CA1100264A - Sizing method and sizing composition for use therein - Google Patents
Sizing method and sizing composition for use thereinInfo
- Publication number
- CA1100264A CA1100264A CA271,958A CA271958A CA1100264A CA 1100264 A CA1100264 A CA 1100264A CA 271958 A CA271958 A CA 271958A CA 1100264 A CA1100264 A CA 1100264A
- Authority
- CA
- Canada
- Prior art keywords
- sizing
- accelerator
- poly
- sizing agent
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/13—Unsaturated aldehydes, e.g. acrolein; Unsaturated ketones; Ketenes ; Diketenes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
- D21H17/08—Isocyanates
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Catching Or Destruction (AREA)
Abstract
Abstract of the Disclosure Disclosed is a method for sizing paper wherein the sizing agent employed is a hydrophobic cellulose reactive sizing agent such as a ketene dimer sizing agent. There is employed in com-bination with the sizing is improved substantially. Disclosed also is a novel sizing composition comprised of the sizing agent and the accelerator, the accelerator being a poly(diallylamine)-epihalohydrin resin.
Description
~ 26~ Dumas Case 5 This invention relates to the production of sized paper and sized paperboard~
In particular, this invention relates to the manufacture of sized paper and sized paperboard wherein the sizing agent employed is a hydrophobic cellulose reactive sizing agent such as a ketene dimer sizing agent and there is employed in combination therewith a new sizing accelerator to provide substantially higher off-the-machine sizing than when the cellulose reactive sizing agent is used alone.
U.S. patent 3,840,486 discloses water-soluble, thermoset-table resinous compositions derived by reaction of dicyandiamide, an ammonium salt, formaldehyde and an acid salt of a water-soluble aminopolyamide such as the water-soluble aminopolyamide derived by reaction of adipic acid and diethylenetriamine. The resinous com-positions of patent 3,840,486 accelerate the sizing imparted to paper by cellulose reactive sizing agents such as ketene dimers, acid anhydrides and isocyanates. By employing the resinous compo-sitionsof patent 3,840,486 in combination with the above sizing agents for paper, higher off-the-machine sizing is provided than 20 when using equivalent amounts of the sizing agent alone.
United Kingdom patent specification No. 1,373,788 discloses the use of dicyandiamide-formaldehyde condensates as sizing accel-erators for ketene dimer sizing agents.
U.S. patent 3,409,500 discloses a process for the manufac-ture of sized paper which comprises separately adding an aqueous anionic dispersion of hydrophobic organic cellulose-reactive paper sizing carboxylic anhydride particles to an aqueous suspension of cellulose papermaking fibers and a water-soluble cellulose-sub-stantive cationic polyamine having a molecular weight in excess of 30 l,000, the amount of said polyamine being at least sufficient to deposit said anhydride particles on said fibers and to accelerate the rate at which said anhydride develops its sizing properties on cellulose fibers at 190F.-250F., sheeting said suspension to form a water-laid web, and drying said web at a temperature between 190F. and 250F.
In U.S. patent 3~409,500, at column 3, lines 61-70, it is stated that among the most efficient cationic polymers are the adipic acid-polyalkylenepolyamide-epichlorohydrin polymers, pre-pared by condensing adipic acid with a polyalkylene-polyamine thereby forming a polyamidepolyamine, and reacting this polymer with epichlorohydrin. Methods for the preparation of agents of this type are disclosed in U.S. patents 2,926,116, 2,926,154 and ` 3,329,657.
The cationic polymers of U.S. patents 2,926,116 and
In particular, this invention relates to the manufacture of sized paper and sized paperboard wherein the sizing agent employed is a hydrophobic cellulose reactive sizing agent such as a ketene dimer sizing agent and there is employed in combination therewith a new sizing accelerator to provide substantially higher off-the-machine sizing than when the cellulose reactive sizing agent is used alone.
U.S. patent 3,840,486 discloses water-soluble, thermoset-table resinous compositions derived by reaction of dicyandiamide, an ammonium salt, formaldehyde and an acid salt of a water-soluble aminopolyamide such as the water-soluble aminopolyamide derived by reaction of adipic acid and diethylenetriamine. The resinous com-positions of patent 3,840,486 accelerate the sizing imparted to paper by cellulose reactive sizing agents such as ketene dimers, acid anhydrides and isocyanates. By employing the resinous compo-sitionsof patent 3,840,486 in combination with the above sizing agents for paper, higher off-the-machine sizing is provided than 20 when using equivalent amounts of the sizing agent alone.
United Kingdom patent specification No. 1,373,788 discloses the use of dicyandiamide-formaldehyde condensates as sizing accel-erators for ketene dimer sizing agents.
U.S. patent 3,409,500 discloses a process for the manufac-ture of sized paper which comprises separately adding an aqueous anionic dispersion of hydrophobic organic cellulose-reactive paper sizing carboxylic anhydride particles to an aqueous suspension of cellulose papermaking fibers and a water-soluble cellulose-sub-stantive cationic polyamine having a molecular weight in excess of 30 l,000, the amount of said polyamine being at least sufficient to deposit said anhydride particles on said fibers and to accelerate the rate at which said anhydride develops its sizing properties on cellulose fibers at 190F.-250F., sheeting said suspension to form a water-laid web, and drying said web at a temperature between 190F. and 250F.
