CA1249388A - Paper sizing method - Google Patents

Abstract

ABSTRACT
Cationically charged water soluble vinyl addtion polymers provide improved emulsification of alkenyl succinic anhydride sizing agents. Sized paper products prepared from alkenyl succinic anhydride emulsions made with the polymers have superior ink holdout and strength.

Description

~493~U~
INTRO~UC~ION
Alkenyl SUcCinic anhydrides (A~A) us2fuL in the sizing of cellulosic materials have qained considerable commercial success. These materials were first fully disclosed in U.S.
3,10 2,064 which dis~loses a certain class of chemical materials generally having the structural formula O / \ R -. , ' 1', . ', wherein R represents a dimethylene or trimetnylene radical, and wnerein R is a nydropho~ic group containinq more than 5 carbon atoms which may be selected from the qroup consistinq of alkyl, alKenyl, aral~yl or aralkenyl qroups.
In describing the use of the ASA sizes disclosed in this reference, tne patentee inaicates tha~ for e~fective utilization, the sizing agents must ~e used in conjunction with a material wnich is either cationic in nature or is, on the otner hana, capa~le of ionizing or disassociating in such a manner to produce one or more cations or otner positively charqed groups. The cationic agents as they are defined in this reference are disclosed as "alum, aluminum chloride, lonq cnain fatty amines, sodium aluminate, polyacrylamide, chromic sulfate, animal qlue, cationic thermosettin~ resins, an~ polyamide polymers". Tne patentee particularly points out as preferred cationic agents various cationic starcn derivatlves includlns primary, secondary, tertiary, or quarternary amine starcn derivatlves and other cationic nitroqen substituteo starch derivatives~ as well as ` ~LZ49381~ ~

cationic sul~onium an~ phosphonium starch derivatives. Such derivatives, as stated by the patentee, may be prepared from all types of starches includinq corn, tapioca, potato, etc.

witn the growing com~ercial use of sizes of the type a~ove described, serious problems have remalned in the application of ~the sizes to paper stoc~ or pulp prior to its formation into ~sheet or otner useful forms. Part of the proDlem has ~een t~at the ASA sizing n\aterials are not water soluble, and must, Ijaccordingly, be uniformly suspenaed in the pulp so that the size i can make adequate contact with the cellulosic fibers and thus create the desired ef~ect on tne final product.
While 'ne cationic agents disclosed in U~S. 3,103,~61 have ! met witn success, there has ~een a need within the paper industry tv produce a more eefective, "cationic a~ent" eor ASA sizes. In addition, such cationic aqent would preferaDly aid ln the ,lretention of the size on the fiher, and would increase, where desired, tne wet and/or dry strenqtn of tne final sheet ma~erial.

~l Accordingly, Ihis invention seeks to provide a group of additives ,; which will serve to emulsify or disperse the ASA size in the pulp and allow for retention of the size onto the fiber.
This invention proposes the use of water soluble cationic vinyl addition polymers having molecular weights above 10,000 and below 1,000,000 as emulsifiers for ASA sizing materials.

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~, , 1 ~
; , ~249388 T~E INVENTION
Our invention, as briefly stated a~ove, is to utilize cationic water SOluDle vinyl addition polymers having molecular weights greater tnan 10,0~0 and below 1,000,000 as additives and emulsi~yinq agents for A~A Sizes, The use of such cationic vinyl addition polymers serve as useful emulsifying agents ~or ASA
size, and in addition, increases tne retention of the size upon the cellulosic sheet.
Tne ASA sizes to wnich tnis inventlon lS applicaDle include those mentiones in U.S. Patent 3,102,061, 4,040,900. 3,968,005.
and 3,821,U69.

Tne ASA sizes use~ul in the suD~ect of this invention are generally described by the followinq structural ~ormula:
O
/c\
O \ R - Rl C

wherein R rePresents a dimethylene or trimetnylene radical, and wherein Rl is a hydropnoDlc group containing more ~nan 5 carbon atoms which may oe selected from tne group consistinq o~ alkyl, al~enyl, aralkyl or aralkenyl groups.

