3 46 Control (Furnish) 88.4 4.7 Therefore, this experiment shows that polysaccharide derivatives and their hydrolyzate increase the rate of dewatering in the early stage of drainage. Particularly, the polysaccharide derivative hydrolyzates of the invention significantly improve the mechanical properties of the pulp product.
Example 8:
Polysaccharides or their hydrolyzates were prepared and dissolved in a warm water (80°C, C"( starch and its hydrolyzate) or room temcarature water (C~iC and its hydrolyzate). After stirring fur 10 minutes, t::e solution was nixed with'Ca(C03)2 solution. After stirring for l0 minutes, :he mixture was added to furnish. The mi:cture contained furnish with 0.106% (w/v) solid, 0.106% (w/v) Ca(CO3)2, and 0.00575% (w/v) polysaccharides or their hydrolyzates. The test for dewatering was repeated. The draining rates were faster in those mixtures containing hydrolyzate than those of high molecular weight polysaccharides (Figure 5).
The amount of drained water, and the final water content of the samples treated with charged polysaccharides and their hydrolyzates are shown in Table 8. Furnish and Ca(C03)2 treated with hydrolyzates showed a higher dewatering rate,' retaining less water than furnish and Ca(C03)2 treated with higher molecular weight polysaccharide derivatives.
Table 8 Furnish Mixture Amount of Water Weight of Retained Treatment Drained (ml) Water (g) (Final Water Content) C;iC Hydrolyzate 98 4 , 3 CMC 90 5.5 CM Starch Hydrolyzate 94 6.4 CM Starch 89 , The curnish mixture thus produced were dried in an oven and the tensile strength was tested. The test results showed that the samples treated with charged polysaccharide hydrolyzate~ ha'd a higher tensile strength and tangential modules than those treated with high molecular weight charged polysaccharide Eor both CMC and CM starch (Table 9).
Table 9 Sample Paper Maximum Tensile Strain Limit Tangential Strength ' (%> Modules (atm) (atm/3) CMC Hydrolyzate 81.2 . 4.5 43 CMC 61.4 4.4 35 C~1 Starch Hydrolyzate 101.7 5.0 61 CMS 85.7 5.6 49 Control (Furnish) 88.9 4.7 51 It will now be apparent to those s:tilied in the art that other embodiments, improvements, details and uses can be made consistent with the letter and spirit of the foregoing disclosure and within the scope of :h:s patent, which is limited only by t:~e following claims, construed in accordance with the ~ paten law, including the doctrine of equivalents.
What is claimed is:
This invention pertains to the field of paper.
pulp and textile making and their chemistry.
BACKGROUND OF THE INVENTION
Of the many raw materials used by the paper industry, cellulose fibers have occupied the dominant position for nearly 2000 years. The techniques of paper, making are known worldwide and the basic principles have not changed. Despite great improvements in papermaking, however, procedures fo: strengthening cellulose fibers in the papermaking process are often e:cpensive, time consuming, and environmentally questionable.
204~~6~
The kraft or sulfate process is probably the most extensively employed method to produce strong cellulose fibers. The active ingredients in pulping wood to its fibrous state axe sodium hydroxide and sodium sulfide, in a strong alkaline solution. The process generates objectionable smells from the sodium sult:ide produced during the process. Kraft pulps are dark in color, difficult to bleach and very strong.
Nevertheless, cellulose fibers obtained from the pulping process are generally unsuited for paper making and muss first be refined. With given pulps, final,paper properties are largely controlled by the type and extent of refining action employed. r1 variety of additive materials can be introduced to the paper-making pulps, commonly called "furnish", during stock preparation. Fillers such as clays, or calcium carbonate are used for the control of sheet opacity and for other reasons. Dyes are used extensively for color control and other additives such as wet-strength agents, and defoamers are used as needed.
For the most part. however, operations designed to inerea-e tlae strength and/or other physical properties of paper take place subsequent to the paper making operation and are called "off-machine converting." These converting operations are highly complex and include embossing, coating, waxing, laminating, Impregnating, saturating, currogating, and printing. For example, food packaging has led to extensive paper utilization with the paper often being coated, waxed, resin-impregnated, or combined with other fcils and films. ~ relatively simple and inexpensive method of improving the paper making process and increasing the stiffness and ultimate strength of paper is needed.
SUMMARY OF T4E INVy'NTIQN
It is an object of the invention to provide materials that improve the properties of paper, pulp and textile products.
It is a further object of the invention to provide a simplified paper-making process by improving the dewatering and draining properties of paper pulp, It is yet another object of the present invention to provide degradation.products of polysaccharide derivatives which are useful as strengthening and dewatering agents for treating paper products or materials.
The invention discloses the manufacture of novel paper materials comprising treating paper wi;,h water soluble or water suspendable mixtures of relative:y low molecular weight polymers. The poly~r.ers are obtained by degrading polysaccharide derivatives, most preferably starch and cellulose derivatives.
The invention further pertains to a paper product treated with a composition comprising a mixture of polymers derived from degradation of a cellulose derivative, the derivative comprising one or more substituents, said mixture of polymers having an average degree of polymerization in the range of about 5 to about 500, and wherein a majority of the polymers has a degree of polymerization and molecular weight such that the polymer conforms to a rod-like configuration.
In accordance with the invention, there is provided a water soluble or water dispersable mixture of polymers derived from a degraded polysaccharide derivative, the mixture of polymers having an average degree of polymerization in the range of about 5 to about 500. The most preferred polysaccharide derivative comprises starch or cellulose. The polysaccharide derivative may be degraded by enzymatic, chemical, physical, or mechanical agents/mechanisms. In embodiments where an enzyme preparation is utilized to perform the degradation, the enzyme preparation is typically selected from the group of polysaccharide degrading enzymes. In the case of starch derivatives, enzymes such as amylases or pullulanases and mixtures thereof are suitable.
In embodiments where degradation of a polysaccharide derivative is to be effected by chemical or physical means, chemical hydrolysis, chemical oxidation and heat treatment are preferred mechanisms for achieving ~he desired polymeric mixtures according to the invention.
By conventional means, a polymer or an initially degraded polysacchride derivative mixture may be further separated into fractions of polymers of differing average chain lengths, e.g. using chromatographic techniques. The viscosity of the various fractions will vary with the degree of average chain length of the polymers contained within in a fraction. Depending on the particular paper product application, one or more fractions are selected from an initial polymeric mixture having a viscosity (average chain length) which is most appropriate for the particular application.
There is provided a method of increasing the strength of paper, comprising treating the paper with a mixture of polymers derived from a substituted cellulose derivative, said mixture having an average degree of polymerization in the range of about 5 to about 500.