In U.S. patent 3~409,500, at column 3, lines 61-70, it is stated that among the most efficient cationic polymers are the adipic acid-polyalkylenepolyamide-epichlorohydrin polymers, pre-pared by condensing adipic acid with a polyalkylene-polyamine thereby forming a polyamidepolyamine, and reacting this polymer with epichlorohydrin. Methods for the preparation of agents of this type are disclosed in U.S. patents 2,926,116, 2,926,154 and ` 3,329,657.
The cationic polymers of U.S. patents 2,926,116 and
2,926,154 are disclosed in U.S. patent 3,483,077 as being useful retention aids for ketene dimer sizing agents whereby sizing is improved as compared to cationic starch retention aid.
U.S. patent 3,575,796 discloses a method for the sizing of paper and paperboard products which comprises intimately dispers-- ing, within the aqueous pulp slurry, or applying to a prepared - paper web, an aqueous emulsion of an N-substituted aziridine com-pound which is prepared by means of the reaction between a car-bonyl substituted, alpha, beta-ethylenically unsaturated compound 20 such as distearyl maleate and an alkyleneimine such as ethylene-imine. The sizing agent can be uniformly dispersed with a cationic emulsifier, such as a cationic starch, for better retention on the fibers. Column 4, lines 1-44 of U.S. patent 3,575,796 discloses other cationic agents for use in aiding in the retention of the sizing agents of the invention among which are cationic thermoset-ting resins such as the reaction products of dibasic acids, poly-alkylenepolyamines and epihalohydrins. It is stated also at column 4, lines 45-62, that the cationic agents are also useful as emulsifiers for the sizing agent.
U.S. patent 3,666,512 discloses compositions comprising hydrophobic cellulose-reactive paper-sizing carboxylic acid anhy-drides and a catalyst which accelerates the rate at which the an-hydride develops its sizing properties when deposited on cellulose from aqueous medium and heated. The catalyst or promoter for the _ 3 _ .
anhydride size is a water-soluble cationic salt of a cellulose-substantive water-soluble polyamine. Suitable cationic agents are set forth in the table in column 7 of the paper. Among the cat-ionic agents is an aminopolyamide--epichlorohydrin resin, the aminopolyamide being derived from diethylenetriamine and adipic acid.
Canadian patent 873,777 discloses a method for improving the wet strength, dry strength and resistance to penetration by liquids of unsized paper comprising imbibing the paper with an 10 amine oxide capable of swelling the paper fibers and a ketene dimer paper sizing agent, heating the paper to swell the paper fibers and removing the amine oxide from the paper.
-U.S. patent 3,046,186 relates to the manufacture of sized ; paper by the beater-addition process wherein an aqueous cationic dispersion of a hydrophobic ketene dimer is added to an aqueous suspension of cellulosic fibers. The sized paper is manufactured by forming an aqueous suspension of cellulose paperma~ing fibers and adding thereto an emulsion of a hydrophobic ketene dimer in an aqueous medium containing a cationic dispersing agent which may be 20 a monomeric or high molecular weight hydrophilic or water-soluble basic nitrogenous surface-active agent. The dispersing agents are set forth in columns 3 and 4 of patent 3,046,186.
U.S. patent 3,006,806 discloses the conjoint use of an or-ganic cationic polymer with a ketene dimer in the sizing of paper.
Cationic polymers disclosed are melamine-formaldehyde resins (as described in U.S. 2,345,543 to Wohnsiedler and Thomas and U.S.
2,559,220 to Maxwell and Lanes); urea-formaldehyde resins (as des-cribed in U.S. 2,657,132 to Daniel, Landes and Suen); cationic corn starch; guanidine-formaldehyde resins (U.S. 2,745,744 to 30 Weidner and Dunlap); alkylenepolyamine-halohydrin resins (as des-cribed in U.S. 2,601,597 to Daniel, Wilson and Landes); and cat-ionic urea-formaldehyde resins (as described in British patents 675,477 and 677,184).
U.S. patent 3,084,092 relates to paper manufactured by the 110~264 `.
conjoint use of an amino resin and a hydrophobic organic isocyanate. Amino resins descrlbed in United States patent 3,084,092 are polyfunctional halo-hydrin resins o Daniel et al, United States patent 2,595,934; The dicyandi-amide-formaldehyde-aminepolymers of Dudley et al, United States patent 2,596,014; the urea-mono-substituted urea resins of Schiller et al, United States patent 2,698,787; the polyaminepolyamide linear polymers of House et al, United States patent 2,729,560; the polymers formed by copolymerizing acryl-amide and acrylic acid in 9:1 molar ratio; the sulfonated dimethylolurea resins of United States patent 2,582,840; and the aminosulfuric acid-melamine-formaldehyde resins of United States patent 2,688,607.
- In accordance with this invention, applicant has found new sizing accelerators for use with hydrophobic cellulose reactive sizing agents such as ketene dimers, acid anhydrides, and organic isocyanates.