In a particular u~e~ul embodiment ot this invention, a surfactant Aas also Deen emPk~yed in ma~ing the ASA sizes of thls invention. Tnis sur~actant may De anionici non-ionic, or cationic in nature. Surfactants employea nave qenerally Deen water solu~le and have had ~L~ values ranging from aDout 8 to about 80 or higher, and preferably from a~out 8-15. ~rhe ~493~8 surfactant is generally used to prepare the ASA size by simply mixing it with the raw ASA material. The ASA size used in this invention accordingly, and in a preferred embodiment of this invention, will generally contain 75-99.5 parts by weight of ASA and preferably 90-99 parts by weight of ASA with 0.5-25 parts, preferably .75-10 parts, and most preferably 1.0-5 parts by weight of surfactant.
The surfactants are preferably added to the ASA prior to emulsification in the aqueous medium. Surfactant can also be added to the aqueous medium prior to the addition of the ASA.
The surfactants useful in this invention are further described in United States 4,040,900. The relevant parts of United States 4,040,900 begin at column 4, line 54 continue through column 5, line 46. Other portions of this patent are, however,relevant.
Classes of materials useful as the surfactants in this invention include: ethoxylated alkyl phenols, such as nonyl phenoxy polyethoxy ethanols and octyl phenoxy polyethoxy ethanols; poly ethyleneglycols such as PEG 400 mono-oleate, and PEG 600 dilaurate; as well as other materials including certain ethoxylated phosphate esters.
Preferred surfactants for use in our invention are GAFAC*
RM510 and GAFAC* RE610, both free acids of complex organic phosphate esters, manufactured by the GAF Corporation.

THE I~ATER SOLUBLE POLYMERS
Water soluble polymers which are useful cationic agents in this invention include water soluble vinyl addition homopolymers * Trade Mark Il 12~3815 ¦and copolymers havinq molecular welghts greater than 10,000 and ¦below 1,000,000 where at least 10 weight percent and up ~o 100 ¦weight percent o~ the mer content of the polymer is a cationic ¦monomer, or cationically modi~ied monomer. Preferably a least ¦15 and up to 95 weight percent o~ the mer uni~s in the polymer ¦may be cationic or cationically modified monomers. ~ost ¦pre~era~ly from 20 ~ 75 weight percent by weight of the mer units ¦in the polymer or copolymer are cationic or cationically modi~ied.
¦ Tne polymers selected for use in this invention qenerally ¦have a molecular weight o~ greater than 10,000 and less than ¦1,000,~00. Polymers o~ this type should qenerally be water ¦soluble, and a pre~erred molecular weight has been ~ound to ~e between 20,000 and 750,000. MOSt prefera~ly, the molecular weignts o~ the polymers employed ran~e from 5U,000 to 150,0U0.
Polymers which can De employed in the practice of tnis invention include, but are not limited to the ~ollowing exemplarY
copolymers and homopolymers: acrylamide-dimethylaminoethyl-acrylate, acrylamide-dimethylaminoethylacrylate quaternaries, ¦acrylamide-diethylaminoethylacrylate, ¦acrylamide-d1ethylaminoethylacrylate quaternaries, acrylamide-dimethylaminoethylmethacrylate, acrylamide-dimethylaminoethylmethacrylate ~uaternaries, acrylamide-diallyldimethyl ammonlum chloride, polydiallyl-dimethyl ammonium chloride, polydimethylaminoetnylme~hacrylate and its ~uaternaries, polymethacrylamidopropyltrimethyl ammonium chloride; and, acrylamide-metnacrylamidoproPyltrimetnyl ammonium chlorlde.