The method of enhancing the dewatering properties of paper pulp comprises treating the pulp with a water soluble or water dispersable mixture of relatively low molecular weight polymers, which polymers are obtained by degrading polysaccharide derivatives, most preferably starch and cellulose.
There is also provided a method of paper manufacture having the steps of:
(a) pulping the fibers;
(b) refining the paper stock;
(c) forming the paper sheet; and (d) drying the paper sheet, wherein the improvement comprises the step of:
treating the paper with a mixture of polymers derived from a cellulose derivative, the derivative comprising one H
or more substituEmt:~, sa:iay riiyt~..ire ~~~~~..~~.~;c° an average degree of polymarirati.on cJ:' af;~cuz~. t:~o :zho at. '~Cn:), a,~.nd wl~arain a majority of tree x>c~~.~~~cners n,_~s ,:z s:lc~ 7i:~:~E ~ a ~:~u Lyrr;er~_z,:~~ i<>n and molecular weight saa,.:h t~:~~t ~.r~e ~~-.;.1..~,,m:,.r~ ~:~o;forms to a rcd-like configuration.
i f, ~~3~~ ~~~
_,_ BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a force-distance curve of Whatman No. 1 filter paper treated with carboxylmethyl cellulose hydrolyzate.
Figute 2 is a force-distance curve of Whatman No. 1 filter paper dipped in distilled water.
Figute 3 is a force-distance curve of untreated 'Ahatman No. 1 filter paper.
figure 4 shows results of drainage tests on furnish treated with carboxymethyl cellulose (CMC) hydrolyzate (~), carboxymethyl cellulose (o), carboxymethyl starch (CM starch) hydrolyzate (D), carboxymethyl starch (CM starch) (,1), and untreated furnish (O).
Figure 5 shows results of drainage tests on furnish/calcium carbonate mixtures treated with carboxymethyl cellulose (C?tC) hydrolyzate (.), carbo~.ymethyl cellulose (o), carboxyn,ethyl starch (CM starch) hydrolyzate (p), and carboxymethyl starch (CM starch) (p), -DETAILc.D DESCRIP:ION OF THE I.WENT_IO_N
:his invention describes paper materials trea:ed with the c:egradation product of a polysaccharide derivative and :r,ethods therefor. ~,'he term "polysaccharide' refers to a polymeric carbohydra~e having a plurality of repeating units comprised of ~d~42a~~
simple sugars. The term "polymeric" or "polymer" is meant to include both oligmeric and polymeric units and, specifically, those polysaccharides having more than four repeating monomeric simple sugar units.
The C-O-C linkage formed between two joined simple sugar units in a polysaccharide chain is called a glycosidic linkage, and continued condensation of monosaccharide units will result in polysaccharides. The most common polysaccharides are amylase and cellulose, both made up of glucose monomers. ~mylose is a major constituent of starch and glycogen. Cellulose is the major structural component of plants. Other polysaccharides useful in this invention have a straight chain or branched polymer backbone including one or more sugar monomers. These polysaccharides include those having sugar monomers such as glucose, galactose.
arabinose, mannose. Fructose, rahmnose, and xylose.
Preferred polysaccharides useful in the article and methods of this invention are cellulose and starch. Nevertheless, examples of other such polysaccharides with branched or straight backLones are carragenan, pullulan. pustulan, laminarin.
sclercglucan, alginate, guar gum, gum arabic, inulin, pectin, whelan, rhamsan, gellan, :canthan, zooglan, met:~ylan, chitin, cyclodextrin and chitosan, The term "derivative" is meant to define ~~4~
_ g _ polysaccharides according to this invention that are substituted. Preferably, the polysaccharide derivative starting material has a degree of derivatization or substitution of between about 0.1 and about 3Ø "Degree of substitution" refers to the number of derivative groups (e. g. carboxymethyl, hydroxypropyl) per monomer unit in the polysaccharide backbons (branch or straight chain backbone). A degree of substitution of 0.2 means, for example that there is about one derivative substituent for every Eive monomer,units in the polysaccharide backbone. ~ degree of substitution of three would mean there are three derivative substituents per every monomer unit in a polysaccharide chain. Typical substituents comprise one or more of sulfate, carboxylic acid (found in carragenan, alginate, pectin), carboxylic ester, pyruvic acid .(found in pectin, xanthan gum, zooglan, and methylan), carboxymethyl, hydroxypropyl, methyl, methylethyl, hydroxyethyl, hydroxyethylmethyl and the like.
Specifically, carboxymethyl starch can be degraded enzymatically to produce correspondii:g carboxymethyl starch hydrolyzates. Ot'~er typical suitable starch derivatives include hydroxypropyl, methylethyl and hydroxyethyl starct:es. :he substituents are typically bonded to a starch 1 ::~
glucose monomer un.. t ,~t, t.h~~ ?, 3 a~~d 6 posit.i.or:,s. Most typically a starcl-: startirr.g materi...;1 ~.~~~;rnpr.ises between about 1~ to 85-'amyl~:~se and <ab~asr:t 1~~'. t~:7 '~~~" amyl_opE-ct.in.
Cellulose der.i~~.:~ti°;re~~ ar~F: c-ommerv~~a.l~,~ a~;railab.ie.
Sucr exemplary products as metriui.c.~~l:Lul,.ac= ,;MC,Methocel* MC.', 64630, I-'luka C~erro~e AG, ..-~~:i'7i.::=~c~-r>, Swi.t~~~rland) , hydroxypropylmetr~nylc~allulc-se ~,~-'fMc';, C-___c~ ~t>~ , S;_gmG Chem.
Co. , St. Louis, M01 and c:~arl::».~ycne:t:C-i.~, 1. ~~~e L~u_i.o::,e (CPfIC
~MF'L?, BlanOSa*, HarC~ll~:~~~ yrle'r"1. l~f'~, , '~~_, ~''>~.~~/ rxl2E~l. ~.-M~~1'rr'Lal;iGn C:adar, Frances all have a ~lef~.~ ~-~E: <af: w ~>:r: i ~.~t:i..c:~r~ k:>etween 0. 1.
and 3. Hydroxypropyl ce:, lu:Lc,t;e:~~ Ar.e K_ L ~,~~~ ,:c_>,znr~i:~~ c::;i<~ l.ly a~~~ai.l.abl.e anc:~ suitable for use~~.