According to one aspect of the invention there is pTovided in the method of producing sized paper wherein there is employed an aqueous emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides, and organic isocyanates, the improvement wherein there is employed in combination with the sizing agent a sizing accelerator, said accelerator being a poly(diallylamine)-epihalohydrin resin in an amount sufficient to increase the off-the-machine sizing effect of the sizing agent.
According to another aspect of the invention there is provided a sizing composition for cellulose fibers consisting essentially of an aqueous emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides and organic isocyanate containing a sizing accelerator, said sizing accelerator being a poly(diallyl-amine)-epihalohydrin resin and being present in an amount sufficient to increase the off-the-machine sizing properties of the sizing agent.
According to a further aspect of the invention there is provided a sizing composition for cellulose fibers consisting essentially of an aqueous emulsion of a hydrophob~c cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides, and organic isocyanates ~ -5-f ~A
`` 11~264 containing a sizing accelerator, said sizing accelerator being selected from a water.soluble poly~diallylamine)~epihalohydrin resin and a water-soluble poly~N~methyldiallylamine).epihalohydrin resin, the proportion of accelerator to sizing agent being in the range of 1:1 to 3:1.
The sizing accelerators used in this invention are poly~diallyl-amine)-epichlorohydrin resins as disclosed and described in United States patent 3,700,623.
The poly~diallylamine)-epihalohydrin resins used in this invention comprise the resinous reaction product of ~A) a linear polymer having units of the formula R ~CH2 R
- H2C-~ C~
2 ~ N ~ 2 R' where R is hydrogen or lower alkyl and R' is hydrogen, alkyl or a substituted alkyl group and (B) an epihalohydrin.
In the above formula, each R can be the sa~e or di~ferent and, as stated, can be hydrogen or lower alkyl. The alkyl groups contain from 1 to 6 !; .carbons and are preferably methyl, ethyl, isopropyl or n-butyl. R' of the formula represents hydrogen, alkyl or substituted alkyl groups. The R' alkyl groups will contain from 1 to 18 carbon atoms ~pree~ably fro~ 1 to 6 carbon atoms) such as -5a-2~4 methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and octadecyl. R' can also be a sub-stituted alkyl group. Suitable substituents include, in general, any group which will not interfere with polymerization through a vinyl double bond. Typically, the substituents can be carboxylate, cyano, ether, amino tprimary, secondary or tertiary), amide, hydrazide and hydroxyl.
Polymers having units of the above formula can be produced by polymerizing the hydrohalide salt of a diallylamine CH~ CH2 !i 11 R-C C-R (II) CE~ CH2 i, .
where R and R ' are as indicated above, either alone or as a mix-ture with other copolymerizable ingredients, in the presence of a free radical catalyst and then neutralizing the salt to give the polymer free base Specific hydrohalide salts of the diallylamines which can be 20 polymerized to provide the polymer units of the invention include diallylamine hydrochloride; N-methyldiallylamine hydrobromide;
2,2'-dimethyl-N-methyldiallylamine hydrochloride; N-ethyldiallyl-amine hydrobromide; N-isopropyldiallylamine hydrochloride; N-n-butyldiallylamine hydrobromide; N-tert-butyldiallylamine hydro-chloride; N-n-hexyldiallylamine hydrochloride; N-octadecyldiallyl-amine hydrochloride; N-acetamidodiallylamine hydrochloride; N-cyanomethyldiallylamine hydrochloride; N-~-propionamidodiallyl-amine hydrobromide; N-carboethoxymethyldiallylamine hydrochloride;
N-~-methoxyethyldiallylamine hydrobromide; N-~-aminoethyldiallyl-30 amine hydrochloride; N-hydroxyethyldiallylamine hydrobromide and N-acetohydrazide substituted diallylamine hydrochloride.
In preparing the homopolymers and copolymers for use in this invention, reaction can be initiated by redox catalytic system. In a redox system, the catalyst is activated by means of a reducing - 1113~2~4 agent which produces free radicals without the use of heat. Re-ducing agents commonly used are sodium metabisulfite and potassium metabisulfite. Other reducing agents include water-soluble thio-sulfates and bisulfites, hydrosulfites and reducing salts such as the sulfate of a metal which is capable of existing in more than one valence state such as cobalt, iron, manganese and copper. A
specific example of such a sulfate is ferrous sulfate. The use of a redox initiator system has several advantages, the most import-ant of which is efficient polymeri~ation at lower temperatures.
10 Conventional peroxide catalysts such as tertiary-butyl hydroper-oxide, potassium persulfate, hydrogen peroxide and ammonium per-sulfate used in conjunction with the above reducing agents or metal activators, can be employed.