~24938~

Also useful are polymers and coPolymerS o~ acrylamide which have been subjected to a "~annicn" reaction with formaldehyde and a lower alkyl secondary amine. These polymers may or may not be quaternized.
As seen, all o~ the polymers use~ul in thls invention are cationically charqed and are wate~-soluDle. ~any are prepared from vinyl addition monomers, althouqn condensation polymers will also worK. Since the nu~ber of possible cationically charqed monomers tnat will produce a water soluDle polymer is essentially unlimited, and it is expected that all water-soluble cationically cnar~ed vinyl addition polymers having a molecular weight o~
10,~00 or ~re but less than 1,000,000 will wor~, we do not wish to De limited to tne above qiven list~
The polymers employed, as stated above, may be coPolymers and even terpolymers of various vinyl additlon monomers. While acrylamide is a preferred nonionic monomer ~or use in preParing copolymers useful in this invention, other nOnlOniC monomers such as methacrylamide and even certain anionically charged monomers sucn as acrylic acid, methacrylic acid, various sulfonated water soluble vinyl addition monomers, etc. can be emPloyed.
Polymers as used ln this invention may oe in the form o~
water-in-oil emulsions (sucn as those described in U.S. Re.
28,474 and 28,576, dry powders, or dilute aqueous solutions.
In order to employ the polymers of the subject in~ention in the emulsificatio-l of ASA sizes, an aqueous solution must fir~t be prepared ¦of the polymer. In the case of the water-in-oil emulsions of vinyl addition p~lymers, we have found the water soluble surfactants used to invert the water-in-oil emulsions 'I
'I

Il . ~24938~ ( have no detrimental ef~ect on the actlVitY of the polymer used to ¦emulsi~y the ASA size. When preparinq a polymer solution from a ¦water-in-oil emulsion polymer, a use~ul method or device ~or ¦~orming the solution is exemplified in U~S. Patent 4,057,223 which discloses a mixing block.
Dependinq upon the molecular weight and cationic charge of the polymer, from 0.01~ tc 25~, and Preferably .01-10~ by weight of the final size emulsion to be added to the pulp ~urnish may be polymer.
The ASA emulsions fed to the pulp slurry accordinq to tnis invention will generally contain:
50 - 99.Y~ ~Y weight water .01 - 50% ~y weign~ ASA
.001 - 25.0% by weight of the water soluble polymer PreferaDly, these emulsions will contaln:
50 - 99.9~ water .01 - 40~ ASA
.~10 - 10~ polymer ~ost pre~eraDly tne ASA emulsion contains .01-7.5 and qenerally .01 - 5.0 parts polymer.
The polymers are thus used in preparation of tne dispersions or emulsions of the ASA sizinq material.
Tne polymers of this invention may be used to emulsify the ASA, or may be added to previously ~ormed A~A emulsions. In ei~ner case, the polymer will increase the per~ormance o~ the emulsion compared to emulsions not containinq tne polymer. ~hen the polymer is added to an A~A emulsion that has already been 4938~ ( formed, conventional emulsifying agents should be used in addition to the polymer. When added or used durin~ the make-up of the ASA emulsion, no additional emulsifier need be employed.
In order to test the subject invention, the ~ollowing experiments were conducted. Tne polymers listed ~elow were obtained commercially or prePared in the form indicated.
'I .
EXAMPLE 1.
Solution acrylamide copolymers o~ types DMAE~-~eCl Quat, MAPTAC, and PolyDADMAc of molecular weights ranging from 10,000 jto 400,000 were evaluated as ASA emulsificaeion and retention aids. Thete novel sizing compositions were compared in terms of ¦ASA particle size, physical emulsion staDility ana sizing performance to conventional ASA emulsions in water or cationic ¦Istarch. Description of these polymers are qiven in TaDle I.
ASA emulsions in water were prepared by com~ining 95 parts of distilled wa~er and 5 parts of ASA in an E~er~acn ~¦semi-microemulsion cup. The mixture was dispersed for 3 minutes ,~at high speed. The emulsion formed was diluted with distilled water to 0.5~ percent ASA solids basis and used in Example 1.
ASA emulsions in cationic starc~ were prepared oy first hydratinq 5 parts of a preqelatinized cationic potato starch in 95 parts o~
~water and agi~ating for 30 minutes. Size emulsions weLe ~hen prepared ~y com~ining 75 parts of the starcn solution with 25 parts of ASA in the emulsion cup and disperslnq for 20 seconds.
! Tnis emulsion was diluted to 0.50 percen~ ASA solids basis and used in Example 2. Lastly, ASA emulsions in vinyl addition polymers were prepared ~y dispersing ASA in Polymer solutions at il _ g _ 1~ ^