As descri.bec~ nn:pre f~~_ril.~~ )... ~t..E,ir~, s ac~r~ p;olysac:~charide derivatives may k:~w decCradc~d tc~ ;~c:.~i yrrw ~ z. ~. mi;~t.u:res of average degree o.f_ pc~lymc~rizt~t ion ;I'~F! L~~:tween abou-t. 5 and about 500 by en:~~~rn::3ti.c-, <:h~:,rr,icv=x_~, ~.sl,~;»3~~r3 cr mec:hanical agents,~means . The pc: i_yme r ic.~ cra :~;tu t:e:a <r-~ ~~:rwrs:~ll.y :referred to as a ~~hydrolyzate". ~'he t:.errn "dectrade~." refers to the procedure whereby y:olysa~~cha.~:z~:~<~ ~1<e:.i~a-:.tines are broken down into smaller oc.i vrn~ ric: l.:n;i_ts .
Exem~:.lary en<:y:n:es _e:.L a.~c. i.r._ cy ac,~:i.ng ~_~ert.ain of the above de;~:::ribed ~,~; y.,,ac ..,i.lax ~_c:lt: dez:uvatives * trademarks are pectinases, lyases, lysozymes, xanthanases.
chitinases and laminarases. Exemplary enzymes which are suitable for degrading cellulose derivatives are various cellulases. They can be produced from a multitude of different microorganisms such as strains of Trichoderma. Asperqillus, Penicillium.
etc. A selected microorganism strain is gro=.m by conventional means in a suitable medium such that the cellulases are produced, the microorganism is separated from the medium, the medium is collected and typically concentrated and dried. Cellulase preparations suitable Eor use herein are, e.g. the commercially available cellulase preparations designated as the Econase series as produced by Alko Ltd., Helsinki, Finland.
A polysaccharide derivative mad be hydrolyzed by treating a polysaccharide derivative with a solution of acid. ~Pypical acid treatment solutions might contain acids such as sulphuric acid, hydrochloric acid, phosphoric acid, or mixtures of the foregoing. The concentration of the acid in the treatment solution and the treatment time and temperature may vary depending on the degree of dagradation of the polysaccharide derivative which is desired. In any event where an acid hydro:hsis treatment is u~ilized, the acid concentration and the treatment time and temperature is selected to ~(~~~~~~
produce a mixture of polymers having an average pp of between S-5oo.
A selected polysaccharide (e.g, starch or cellulose) derivative may be degraded by oxidation with such a,ients as chlorine,t~oxygen or hydrogen peroxide. Such oxidative treatments and reaction conditions are well known in the art. It may also be possible to use physical methods like heat or mechanical shear treatment or sonication when cleaving the chain backbone of polysaccharide derivatives.
Whatever conventional chemical ('hydrolytic, oxidative or otherwise) or physical treatments are employed, the conditions and the degree o~ treatment are selected such that the poly",eric mixture resulting from the initial treatment has an aveCage Dp of between about 5 and about 500.
Enzymes which may be Used with res pect to paper products prepared or coated with degraded starch derivatives, are various amylolytic enzyme preparations. They can be produced from a multitude of different microorganisms such as strains of Bacillus, K~Siella, Clostridium, ~illus, ----------_ as oe r RSizo us. Typical commercially -available enzyme preparations suitable for use herein are amylolytic preparations (such as alpha and beta amylases), pulluianases; and cyclodextrin glycosyltransEer ses ~~~~r~~~
(CGTase).
The polymers described above are used in the method of the invention to improve the properties of paper products and to strengthen paper produc t . In its broadest embodiment, the method comprises preparing a polymeric mixture of substituted polysaccharides having an average degree of po~ymerization (DP) in the range of 5-500. Next.
the mixture is then contacted with paper for a period of time sufficient to treat the paper with the polymer mixture.
This invention relates more specifically to a paper or paper product treated with water soluble or dispensable mixture of polymers derived from a polysaccharide derivative. The polymeric mixtures are characterized by having an average degree of polymerization (DP) in the range of about 5-500.
Preferably, the DP range is between 7-200.
The terms "paper" and "pulp products" are intended to include a variety of products made from cellulose, synthetic or other fibers, such p:oducts being recognized by those skilled in the art as paper, boards, construction paper, in addition, these terms refer to ar;.icles prepared frcm cellulose, synthetic, or other fibers or filamenatous materials such as those used in the textile industry. Specific examples include :eited or matted sheets of cellulose Fibers, fcrmed on a Fine wire sc:een from a dilute water suspension, and bonded together as the water is removed ar:d the sheet is dried. These terms may also include sheet materials produced from other types of fibers, particularly mineral or synthetic'fibers, formed and bonded by other means. These terms also include liquified or semi-solid mixtures of pulped fibers, commonly called "furnish", to which i,s added various materials such as fillers (clays, calcium carbonate), dyes, wet-strength agents and the like during the typical paper-making process.
Methods of paper manufacture include the basic steps of pulping fibers. refining the pulp by addition of various materials, as described below.
forming the paper on mesh screens, and drying the matted fibers.
The polymer mixtures can be applied after the paper is made, in the so-called "off-machine converting" procedures. The mixtures can be applied using methods well known in the art suet. as dipping, spraying, and rolling.
Not wishing to be bound by any theory, it is believed that the polysaccharide derivative mixture thus prepared coats the surface of the paper and becomes fixed thereon by attraction between the polysaccharide mixture and ~he polysaccharide .
components o: the paper including by physical :orces such as hydrogen binding, Van der Waals Forces and the like. The low molecular weight Folyzners cf the invention are aligned along the cellulose, or other fibers. As a result, the intermolecular attraction per unit length increases, facilitating the quality of the final product and improving the p:ocessability of the paper or pulp product.
The polymeric mixtures can also be incorporated into the papar furnish during pulp refining procedures. In this embodiment, the mixture of degraded polysaccharides can be incorporated into the pulp furnish along with other dyes, colorants.
wet-strength agents (agents capable of increasing the strength of wet or suspended materials), defoamers, and the like. In this procedure, the polysaccharides will become impregnated into the matri:c of the paper fibers, The term "treated" or "treatment" are intended to include means or methods for contacting paper products with the polymeric mixtures so that at least one effect of such contact is to strengthen the paper, coat or impregnate the paper, improve the paper or pulp handling properties during manufacturing, improve the paper or pulp handling properties during manufacture, and/or increase the dewatering capacity of the paper pulp. Examples cf a methods of treatment include the two methods of inr.roducing the polymer derivatives of the invention to the paper or paper products,described above.
Paper produced according to the method of this invention may be stronger than non-treated papec.
rloreover, treated paper may less water spreading than untreated paper. Furnish treated with the polymers of the invention show an increased rate of dewatering during the early stages of draining.
This invention will now be more particularly described using the following examples.