As stated above, the linear polymers of diallylamines can contain different units of formula ~I) and/or contain units of one or more other copolymerizable monomers. Typically, the comonomer is a different diallylamine; a monoethylenically unsaturated com-pound containing a single vinyl or vinylidene group; or sulfur di-oxide, and is present in an amount ranging from 0 to 95 mole per-20 cent of the polymer. Thus the polymers of diallylamine are linearpolymers wherein from 5% to 100% of the recurring units have the formula (I) and from 0 to 95~ of the recurring units are monomer units derived from ~1) a vinyl or vinylidene monomer and/or (2) sulfur dioxide. Preferred comonomers include acrylic acid, meth-acrylic acid, methyl and other alkyl acrylates and methacrylates, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers such as the alkyl vinyl ethers, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, vinyl sulfonamide, sulfur dioxide or a different diallylamine embraced 30 by the above formula (II).
Specific copolymers which can be reacted with an epihalo-hydrin include copolymers of N-methyldiallylamine and sulfur di-oxide; copolymers of N-methyldiallylamine and diallylamine; copoly-mers of diallylamine and acrylamide; copolymers of diallylaminé
and acrylic acid; copolymers of N-methyldiallylamine and methyl acrylate; copolymers of diallylamine and acrylonitrile; copolymers of N-methyldiallylamine and vinyl acetate; copolymers of diallyl-amine and methyl vinyl ether; copolymers of N-methyldiallylamine and vinylsulfonamide; copolymers of N-methyldiallylamine and methyl vinyl ketone; terpolymers of diallylamine, sulfur dioxide, and acrylamide; and terpolymers of N-methyldiallylamine, acrylic acid and acrylamide.
- The epihalohydrin which is reacted with the polymer of a di-10 allylamine can be any epihalohydrin, i.e., epichlorohydrin, epi-bromohydrin, epifluorohydrin or epiiodohydrin and is preferably epichlorohydrin. In general, the epihalohydrin is used in an amount ranging from about 0.5 mole to about 1.5 moles and prefer-ably about 1 mole to about 1.5 moles per mole of secondary plus tertiary amine present in the polymer.
The poly~diallylamine)-epihalohydrin resin can be prepared by reacting a homopolymer or copolymer of a diallylamine as set forth above with an epihalohydrin at a temperature of from about 30C. to about 80C. and preferably from about 40C. to about 60C.
20 until the viscosity measured on a solution containing 20% to 30%
solids at 25C. has reached a range of A to E and preferably about C to D on the Gardner-Holdt scale. The reaction is preferably carried out in aqueous solution to moderate the reaction, and at a pH of from about 7 to about 9.5.
When the desired viscosity is reached, sufficient water is added to adjust the solids content of the resin solution to about lS~ or less and the product cooled to room temperature (about 25C.) The resin solution can be stabilized against gelation by add-ing to the aqueous solution thereof sufficient water-soluble acid 30 (such as hydrochloric acid and sulfuric acid) to obtain and main-tain the pH at about 2. The resulting acid-stabilized resin solu-tion can be used as such in carrying out this invention, or, if desired, it may be reactivated by known means prior to use. Such acid-stabilized resin solutions and means of reactivating same are disclosed and described in patent 3,833,531. The disclo~urcs of thiE patont aro incorporatod h0rein by refHrence.
Prior to stabilization against gelation the resin of the solution, which is in its active or easily crosslinkable form can be represented as follows:
R CH~ R
H2C ~ /CH2 (III) R CH2C~I,CH2 O
~hen stabilized against gelation, by HCl for example, the -CH2CH/CH2 of (III) becomes -CH2CHCIH2 (IV) where X is halogen such O 0~ X
as chlorine. On reactivation of resin, by addition of aqueous NaOH to the resin solution for example, (IV) reverts to the epox-ide form shown in (III).
The -cH2cH5H2 of (III) can be converted, if desired, O
to -CH2CIH7H2 (V) by adding sodium bicarbonate to the solution of OH OH
tIII) and heating the resulting solution at about 100C. for about 1-1/2 hours. In form (V) the resin will not crosslink nor can it 20 be reconverted to (III). It is in glycol form and is an inert cationic polymer.
All forms of the resin as above shown can be used in this invention and the expression poly(diallylamine)-epihalohydrin resin as used herein and in the claims includes all resins wherein the epihalohydrin moiety is in the form shown in (III), (IV) and (V). Thus, the resin used in this invention can be represented as follows: R CH2 R
-H2C-C `C-(VI) ;N
R' E
where E is -CH CHCH2, -CH CH CH2 or --CH2CH C~2.
O OH Cl OH OH
`` " 11~3~2~4 ~ ' The following examples illustrate the preparation of the - polytdiallylamine)-epichlorohydrin resins used in this invention.
Example 1 A solution of 69.1 parts of N-methyldiallylamine and 197 parts of 20 Be hydrochloric acid in 111.7 parts of demineralized water was sparged with nitrogen to remove air, then treated with 0.55 part of tertiary butyl hydroperoxide and a solution of 0.0036 part of ferrous sulfate in 0.5 part of water. The resulting solu- -tion was allowed to polymerize at 60-69C. for 24 hours to give a 10 polymer solution containing about 52.1% solids with an RSV of 0.22.
122 parts of the above solution was adjusted to F~ ~.5 by the addi-ticn of 95 parts of 3 8% sodium hydrox~de and thèn diluted with 211 parts of water and combined with 60 parts of epichlorohydrin.