4~3~ `

a ratio o~ 5:1 dry solids basls. These emulslons were diluted to 0.50 percent A~A solids basis by the me~hod described above.
Examples 3-8 lllustrate the novel use o~ tnese addition polymers.

The ASA emulsions were tested seParately in a Paper slurry of composition 50 percent recycled corrugated box~oard, 50 percent recycled newsprint. otner slurry parameters were 0.5 percent consistency, 400 Canadian Standard Freeness, pH 7.5, and 25 deqrees Celsius to wnich was added 12.5 parts per million o~
hydrated aluminum sulf ate. Handsheets of basls weight 50 pounds per 3300 square feet were prepared in accordance with TAPPI T-205 procedures. The sizinq compositions listed above were added to tne paper slurry shortly be~ore wet-web foFmation at dosages o~
0.10 and 0.15 percent on paper soLids. Handsheets were immediately aried on rotary drum to 98 percent solids basis.
Results are shown in Ta~le I.

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EXA~PLE ~.
___ Vinyl addi~ion polymers, such as copolymers of acrylamide with D~AEM-MeCl quat or MAPTAC, and polyDADMAC, were further evaluated as ASA emulsif ication and retention aids. These novel s~zinq compositionS were comPared in terms of ASA emulsion particle size, physical emulsion staDility with aging, and sizinq ¦per~ormance to conven~ional ASA emulsions in water or cationic starcn. Tne molecular weight of these polymers ranged from ~10,000 to 400,000. A description of these polymers is shown in I TabLe II.

il ASA emulsions in water were preparea by comDininq 95 parts of Ildistilled .!ater and 5 parts o~ ASA in a la~oratory 8 ounce j¦Osterizer cup. The mixture was dispersed at hi~h speed for 3 l¦minutes. The emulsion ~ormed was diluted with distilled water to ¦10.50 percent ASA solids basis and used in Example 9. ASA
! emulsions in cationic starcn solutions were prepared by first hydrating 5 parts of a pregelatinized cationic potato starch in ~i95 parts of water and agitating ~or 30 minutes. Size emulsions ''were then prepared by COmDining ~5 parts of the starch solution ¦Iwith 5 parts of ASA in the Osterizer cu~ and dispersinq the size ! for 25 seconds. Tnis emulsion was diluted to 0.50 percent ASA
solids basis and used in Example 10~ ASA emulsions in vinyl addition polymers were preparea by dispersing ASA in the polymer solutlons at a ratio of 1:1 ASA to polymer solids in the !jOsterizer cup ~or 5 to 30 seconas. These emulsions are then dil-uted to 0.50 percent ASA solids as describeâ ahove. ExamPles 11-16 illustrate the novel use o~ ;nese vinyl adaition polymers.

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Il Il ~z493~
Each ASA emulsion was tested sep~rately in a paper slurry of composition S0 percent ~leached softwood kraft and 50 percent bleached hardwood kraft pulps. The other slurry parameters were 0.5 percent consistency, 330 Canadian Standard Freeness, pH 7.3, and 27 de~rees Celcius. Handsneets of Dasis weight 50 pounds per 3300 square feet were prepared in accordance with TAPPI T-205 procedures. Tne sizing composltions listed aoove were added to the paDer slurry snortly before wet we~ formation at the dosa~e of 0.20 percent ASA solids on paper solias. ~an~sheets were immediately pressed to approximately 50 percent residual moisture and dried on-a rotary drum dryer to 98 percent paper solids basis. Results are shown in the attached Ta~le II.