Example 1: Pretiaration of a S
Nydrolyzate . -------- tarc=rec=
Starch derivative hydrolyzates may be prepared from starch derivatives as defined above.by an enzymatic hydrolysis utilizing an amylolytic preparation having a-amylase as the main active hydrolytic agent such that only insignificant amounts of mono- arid disaccharides are produced.
The hydrolysis procedure is generally carried out by dissolving the starch derivative in water, adjusting the pft and the temperature to tt:e value suitable for the enzyme activity, adding the enzyme to the solution and allowing the enzyme to react for a suitable time. After the enzyme reaction, enzyme is inac~ivated by heating the solution up to about loo°C and the hydrolyzate product is concentrated and dried. The average degree of poly;r,erization (DP) of the products formed by such a ~. f l hydrolysis is less tharu ':~00 as ~_~eter:r'i.na:a by the reducing end group measureme.,..it, ~c..cc'rd.i.ry t<::- ;~~on,~>~~~~%i, M. ~~. Bial.
Chem. 19'J, 19-33, ( : 9'.p:~. . '~r:e s peci.i.i c: c ondit.ions :_aui table for and the spec:.fic t.in;c-~ :~m~ticient to sec~.~re the desirab:Le hydrolysis-: may bc:~ ra~ac:.i.l. ~ '.:letr=rrniried f~::or each selected s parch aF~rz~r at :i.v~> «nd ~:=-'~h se_iected enzyme preparation.
Similarly, what~a c~ar~r ~.l~ti-~;rv; i ' a~rr.ia:~ o~.zt:: l.rsing chemical or physical meain~., .Lv~!:: ~c~ ~x-~~~1~.,: I >' a~;:f. ~:he~
c:o.l.icTomer~s is less than 500.
60 g of= carbox.,~methy~L =~i,:;~:rt:::kz (C"1~1 :>t,irvc~hu; deri_~red. from potato starch (F.rimojel ~; ~-lve~r~E:, ~~~;0! ~>',T' FoxTuc>l, The Netherlands) was mi~~'::;d il~ 12i)~:~ rr::l. ~~:~ uaat'.er. Tne ter~~tlerature of the mixture was raisec::i t..o ~a~>''C: :3ri'~.i t rve suspens ion was mixed cont.inuous:iy. About 1.. '~: m1 ~~f arr;y_Ta:,e (l3an* 120h, Novo, Industri A!S, Nova ??~ lc~, ~8~~:~ Bags>vaerd, t:?enmark) diluted 1i50 by volu:rne was a,adecx t:o f.t:e si.x~,pension rrx.ixt.ure.
After, hydrolysis c_w.f= ahout ~i~ m:i r...~ t:es r.~ie ersz~;~me was inactivated by he~~ti..ng ;:i..;n0''C, l_ia ro':ii~.. '.1'l:e huvci~:olyzate waa then Breeze-dri..e'::k.
Tha hydrc:>lyzat i~' s vra 1 ~aF: c:~f e::cTUCi. cug s~.zgar_ s was 0.:'T3o. Tha v_i.scot;a;:y c:_~f a ~,:°a! i~~y ~ra.:.lic.;~ht~
susp~~n~:;-ion of the hydrolyzate, :r~easu:r°E~ra .~,~.i.r~ng E-Taake--Rc:~toviscc RV 12 viscometer w~~itf's. seru:ac.:.t~ sy:.~i_c~~rns T~~J; iF~Ca~ lsruhe, "..G . ~7 Federal Republic: ~f Garm,:;:.~"~i ~:~:. .... . wa~> > mPa.s us:i._ng the sr~e,:~r r :~t=.a sir Yy 7 ~',.. t~.:- vis~c~=.,i.ty ~~f * trademark ~~~~~6~
- la -the unhydrolysed raw C~1 starch material was 106 mPa.s (25°C, 692 1/s).
Example 2: Preparation of a Cellulose Precursor ~drolyzate ----Cellulose derivative hydrolyzates may be prepared :rom soluble cellulose derivatives as discussed above by an enzymatic hydrolysis utilizing a cellulase preparation having endo- i, 4-beta-glucanase as the sole active hydroly.~_ie agent.
The average degree of polymerisation (DP) of the polymers formed by such a hydrolysis is less than about SoO, and thus the viscosity of solutions of the hydrolyzate is reduced significantly compa:ed to the viscosity of solutions of the unhydrolysed cellulose derivatives. The specific conditions suitable for and the specific time sufficient to secure the desired hydrolysis may be readily determined for each selected cellulose derivative and each selected enzyme preparation.
Similar?y in other embodiments of the invention where degradation is carried out using chemical or physical means, the average DP of the polymers is less than 500 and the viscosity of the resulting mixture is significantly reduced.
_ 19 -Example 3: Preparation of Specific Cellulose Derivative Enzyme Hydrolyzates a. Methylcellulose hydrolyzate 30 g of methylcellulose (14C, hlethocel MC, 64630, Fluka Chemie AG, CH-9470 Buchs, Switzerland) was mixed in 3 1 of watt;r and the pH of the solution was adjusted to 5.5 with 15% phosphoric acid and the temperature ways raised to 40°C. 0.3 ml of the enzyme preparation having a total endo-1, 4 beta-glucanase activity of 1680 nkat from which the beta-g111CO51dase activity was removed chromatcgraphically (as described above) was added to the solution. After hydrolysis for 24 hours the enzyme was inactivated by heating (90°C. 15 min.). The hydrolyzate solution was subsequently cooled and freeze-dried.
The hydrolyzate product contained less than 0.5°a by weight of glucose and cellobiose.
b. H~drox rwlmeth ly cellulose h~drol.yz~tP
20 g of hydroxypropylmethylcellulose (HPP1C, H-9262, Sigma Chemical Company, St. Louis, DtO, U.S..1. ) was ;ni:ced in 1 1 of water and the pH of the solution was adjusted to 5.5 with 15~ phosphoric acid and the temperature was raised to ~;o° C.
0.24 m: of tha enzyme preparation haviag a tctal Pndo-1. 4 beta-glucanase activity of 1340 ni:at Erom ~~~~~6~
which the beta-glucosidase activity was removed chCOitIatographically (as described above) was added to the solution. After two hours another tog of hydroxyprOpylmethylcellulose was added to the solution. After th a hydrolysis of 22 hours the enzyme was inactivated by heating (90°C, is min.). Finally the hydrolyzate solution was cooled and freeze-dried.