The mixture was heated at 45-55C. for 1.35 hours, until the Gardner-Holdt viscosity of a sample, cooled to 25C., reached B+.
The resulting solution was acidified with 25 parts of 20 Be hydrochloric acid and heated at 60C, until the pH became constant - at 2,0. The resulting resin solution had a solids content of 20.8~ and a Brookfield viscosity = 77 cps. (measured using a 20 Brookfield Model LVF Viscometer, No, 1 spindle at 60 r.p.m. with guard).
Example 2 25 parts of a 9.58% solids solution of resin prepared in accordance with Example 1 was combined with a solution of 1.62 parts of 10 N sodium hydroxide in 11.25 parts of water and aged 0.5 hour.
Example 3 150 parts of a 20~ solids solution of resin prepared in accordance with Example 1 was diluted with 172.5 parts water. To 30 the solution was then added a solution of 7.2 parts NaOH in 160 parts water. The resulting solution was allowed to stand for 5 minutes and then there was added thereto 10.5 parts NaHCO3. The solution was then heated to reflux and refluxed for 1.5 hours and then cooled to room temperature. The resulting solution had a ~ 10 -solids ~modified resin) content of 9.2% and a Brookfield viscosity = 77 cps. (measured using Brookfield Model LVF Viscometer, No. 1 spindle at 60 r.p.m. with guard).
The sizing accelerators of this invention are employed in combination with hydrophobic cellulose reactive sizing agents such as ketene dimers, acid anhydrides and isocyanates. These sizing B agents are well known in the art and are usually employed as~-aqueous emulsions. The term "emulsion" is used herein, as is customary in the art, to mean either a dispersion of the liquid-10 in-liquid type or of the solid-in-liquid type.
Hydrophobic acid anhydrides useful as cellulose reactive sizing agents for paper include (A) rosin anhydride (see patent
U.S. patent 3,575,796 discloses a method for the sizing of paper and paperboard products which comprises intimately dispers-- ing, within the aqueous pulp slurry, or applying to a prepared - paper web, an aqueous emulsion of an N-substituted aziridine com-pound which is prepared by means of the reaction between a car-bonyl substituted, alpha, beta-ethylenically unsaturated compound 20 such as distearyl maleate and an alkyleneimine such as ethylene-imine. The sizing agent can be uniformly dispersed with a cationic emulsifier, such as a cationic starch, for better retention on the fibers. Column 4, lines 1-44 of U.S. patent 3,575,796 discloses other cationic agents for use in aiding in the retention of the sizing agents of the invention among which are cationic thermoset-ting resins such as the reaction products of dibasic acids, poly-alkylenepolyamines and epihalohydrins. It is stated also at column 4, lines 45-62, that the cationic agents are also useful as emulsifiers for the sizing agent.
U.S. patent 3,666,512 discloses compositions comprising hydrophobic cellulose-reactive paper-sizing carboxylic acid anhy-drides and a catalyst which accelerates the rate at which the an-hydride develops its sizing properties when deposited on cellulose from aqueous medium and heated. The catalyst or promoter for the _ 3 _ .
anhydride size is a water-soluble cationic salt of a cellulose-substantive water-soluble polyamine. Suitable cationic agents are set forth in the table in column 7 of the paper. Among the cat-ionic agents is an aminopolyamide--epichlorohydrin resin, the aminopolyamide being derived from diethylenetriamine and adipic acid.
Canadian patent 873,777 discloses a method for improving the wet strength, dry strength and resistance to penetration by liquids of unsized paper comprising imbibing the paper with an 10 amine oxide capable of swelling the paper fibers and a ketene dimer paper sizing agent, heating the paper to swell the paper fibers and removing the amine oxide from the paper.
-U.S. patent 3,046,186 relates to the manufacture of sized ; paper by the beater-addition process wherein an aqueous cationic dispersion of a hydrophobic ketene dimer is added to an aqueous suspension of cellulosic fibers. The sized paper is manufactured by forming an aqueous suspension of cellulose paperma~ing fibers and adding thereto an emulsion of a hydrophobic ketene dimer in an aqueous medium containing a cationic dispersing agent which may be 20 a monomeric or high molecular weight hydrophilic or water-soluble basic nitrogenous surface-active agent. The dispersing agents are set forth in columns 3 and 4 of patent 3,046,186.
U.S. patent 3,006,806 discloses the conjoint use of an or-ganic cationic polymer with a ketene dimer in the sizing of paper.
Cationic polymers disclosed are melamine-formaldehyde resins (as described in U.S. 2,345,543 to Wohnsiedler and Thomas and U.S.
2,559,220 to Maxwell and Lanes); urea-formaldehyde resins (as des-cribed in U.S. 2,657,132 to Daniel, Landes and Suen); cationic corn starch; guanidine-formaldehyde resins (U.S. 2,745,744 to 30 Weidner and Dunlap); alkylenepolyamine-halohydrin resins (as des-cribed in U.S. 2,601,597 to Daniel, Wilson and Landes); and cat-ionic urea-formaldehyde resins (as described in British patents 675,477 and 677,184).