~Z~38~

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` 124938B
EXA~PLE 3 The followin9 examples further illustrate tne novel use of acrylamide copolymers o~ type DMAEM-~eSQ, D~AEA-~eSQ, D~AEA-~eSQ
ana DADMAC o~ molecular weiqhts qreater than 1,000,000 as emulsi~iers and retention aids for alkenyl succinic anhydride sizin~ compositlons. The ASA emulsions thus formed were compared ¦in terms of particle size and sizing performance with respect to ! ASA water emulsions and conventional emulsions prepared from ilcationic starcn.
¦~ For comparison, ASA emulsions in water were prepared by ¦¦combininq 95 parts o~ distilled water and 5 parts o~ A~A in an EberDach semi-microemulsion cup and dispecsin~ the size for 60 I! seconds. The resulting emulsion was diluted to 0.50 percent ASA
¦lsolids basis with water and used in Example 17. The ASA
¦ emulsions in cationic starch were Prepared ~y first hydrating three parts o~ a preqelatinized cationic potato starch in 97 parts agitated cold water for 30 minutes. Emulsions were then jprepared a~ two AS~ to starcA solid ratios o~ 10:1 and 3:1 by dispersinq 30 parts of A~A in 70 parts of 3 percent cationic starch or 9 parts of ASA in 91 parts of 3 percent cat1onlc starch llrespectively with the aid of the seml-microemulsion cup. The l,resulting emulsions were diluted to ~.S percent ASA solids ~asis i witn water and used in Examples 19 and 20 accordin~lv.
¦ Polymer solutions were prepared Dy hyarating 0.6 parts (as j~polymer solids) of those copolymers of acrylamide listed ~elow in ¦Ig9.4 parts ot water respectively, allowin9 suf~lcient time and 'Imixinq for comPlete hydration. Emulsions were than prepared at ~two ASA to polymer solids ratios of 10:1 and 3:1 Dy dlspersinq 6 l l l 'I !

lZ~938~
parts of ASA ln ~4 parts of 0.6 percent polymer solids solution or 1.8 parts of ASA in 98.2 parts o~ 0.6 percent polymer solids solu~ion respectively with tne aid of the seml-microemulsion cuP.
A further dilution to 0.5 percent ASA solids was then taken.
Tne ollowing example illustrates the advantages offered by this invention: the ability o~ these cationic water soluble acrylamide copolymers to initiate an ASA emulsion and to render the ASA emulsion particles cellulose su~stantive.
Eacn of the oelow cited ASA emulsions were separately added to a 0.5 percent conslstency pulp slurry o~ composition 40 percent bleacned nardwooa s~l~ate pulp, 40 percent bleached softwood sulfate pulp, and 2~ Percent calcium carbonate of 300 Canadian Standard Freeness (pH d.2). Handsheets o~ oasis weiqht 50 pounds per 3300 square ~eet were prepared in accordance with TAPPI T-205 procedures. Emulsions o~ ASA were added to the pul~
slurry shortly be~ore wet-weD ~ormation at dosages ~f 0.250 and ~.00 percent on dry pulp solias. Handsheets were immediately dried on a rotary drum dryer to 98 percent solids basis (~ percent residual moisture). Results are shown in Table III.
Tnls example clearly illustrates tne novel use o~ cationic vinyl aàdition copolymers as ASA emuls1~ication aids and emulsion retentisn aids. Improved water resistance i5 realized over conventional ASA in water or cationic starch emulsions.
Secondly, the imProvea water resistance offered by thls invention cannot be attrlbuted sim~oly to improved papermachine retention as demonstrated by separate additions o~ tnPse same cationlc polymers to tne paper ~urnisn.

1~4938~

The use of polymers in this molecular weiqht ranqe, however, led to the formation of tacky deposits and unstable emulsions.
Fusther researcn as exemplified herein has shown that polymers having a molecular weiqht greater than 10,000 ~ut lower than 1,000,000, and preferably ~rom 20,000 to 750,000, per~ormed essentially equivalent to polymers havinq higher molecular weiqnt. In addition, the use of polymers having molecular weights in our preferred range of from 50,000 - 150,000 led to the elimination o~ the deposit formation noted above, and increased, we believe, the stability of the ASA emulsi~ns so prepared.