'The F:.oduct contained less than 0.05 by weight of glucose and cellobiose.
c. Carboxvmethylcellulose hvdrolyzate (i) E~dralYsis with Trichoderma reesei dPr,vo,y enZYme prepar=
20 'cg of carboxymethylcellulose (CbSC 7MFD-type, a cellulose gum, also designated by the tradename Hlanose and available from Hercules Chemical Company, 9250, Rueil-Malmaison Ceder, France; 7:~tFp designates a medium viscosity, food grade carboxymethylcellulose having 7 out of 10 glucose units substituted with carbo:cymethyl) was mixed in 320 1 Of water and the pH of the solution was adjus:ed to 5.5 with 15~ phosphoric acid and the temperature was raised to ~IOOC. about 0.27 1 of the' e::zy~ne preparation having a total endo-l, 4 beta-glucanase activity of 1,700,000 n kat from which the beta-glucosidase activity was removed J:1 chromatographic:aily (yaw c~es~:x-~i~;~4-i:I ~:~I_~c~t~~r:a saa.s adcleci t:a the CMC salut~ior~. Afi_~r onr~ ~icn_~i ,~ru,7t-t-,e:'~_:' i .~ ~>:f: c~'MC.:
w<::~s added to the solution. After rnyd~ ;:Lye=~i:-,, hours t_hf::r enzyme L ~_, was inactivated by heating '~j0e,, J=a m: r~. i . Final ly, the hydrolysis solut:ior. wa; c=~tn~:e~t:r.~i:ed try ror,vf~ntional evaporating and spray-d-ryi.ng.
The product c~~r~:ta:irned ~'~e~;s tharu _ weigr:t of glucose _ and cellobiose. WhE.tn t. icy ,~~<ctclc~~ :~ wa.s c.arr.ied lcydr~ l.y,z out with tha origin<:~ i ~:FS : Ii.a 1 mt:>~~ t_:~raparat i.or~
c:: -~yrna o.f Trichoderma reesei-vung~.r,~, t:.he ~~mo~_zr~tF-x~odut~.eci glucose a' and cellobiose was <<bave ~~ ~ k:-y we=l.gl-~r_ , (ii) Hydroid:-s _wi;'rr .~~er ill.us and ~~enicillium derived enzyme pre~:~at_~or:s The enzyrrue l:~rF::~par~.~to..cui~! : ~.l.er_wcere c,:mn::~r<:iall.y t.::~::1 availab:la ~w~al:1 u?..a~;c-~ F~~=~" ::~ (~lrn<arc:~rrr~a~c~:~~at:.~
Fl~ c:a:t L C:o. , Ltd. , Nagoya, ~Ja~>~:an) prc:dv,.n....c_--~d~~n ,~l:~p~~rgillas - ~::..a ng strain and Cellulas~} CP c;St~.srgt> Enzymes,North Yo~~kshire, England) produced using a ~;-eni cillium strain.
Carboxymethylcell_ulc~3e hyc,~is c;iy at.e=; .re orepal.~ed as we described it I,;xam,plE', c ( i.;~ ~ F ~c~ c::~i CMC.-'fMF'D
< ~.~',I t_ t.r~,~t,. ~ was asad in 1 1 of wat.arr ,:~~ar:l th~.- ~.ur~.:~~.~r~t-'n:~~,~rnes ~:~dc:Cacl . ,~f war.a 0.0?8 g of Ce:L.lul_aso APB ~ yreav:~nc~ az ,v,~~ endo~-~.., t;at ~ beta.-gl~_~canase activity of i.~5~) ;~ka~t:) t .nd ,;.048 g of * trademark ~~~~ ~~0 Cellulase CP (having a total endo-1, q beta-glucanase activity of 1350 nkat). The viscosities anti molecular weight distributions of the hydrolyzates produced by either cellulase were similar to the hydrolyzate produced with enzymes derived from Trichoderm~epsei.
The viscosities of the various cellulose derivatives and their hydroly:;ates as described above we:e measured using a Haake-Rotovisco viscometer with sensor systems h1V (Karlsruhe, Federal Republic of Germany) (Table 1). The viscosities were measured in water solutions at 25oC. Table 1 sets forth the concentrations (by weight) of a variety of solutions all having the same viscosity.
Concentrations of cellulose derivatives and their respective hydrolyzates in solution all having a viscosity °f 20 mPa.s (milli-Pascals-second) at 25oC.
Cellulose_Derivative--------------====concentration (by a~ei h~
___________ _ __ 9 ..) Methylcellulose -------2%
Methylcellulose hydrolyzate 5%
Hydroxypropylmethylcellulose 3%
t-tydroxyprcpylmethylcellulose10'1 hydroiyzat e Carbcxymethylcellulose 2'1 Carbo:cymethylcellulose 20%
hydroiyzate As the data in Table 1 a_ndic:~ak:~::, l:r:e toydrolyzate of a cellulose derivatiwk? k~a,> a -,,~.zi~~~ar~.:::c.~l._y l.owe:~:, vi.scosity than an equal amaur~ :. b~ ,~c.sca-?~ k: ~ n ,.... ~ ~~.V c~ a : ol. ui::
ic~ru of the cellulose deri~ratioTtwe it pelt: .
Example 4: Carbox~mE,?~~~sces? lulase-.:~herr;iua..1-?-I,ydrolys:i_s 2 gms of cark>oxym<>.thy:l.:~ell.l~lca~;e (J3:l.anase* n~~llulose Gum 7 LfD, Hercu i_u=~,.; i~W..r.;:i.c v:v L :c::~ . , , _~ ~~CnE' , Ruei.l_-Ma lma.it,on Y~ . ;e ~ ~ 4. 100 ml Cedar, France) w~:r~ ~uydn:~l. y ~~c t~~>~. ~.,. a:e.. hourm~
c.l 7.z:v n of 1M sulphuric ~~cid oluti.,.n at ai~c>.~t: 100c.";. After hydrolysis tha sc.~l~:t::~.c~ii c:;~~: ~I~~c:~ t:r.~ abot;it ~a,:as raom temperature, neutralized to airac~.~t ~-i ~~ ~ait.ti 25 ml of 25=a (w/w) of NaOH solw'~ ic.rl and f rs~eze~-d, ~~ec. ~t't~is hy:frolysi.s treatment prodvzcf~cl z ma..:~t.uYc~ p~~ mez s c:::oraaini-n.g c:~ _ es;
than about 4'~ by ~~;ez.~.~~~lt ~ I ,Y Ik ~r i r::le ~ ( ce.l.l.