U.S. patent 3,084,092 relates to paper manufactured by the 110~264 `.
conjoint use of an amino resin and a hydrophobic organic isocyanate. Amino resins descrlbed in United States patent 3,084,092 are polyfunctional halo-hydrin resins o Daniel et al, United States patent 2,595,934; The dicyandi-amide-formaldehyde-aminepolymers of Dudley et al, United States patent 2,596,014; the urea-mono-substituted urea resins of Schiller et al, United States patent 2,698,787; the polyaminepolyamide linear polymers of House et al, United States patent 2,729,560; the polymers formed by copolymerizing acryl-amide and acrylic acid in 9:1 molar ratio; the sulfonated dimethylolurea resins of United States patent 2,582,840; and the aminosulfuric acid-melamine-formaldehyde resins of United States patent 2,688,607.
- In accordance with this invention, applicant has found new sizing accelerators for use with hydrophobic cellulose reactive sizing agents such as ketene dimers, acid anhydrides, and organic isocyanates.
According to one aspect of the invention there is pTovided in the method of producing sized paper wherein there is employed an aqueous emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides, and organic isocyanates, the improvement wherein there is employed in combination with the sizing agent a sizing accelerator, said accelerator being a poly(diallylamine)-epihalohydrin resin in an amount sufficient to increase the off-the-machine sizing effect of the sizing agent.
According to another aspect of the invention there is provided a sizing composition for cellulose fibers consisting essentially of an aqueous emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides and organic isocyanate containing a sizing accelerator, said sizing accelerator being a poly(diallyl-amine)-epihalohydrin resin and being present in an amount sufficient to increase the off-the-machine sizing properties of the sizing agent.
According to a further aspect of the invention there is provided a sizing composition for cellulose fibers consisting essentially of an aqueous emulsion of a hydrophob~c cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides, and organic isocyanates ~ -5-f ~A
`` 11~264 containing a sizing accelerator, said sizing accelerator being selected from a water.soluble poly~diallylamine)~epihalohydrin resin and a water-soluble poly~N~methyldiallylamine).epihalohydrin resin, the proportion of accelerator to sizing agent being in the range of 1:1 to 3:1.
The sizing accelerators used in this invention are poly~diallyl-amine)-epichlorohydrin resins as disclosed and described in United States patent 3,700,623.
The poly~diallylamine)-epihalohydrin resins used in this invention comprise the resinous reaction product of ~A) a linear polymer having units of the formula R ~CH2 R
- H2C-~ C~
2 ~ N ~ 2 R' where R is hydrogen or lower alkyl and R' is hydrogen, alkyl or a substituted alkyl group and (B) an epihalohydrin.
In the above formula, each R can be the sa~e or di~ferent and, as stated, can be hydrogen or lower alkyl. The alkyl groups contain from 1 to 6 !; .carbons and are preferably methyl, ethyl, isopropyl or n-butyl. R' of the formula represents hydrogen, alkyl or substituted alkyl groups. The R' alkyl groups will contain from 1 to 18 carbon atoms ~pree~ably fro~ 1 to 6 carbon atoms) such as -5a-2~4 methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and octadecyl. R' can also be a sub-stituted alkyl group. Suitable substituents include, in general, any group which will not interfere with polymerization through a vinyl double bond. Typically, the substituents can be carboxylate, cyano, ether, amino tprimary, secondary or tertiary), amide, hydrazide and hydroxyl.
Polymers having units of the above formula can be produced by polymerizing the hydrohalide salt of a diallylamine CH~ CH2 !i 11 R-C C-R (II) CE~ CH2 i, .
where R and R ' are as indicated above, either alone or as a mix-ture with other copolymerizable ingredients, in the presence of a free radical catalyst and then neutralizing the salt to give the polymer free base Specific hydrohalide salts of the diallylamines which can be 20 polymerized to provide the polymer units of the invention include diallylamine hydrochloride; N-methyldiallylamine hydrobromide;
2,2'-dimethyl-N-methyldiallylamine hydrochloride; N-ethyldiallyl-amine hydrobromide; N-isopropyldiallylamine hydrochloride; N-n-butyldiallylamine hydrobromide; N-tert-butyldiallylamine hydro-chloride; N-n-hexyldiallylamine hydrochloride; N-octadecyldiallyl-amine hydrochloride; N-acetamidodiallylamine hydrochloride; N-cyanomethyldiallylamine hydrochloride; N-~-propionamidodiallyl-amine hydrobromide; N-carboethoxymethyldiallylamine hydrochloride;
N-~-methoxyethyldiallylamine hydrobromide; N-~-aminoethyldiallyl-30 amine hydrochloride; N-hydroxyethyldiallylamine hydrobromide and N-acetohydrazide substituted diallylamine hydrochloride.
In preparing the homopolymers and copolymers for use in this invention, reaction can be initiated by redox catalytic system. In a redox system, the catalyst is activated by means of a reducing - 1113~2~4 agent which produces free radicals without the use of heat. Re-ducing agents commonly used are sodium metabisulfite and potassium metabisulfite. Other reducing agents include water-soluble thio-sulfates and bisulfites, hydrosulfites and reducing salts such as the sulfate of a metal which is capable of existing in more than one valence state such as cobalt, iron, manganese and copper. A
specific example of such a sulfate is ferrous sulfate. The use of a redox initiator system has several advantages, the most import-ant of which is efficient polymeri~ation at lower temperatures.