~;~4938B

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Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In an improved method for the preparation of an emulsified alkenyl succinic anhydride sizing agent useful in the preparation of sized paper products, such emulsion containing water, an alkenyl succinic anhydride, and a cationic agent, the improvement comprising using as the cationic agent a water soluble cationic vinyl addition polymer having a molecular weight of between 10,000 and 1,000,000.

2. The method of claim 1 wherein the cationic vinyl addition polymer is selected from water soluble vinyl addition polymers having molecular weights greater than 10,000 and less than 1,000,000, said polymer having at least 10 weight percent and up to 100 weight percent of the mer content of the polymer made from a cationic or cationically modified vinyl addition monomer.

3 The method of Claim 2 wherein the cationic or cationically modified vinyl addition monomer is selected from the group consisting of:
a. diallyldimethyl ammonium chloride;
b. methacrylamidopropyltrimethyl ammonium chloride;
c. dimethylaminoethylmethacrylate;
d. dimethylamlnoethylmethacrylate quaternaries;
e. dimethylaminoethylacrylate;
f. dimethylaminoetnylacrylate quaternaries;
g. diethylaminoethylacrylate;
h. diethylaminoethylacrylate quaternaries;
i. acrylamide reacted with formaldehyde and a lower secondary amine through the Mannich reaction; and j. manniched acrylamide quaternaries.

4. The method of Claim 1 wherein the polymer is present in the alkenyl succinic anhydride size emulsion at a level of from 0.01 - 10.0 percent parts by weight polymer solids.

5. The method of Claim 1 wherein the polymer is present in the alkenyl succinic anhydride size emulsion at a level of from .01 - 5.0 percent parts by weight polymer solids.

6 In a method for the sizing of paper using an alkenyl succinic anhydride size wherein an emulsion of alkenyl succinic anhyride is applied to the paper stock, the improvement comprising using as an emulsifier for the alkenyl succinic anhydride size, a water soluble cationic vinyl addition polymer having a molecular weight greater than 10,000 and less than 1,000,000.

7. The method of Claim 6 wherein the cationic water soluble vinyl addition polymer is selected from the group consisting of homo and copolymers of one or more of the following monomers:
a. diallyldimethyl ammonium chloride;
b. methacrylamidopropyltrimethyl ammonium chloride;
e. dimethylaminoethylmethacrylate;
d. dimethylaminoethylmethacrylate quaternaries;
e. dimethylaminoetnylacrylate;
f. dimethylaminoethylacrylate quaternaries;
g. diethylaminoethylacrylate;
h. diethylaminoethylacrylate quaternaries;
i. acrylamide reacted with formaldehyde and a lower secondary amine through the Mannich reaction; and j. manniched acrylamide quaternaries.

8 The method of Claim 6 wherein the emulsion containing the water soluble polymer is added to the paper stock-

9 An emulsion of alkenyl succinic annydride comprising:
a. 50 - 99.9 percent by weight water b. .01 - 40 percent by weight of an alkenyl succinic anhydride c. .001 - 10.0 percent by weight polymer solids of a water soluble cationic vinyl addition polymer having a molecular weight greater than 10,000 and less than 1,000,000.

10. The emulsion of Claim 9 wherein the water soluble cationic vinyl addition polymer is selected from the group consisting of homo and copolymers of:
a. diallyldimethyl ammonium chloride;
b. methacrylamidopropyltrimethyl ammonium chloride;
c. dimethylaminoethylmethacrylate;
d. dimethylaminoethylmethacrylate quaternaries;
e. dimethylaminoethylacrylate;
f. dimethylaminoethylacrylate quaternaries;
g. diethylaminoethylacrylate;
h. diethylaminoethylacrylate quaternaries;
i. acrylamide reacted with formaldehyde and a lower secondary amine through the Mannich reaction; and j. manniched acrylamide quaternaries.