~: ~ : c~,bi;.>s~ and glucose) . The vi~~::osit~~u~ ;ar~rcl ~~fc?~_~.=~c:e DE') ct this hydrolyzate is s_G.mi_a.ar to the v-..sc~<~:>i.r:i..es ;and a~,re~vage D
of the hydrolyzatt~s. pr~~c~iacec~ t.~~s:~ c~rr y~mruti.c~
b~~> tr~~. at:ments described above c.at ~.. izs.ng er~~:yc;~e-r.irre i i.r_c:>rv ~n~=s '1'ri~~:hoderrr~a.
re~asel.
C arboxymethy.l cvelii.zlos<~ ;i~Mt.) raydr..ta.~.yr.ates can be prepared by ~:~nz,ymt.a t.i.cv, ~:~1~~enn:i. ~ t:~ 1 c.~x~ >Ii ;r:~ ~.c:::a:l, rcnethods .
CMS:: hydrolyzates. u.>ed in ~;r_ sFit...~t irr ezitic:,n Eu~ave the average degree of pol~.;rneri_::~t i.:~_u a t:l-~r~ range of 5 * t:rademax:k to 500, based on the viscosity average molecular weight. The viscosity average molecular weights of the C:AC hydrolyzates were calculated using the Mark-Houwink equation:
( n 1 = Zcrt~
where (n) is intrinsic viscosity, My is the viscosity average molecular weight of the polymer and K and a are hydrodynamic constants caracteristic of the particular polymer-solvent system. The values of K and a for CMC, which were used in this study, were K = 0.043 in 0.2 M NaCl and a = 0.76 in 0.2 bS NaCl as described in Brown and Henley, Studies on Cellulose Derivatives Part IV. The Configuration of the Polyelectrolyte in Sodium Chloride Solutions.
Macromol. Chem " Vol. 79, 68-88 (1964). It is noted that a variety of methods for determining average molecular weights exist, and therefore the values of average molecular weights determined, as well as the average DP values calculated from them, depend upon the experimental method and the basis Eor calculation. CMC hydrolysates described in this invention have an intrinsic viscosity of between 50 ml. per gram to 3 ml, per gram, when determined in o.2M sodium chloride. The C;1C hydrolysates h..ve the viscosity value in the range oi' from S to l00 mPa.s, when measured in 20% (by weight) solutian at 25°C
with shear rate 584s 1 using a Haake Viscotester, _ 25 _ VI 500 with sensor system NV (Karlsruhe, Federal Republic of Germany).
Example S: Treatment of Paper with Polymers derived from Carboxymethyl cellulose (CMC) Ten percent of carboxylic cellulose hydrolyzate (intrinsic viscosity = 31.4 ml per gram) dispersion was prepared with deionized water by stirring overnight. The process was carried out by dipping Whatman No. 1 filter pager in the hydrolyzate dispersion in water for 5 minutes. After dipping, the papers were dried in an oven overnight. Three paper samples (hydrolyzate heated, water treated, and untreated papers) were tested for tensile strength, strain limit, modules. and water and oil spreading. For the tensile test, paper was cut to 50 x 2 mm and loaded in the grip of an Instron Universal Testing Machine (Model 1122, Canton PG1 02021).
Results After dipping into hydrolyzate solution, the treated paper was dried and tested. (Table 3).
Table 3. The Change in Properties" of Paper Treated with Carboxymethyl Cellulose Hydrolyzate (ChC) Sample Paper Maximum TensileTangentialStrain Strength Modulus Gimit (atm) (atm!%) (%) CT~SC Hydrolyzate286 168 3.6 C?1C Hydrolyzate385 184 4.2 b2 C;1C Hydrvlyzate297 211 3.0 Water 120 73 3.9 Untreated 160 , 90 2.7 Values are the average of 10 tests for each sample.
Force-elongation tests were performed with a cross-head speed of 5 mm min 1, a chart speed of 500 mm min 1, and a maximum load of 2000gf.
FIGS. 1. 2. 3 for hydrolyzate-treated, water-treated, and untreated papers, respectively.
The resultant values of the maximum tensile strength before rupturing of treated paper showed a 2 to fold increase over untreated or water treated papers when tt:e paper was ~reatetl with the hydrolyzate.
.\lso, the stain limit and mcdulus i7creased by dipping paper in hydrolyzate (Table 3). Dipoi:~g paper in water alor:e decreased t:~e Techanical ~~ ~~r~~
_ 27 strength and increased the strain limit (Table 3).
water and oil spreading on the papers were also tested (Table 4). Paper dipped in the water did not show any difference in water spreading compared to untreated paper, however, it showed more spreading of oil compared to untreated paper.
Hydrolyzate-dipped paper showed much less water spreading than untreated paper.
Table 4. Water and oil spreading on treated and untreated papers Sample Water spreadingl Oil spreading2 (diamqter, mm) (diameter, mm) Carboxymethyl cellulose hydrolyzate-treated 13 26 Water-treated 21 25 Untreated 20 23 Average of Triplicate (-~ s.e.) 1 Measured diameter 5 minutes after spotting 20u1 of water.
2 Measured diameter 30 minutes after spotting 20N1 of oil.
Example 6: Treatment of Paoer with Polymers derived from CarboxymethYl Starch (CMS) -Five percent carboxymethyl starch (C"1S) and carboxyme~hyl starch hydrolyzate (CMSH) dispersions were prepared with deionized water. Two sets of dispersions were made; one was mixed (l0 minutes) at room temperature and the other at' y0°C (to achieve gelatinization). :he coating process was carried out by dipping whatman No. 1 filter paper in each polymer dispersion for S minutes. After dipping, the papers were dried in an oven overnight. The paper samples were tested for tensile strength, strain limit and modules. For the tensile test, paper was cut to 50 x 2 mm and loaded in the grip of an Instron Universal Testing Machine (Model 1122, Canton, MA 02021).
In both sets of samples prepared at roam temperature and at 90°C, the paper treated with carboxymethyl starch hydrolyzate had highe: tensile strength and strain limit than the paper treated with carboxymethyl starch of higher molecular weight. (Table 5). This shows, that the mechanica:
properties of the paper can be improved core using carboxymethyl starch or icwer me?ecu:ar weight.
:,lso the modules was higher when the paper was treated with carboxy~nethyl starch !~ydrolyzates, suggesting an increase in the sti:fness of the paper (Table 5).