10 Conventional peroxide catalysts such as tertiary-butyl hydroper-oxide, potassium persulfate, hydrogen peroxide and ammonium per-sulfate used in conjunction with the above reducing agents or metal activators, can be employed.
As stated above, the linear polymers of diallylamines can contain different units of formula ~I) and/or contain units of one or more other copolymerizable monomers. Typically, the comonomer is a different diallylamine; a monoethylenically unsaturated com-pound containing a single vinyl or vinylidene group; or sulfur di-oxide, and is present in an amount ranging from 0 to 95 mole per-20 cent of the polymer. Thus the polymers of diallylamine are linearpolymers wherein from 5% to 100% of the recurring units have the formula (I) and from 0 to 95~ of the recurring units are monomer units derived from ~1) a vinyl or vinylidene monomer and/or (2) sulfur dioxide. Preferred comonomers include acrylic acid, meth-acrylic acid, methyl and other alkyl acrylates and methacrylates, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers such as the alkyl vinyl ethers, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, vinyl sulfonamide, sulfur dioxide or a different diallylamine embraced 30 by the above formula (II).
Specific copolymers which can be reacted with an epihalo-hydrin include copolymers of N-methyldiallylamine and sulfur di-oxide; copolymers of N-methyldiallylamine and diallylamine; copoly-mers of diallylamine and acrylamide; copolymers of diallylaminé
and acrylic acid; copolymers of N-methyldiallylamine and methyl acrylate; copolymers of diallylamine and acrylonitrile; copolymers of N-methyldiallylamine and vinyl acetate; copolymers of diallyl-amine and methyl vinyl ether; copolymers of N-methyldiallylamine and vinylsulfonamide; copolymers of N-methyldiallylamine and methyl vinyl ketone; terpolymers of diallylamine, sulfur dioxide, and acrylamide; and terpolymers of N-methyldiallylamine, acrylic acid and acrylamide.
- The epihalohydrin which is reacted with the polymer of a di-10 allylamine can be any epihalohydrin, i.e., epichlorohydrin, epi-bromohydrin, epifluorohydrin or epiiodohydrin and is preferably epichlorohydrin. In general, the epihalohydrin is used in an amount ranging from about 0.5 mole to about 1.5 moles and prefer-ably about 1 mole to about 1.5 moles per mole of secondary plus tertiary amine present in the polymer.
The poly~diallylamine)-epihalohydrin resin can be prepared by reacting a homopolymer or copolymer of a diallylamine as set forth above with an epihalohydrin at a temperature of from about 30C. to about 80C. and preferably from about 40C. to about 60C.
20 until the viscosity measured on a solution containing 20% to 30%
solids at 25C. has reached a range of A to E and preferably about C to D on the Gardner-Holdt scale. The reaction is preferably carried out in aqueous solution to moderate the reaction, and at a pH of from about 7 to about 9.5.
When the desired viscosity is reached, sufficient water is added to adjust the solids content of the resin solution to about lS~ or less and the product cooled to room temperature (about 25C.) The resin solution can be stabilized against gelation by add-ing to the aqueous solution thereof sufficient water-soluble acid 30 (such as hydrochloric acid and sulfuric acid) to obtain and main-tain the pH at about 2. The resulting acid-stabilized resin solu-tion can be used as such in carrying out this invention, or, if desired, it may be reactivated by known means prior to use. Such acid-stabilized resin solutions and means of reactivating same are disclosed and described in patent 3,833,531. The disclo~urcs of thiE patont aro incorporatod h0rein by refHrence.
Prior to stabilization against gelation the resin of the solution, which is in its active or easily crosslinkable form can be represented as follows:
R CH~ R
H2C ~ /CH2 (III) R CH2C~I,CH2 O
~hen stabilized against gelation, by HCl for example, the -CH2CH/CH2 of (III) becomes -CH2CHCIH2 (IV) where X is halogen such O 0~ X
as chlorine. On reactivation of resin, by addition of aqueous NaOH to the resin solution for example, (IV) reverts to the epox-ide form shown in (III).
The -cH2cH5H2 of (III) can be converted, if desired, O
to -CH2CIH7H2 (V) by adding sodium bicarbonate to the solution of OH OH
tIII) and heating the resulting solution at about 100C. for about 1-1/2 hours. In form (V) the resin will not crosslink nor can it 20 be reconverted to (III). It is in glycol form and is an inert cationic polymer.
All forms of the resin as above shown can be used in this invention and the expression poly(diallylamine)-epihalohydrin resin as used herein and in the claims includes all resins wherein the epihalohydrin moiety is in the form shown in (III), (IV) and (V). Thus, the resin used in this invention can be represented as follows: R CH2 R
-H2C-C `C-(VI) ;N
R' E
where E is -CH CHCH2, -CH CH CH2 or --CH2CH C~2.