Table 5. The Change in Properties" of Paper Treated with Carboxymethyl Cellulose Hydrolyzate (i.?1C) Sample Paper Maximum Tensile Strain Tangential Strength Limit Plodulus (atm) (%) (atm/%) CM Starch 79 3.2 48 (room temp.) CM Starch (90°C) 80 4.9 A3 CM Starch 209 5.2 1'00 Hydrolyzate (CHSH) (room temp.) CM Starch 234 6.9 117 Hydrolyzate C:yISH
(90°C) Example 7: Hydrolyzed Polysaccharide Derivatives as Dewaterinq Aids Polysaccharide derivatives or their hydrolyzates were prepared and dissolved in water. After stirring Eor 10 minutes, the solution was added to Furnish. The Final mixture contained furnish (0.106% w/v solid) and 0.0053°s (w/v) polysaccharide derivatives or their hydrolyzates. The ni:cture was mixed for 10 minutes and pou:ed on basenent paper which serves ~s a screen. ;:~e amount o: water drained was recorded for ~he determination of dewatering rate and final water content was f.
measured. The furnish was dried in the oven and used in the tensile strength test.
Drainage tests Eor furnish treated with charged polysaccharides aad with their hydrolyzates showed initial drainage rates higher than that of furnish alone. (FIG, 4).
T:~e amount of drained water (i.e. an index of dewatering) and the water content of the furnish (i.e. an index of draining) treated with charged polysaccharide derivatives and their hydrolyzates are shown in Table 6, Table 6 Furnish Treatment amount of Water Weight of Retained Drained (ml) Water (g) (Final water Content) CrIC Hydrolyzate 95 5.3 CP1C 9 2 4 . 5 CM Starch Hydrolyzate 94 6.2 CM Starch 94 5.4 Control (Furnish) 93 5.0 :ensile strength ~ests showed that the Eurniah treated with charged polysaccharide hydrolyzates gave high er tensile strength and ;.angential modules than those tested with high molecular weight charged polysaccharides (Table 7), Table 7 Sample Furnish Maximum Tensile Strain Limit Modulus Treatment Strength (~) (atm ~) (atm) CMC Hydrolyzate 114.0 4.7 60 CMC 75.8 5.S 58 CM Starch Hydrolyzate100.0 4.7 CM Starch 85.7 4.3 46 Control (Furnish) 88.4 4.7 Therefore, this experiment shows that polysaccharide derivatives and their hydrolyzate increase the rate of dewatering in the early stage of drainage. Particularly, the polysaccharide derivative hydrolyzates of the invention significantly improve the mechanical properties of the pulp product.
Example 8:
Polysaccharides or their hydrolyzates were prepared and dissolved in a warm water (80°C, C"( starch and its hydrolyzate) or room temcarature water (C~iC and its hydrolyzate). After stirring fur 10 minutes, t::e solution was nixed with'Ca(C03)2 solution. After stirring for l0 minutes, :he mixture was added to furnish. The mi:cture contained furnish with 0.106% (w/v) solid, 0.106% (w/v) Ca(CO3)2, and 0.00575% (w/v) polysaccharides or their hydrolyzates. The test for dewatering was repeated. The draining rates were faster in those mixtures containing hydrolyzate than those of high molecular weight polysaccharides (Figure 5).
The amount of drained water, and the final water content of the samples treated with charged polysaccharides and their hydrolyzates are shown in Table 8. Furnish and Ca(C03)2 treated with hydrolyzates showed a higher dewatering rate,' retaining less water than furnish and Ca(C03)2 treated with higher molecular weight polysaccharide derivatives.
Table 8 Furnish Mixture Amount of Water Weight of Retained Treatment Drained (ml) Water (g) (Final Water Content) C;iC Hydrolyzate 98 4 , 3 CMC 90 5.5 CM Starch Hydrolyzate 94 6.4 CM Starch 89 , The curnish mixture thus produced were dried in an oven and the tensile strength was tested. The test results showed that the samples treated with charged polysaccharide hydrolyzate~ ha'd a higher tensile strength and tangential modules than those treated with high molecular weight charged polysaccharide Eor both CMC and CM starch (Table 9).
Table 9 Sample Paper Maximum Tensile Strain Limit Tangential Strength ' (%> Modules (atm) (atm/3) CMC Hydrolyzate 81.2 . 4.5 43 CMC 61.4 4.4 35 C~1 Starch Hydrolyzate 101.7 5.0 61 CMS 85.7 5.6 49 Control (Furnish) 88.9 4.7 51 It will now be apparent to those s:tilied in the art that other embodiments, improvements, details and uses can be made consistent with the letter and spirit of the foregoing disclosure and within the scope of :h:s patent, which is limited only by t:~e following claims, construed in accordance with the ~ paten law, including the doctrine of equivalents.
What is claimed is:
Claims (20)
1. A paper product treated with a composition comprising a mixture of polymers derived from degradation of a cellulose derivative, the derivative comprising one or more substituents, said mixture of polymers having an average degree of polymerization in the range of about 5 to about 500, and wherein a majority of the polymers has a degree of polymerization and molecular weight such that the polymer conforms to a rod-like configuration.
2. The paper product of claim 1, wherein the paper product is coated with the polymer mixture.
3. The paper product of claim 1, wherein the polymer mixture is incorporated within the paper product.
4. The paper product of claims 2 or 3, wherein the substituents of the cellulose derivative are selected from the group of carboxymethyl, methyl, hydroxypropyl, methylethyl, hydroxyethyl, hydroxymethylethyl, hydroxy-propylmethyl, sulfate, carboxylic acid, carboxylic acid ester, and pyruvate.
5. The paper product of claim 4, wherein the mixture of polymers has an average degree of polymerization in the range of about 7 to about 200.
6. The paper product of claim 1, having a tangential modulus of about 43 atm/percent to about 211 atm/percent.
7. The paper product of claims 1 or 6, having a tensile strength of about 81.2 atm to about 385 atm.
8. The paper product of claim 7, having a strain limit of about 3.0 percent to about 5.0 percent.
9. The paper product of claims 1 or 8, having a strain limit of about 3.0 percent to about 5.0 percent.
10. The paper product of claims 2 or 3, having a tangential modulus of about 117 atm/percent to about 211 atm/percent.
11. The paper product of claims 2 or 3, having a tensile strength of about 209 atm to about 385 atm.
12. The paper product of claims 2 or 3, having a strain limit of about 3.0 percent to about 6.9 percent.
13. A method of increasing the strength of paper, comprising treating the paper with a mixture of polymers derived from a cellulose derivative, said mixture having an average degree of polymerization in the range of about 5 to about 500.
14. A method of paper manufacture having the steps of:
(e) pulping the fibers;
(f) refining the paper stock;
(g) forming the paper sheet; and (h) drying the paper sheet, wherein the improvement comprises the step of:
treating the paper with a mixture of polymers derived from a cellulose derivative, the derivative comprising one or more substituents, said mixture having an average degree of polymerization of about 5 to about 500, and wherein a majority of the polymers has a degree of polymerization and molecular weight such that the polymer conforms to a rod-like configuration.
(e) pulping the fibers;
(f) refining the paper stock;
(g) forming the paper sheet; and (h) drying the paper sheet, wherein the improvement comprises the step of:
treating the paper with a mixture of polymers derived from a cellulose derivative, the derivative comprising one or more substituents, said mixture having an average degree of polymerization of about 5 to about 500, and wherein a majority of the polymers has a degree of polymerization and molecular weight such that the polymer conforms to a rod-like configuration.
15. The method of claim 14, wherein said substituents are selected from the group of carboxymethyl, methyl, hydroxypropyl, methylethyl, hydroxyethyl, hydroxyme-thylethyl, hydroxypropylmethyl, sulfate, carboxylic acid, carboxylic acid ester and pyruvate.
16. The method of claim 14, wherein the step of treating the paper comprises impregnating the paper product with the polymer mixture.
17. The method of claim 14, wherein the step of treating the paper comprises coating the paper product by a method selected from dipping, spraying, or rolling.
18. The method according to any one of claim 14, wherein the step of treating comprises combining the mixture of polymers with furnish.
19. The paper product of claims 2 or 3, wherein the paper product is selected from pulp, paper, and textile products.
20. The method of claim 13, wherein the paper is selected from the group of pulp and paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56601390A | 1990-08-10 | 1990-08-10 | |
| US07/566,013 | 1990-08-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2042560A1 CA2042560A1 (en) | 1992-02-11 |
| CA2042560C true CA2042560C (en) | 2006-07-11 |
Family
ID=24261084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002042560A Expired - Fee Related CA2042560C (en) | 1990-08-10 | 1991-05-14 | Paper composition and uses therefor |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0470871B1 (en) |
| JP (1) | JPH04245997A (en) |
| KR (1) | KR920004666A (en) |
| AT (1) | ATE129764T1 (en) |
| AU (1) | AU648094B2 (en) |
| CA (1) | CA2042560C (en) |
| DE (1) | DE69114208T2 (en) |
| DK (1) | DK0470871T3 (en) |
| ES (1) | ES2081439T3 (en) |
| NZ (1) | NZ239350A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994112A (en) * | 1989-10-30 | 1991-02-19 | Aqualon Company | Hydrophobically modified cellulosic thickeners for paper coating |
| KR100337995B1 (en) * | 2000-03-15 | 2002-05-24 | 정삼열 | Method of making recycleable paper that has touch ffeeling of leather |
| GB0219281D0 (en) * | 2002-08-19 | 2002-09-25 | Unilever Plc | Fabric care composition |
| EP2370511B1 (en) * | 2008-12-03 | 2016-08-24 | Beardow and Adams (Adhesives) Limited | Use of a polysaccharide containing composition in forming protective film on surfaces selected from concrete, metal, stone, glass, wood, cloth, tissue, weave and paper |
| US8652610B2 (en) | 2008-12-19 | 2014-02-18 | Kimberly-Clark Worldwide, Inc. | Water-dispersible creping materials |
| US8506978B2 (en) | 2010-12-28 | 2013-08-13 | Kimberly-Clark Worldwide, Inc. | Bacteriostatic tissue product |
| WO2012130880A1 (en) * | 2011-03-29 | 2012-10-04 | Basf Se | Method for the coating of a cellulose material by using a glucan |
| CN103946448B (en) * | 2011-11-18 | 2016-12-28 | 罗盖特公司 | Coating based on partly soluble high molecular dextrin |
| US11286621B2 (en) | 2015-08-14 | 2022-03-29 | Basf Se | Aqueous surface treatment composition for paper and board |
| CN113502689A (en) * | 2021-07-06 | 2021-10-15 | 云南中烟工业有限责任公司 | Microbial polysaccharide enhanced high-transparency filter stick forming paper and preparation method thereof |
| CN116005489B (en) * | 2022-12-13 | 2024-04-26 | 大家智合(北京)网络科技股份有限公司 | Tea dreg molding packaging paper and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2636951A1 (en) * | 1976-08-17 | 1978-02-23 | Pelikan Werke Wagner Guenther | Degrading starch or starch derivs. in paper prodn. - by treating with amylase to reduce viscosity and simplify coating process |
| CA1254316A (en) * | 1983-02-16 | 1989-05-16 | Donald N. Van Eenam | Functionalized polyacrylamide grafted starch polymer wet strength additives |
| DE3724646A1 (en) * | 1987-07-25 | 1989-02-02 | Basf Ag | METHOD FOR PRODUCING PAPER, CARDBOARD AND CARDBOARD WITH HIGH DRY RESISTANCE |
| FI103583B (en) * | 1989-02-10 | 1999-07-30 | Alko Yhtioet Oy | Enzymatically prepared hydrolyzate of a water-soluble carboxymethyl cellulose |
| FI895708A0 (en) * | 1989-02-10 | 1989-11-29 | Alko Ab Oy | VATTENLOESLIG SOENDERDELNINGSPRODUKT. |
-
1991
- 1991-05-14 CA CA002042560A patent/CA2042560C/en not_active Expired - Fee Related
- 1991-08-10 JP JP3224888A patent/JPH04245997A/en active Pending
- 1991-08-10 KR KR1019910013840A patent/KR920004666A/en not_active Application Discontinuation
- 1991-08-12 AT AT91307417T patent/ATE129764T1/en not_active IP Right Cessation
- 1991-08-12 AU AU81743/91A patent/AU648094B2/en not_active Ceased
- 1991-08-12 DK DK91307417.5T patent/DK0470871T3/en active
- 1991-08-12 DE DE69114208T patent/DE69114208T2/en not_active Expired - Fee Related
- 1991-08-12 NZ NZ239350A patent/NZ239350A/en unknown
- 1991-08-12 ES ES91307417T patent/ES2081439T3/en not_active Expired - Lifetime
- 1991-08-12 EP EP91307417A patent/EP0470871B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0470871A1 (en) | 1992-02-12 |
| CA2042560A1 (en) | 1992-02-11 |
| EP0470871B1 (en) | 1995-11-02 |
| ES2081439T3 (en) | 1996-03-16 |
| DE69114208T2 (en) | 1996-04-25 |
| JPH04245997A (en) | 1992-09-02 |
| DK0470871T3 (en) | 1995-12-04 |
| KR920004666A (en) | 1992-03-27 |
| NZ239350A (en) | 1994-01-26 |
| AU648094B2 (en) | 1994-04-14 |
| DE69114208D1 (en) | 1995-12-07 |
| AU8174391A (en) | 1992-02-13 |
| ATE129764T1 (en) | 1995-11-15 |
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| EEER | Examination request | ||
| MKLA | Lapsed |