O OH Cl OH OH
`` " 11~3~2~4 ~ ' The following examples illustrate the preparation of the - polytdiallylamine)-epichlorohydrin resins used in this invention.
Example 1 A solution of 69.1 parts of N-methyldiallylamine and 197 parts of 20 Be hydrochloric acid in 111.7 parts of demineralized water was sparged with nitrogen to remove air, then treated with 0.55 part of tertiary butyl hydroperoxide and a solution of 0.0036 part of ferrous sulfate in 0.5 part of water. The resulting solu- -tion was allowed to polymerize at 60-69C. for 24 hours to give a 10 polymer solution containing about 52.1% solids with an RSV of 0.22.
122 parts of the above solution was adjusted to F~ ~.5 by the addi-ticn of 95 parts of 3 8% sodium hydrox~de and thèn diluted with 211 parts of water and combined with 60 parts of epichlorohydrin.
The mixture was heated at 45-55C. for 1.35 hours, until the Gardner-Holdt viscosity of a sample, cooled to 25C., reached B+.
The resulting solution was acidified with 25 parts of 20 Be hydrochloric acid and heated at 60C, until the pH became constant - at 2,0. The resulting resin solution had a solids content of 20.8~ and a Brookfield viscosity = 77 cps. (measured using a 20 Brookfield Model LVF Viscometer, No, 1 spindle at 60 r.p.m. with guard).
Example 2 25 parts of a 9.58% solids solution of resin prepared in accordance with Example 1 was combined with a solution of 1.62 parts of 10 N sodium hydroxide in 11.25 parts of water and aged 0.5 hour.
Example 3 150 parts of a 20~ solids solution of resin prepared in accordance with Example 1 was diluted with 172.5 parts water. To 30 the solution was then added a solution of 7.2 parts NaOH in 160 parts water. The resulting solution was allowed to stand for 5 minutes and then there was added thereto 10.5 parts NaHCO3. The solution was then heated to reflux and refluxed for 1.5 hours and then cooled to room temperature. The resulting solution had a ~ 10 -solids ~modified resin) content of 9.2% and a Brookfield viscosity = 77 cps. (measured using Brookfield Model LVF Viscometer, No. 1 spindle at 60 r.p.m. with guard).
The sizing accelerators of this invention are employed in combination with hydrophobic cellulose reactive sizing agents such as ketene dimers, acid anhydrides and isocyanates. These sizing B agents are well known in the art and are usually employed as~-aqueous emulsions. The term "emulsion" is used herein, as is customary in the art, to mean either a dispersion of the liquid-10 in-liquid type or of the solid-in-liquid type.
Hydrophobic acid anhydrides useful as cellulose reactive sizing agents for paper include (A) rosin anhydride (see patent
3,582,464); (B) anhydrides having the structure Rl--C
~ (VII) Rl C~
o where Rl is a saturated or unsaturated hydrocarbon radical, the 20 hydrocarbon radical being a straight or branched chain alkyl radi-cal, an aromatic substituted alkyl radical or an alkyl substituted aromatic radical so long as the hydrocarbon radical contains a total of from about 14 to 36 carbon atoms; and (C) cyclic dicar-boxylic acid anhydrides having the structure Il ,C (VIII) \ C/
Io 30 where R" represents a dimethylene or trimethylene radical and where R" ' is a hydrocarbon radical containing more than 7 carbon a~oms which are selected from the group consisting of alkyl, alkenyl, aralkyl or aralkenyl. Substituted cyclic dicarboxylic acid anhyd-rides falling within the above formula (VIII) are substituted suc-cinic and glutaric anhydrides. In formula (VII) above each Rl can 11t)~264 be the same hydrocarbon radical or each Rl can be a different hydrocarbon radical.
Specific examples of anhydrides of formula (VII) are myris-toyl anhydride; palmitoyl anhydride; oleoyl anhydride; and stear-oyl anhydride.
Specific examples of anhydrides of formula (VIII) are iso-octadecenyl succinic acid anhydride; n~hexadecenyl succinic acid anhydride; dodecyl succinic acid anhydride; decenyl succinic acid anhydride; octenyl succinic acid anhydride; and heptyl glutaric 10 acid anhydride.
Hydrophobic organic isocyanates used as sizing agents for paper are well known in the art. Best results are obtained when the hydrocarbon chains of the isocyanates contain at least 12 car-bon atoms, preferably from 14 to 36 carbon atoms. Such isocyan-ates include rosin isocyanate; dodecyl isocyanate; octadecyl iso-cyanate; tetradecyl isocyanate; hexadecyl isocyanate; eicosyl iso--` cyanate; docosyl isocyanate; 6-ethyldecyl isocyanate; 6-phenyl-decyl isocyanate; and polyisocyanates such as 1,18-octadecyl di-isocyanate and 1,12-dodecyl diisocyanate, wherein one long chain 20 alkyl group serves two isocyanate radicals and imparts hydrophobic properties to the molecule as a whole.
Ketene dimers used as cellulose reactive sizing agents are well known in the art and are dimers having the formula [R2CH=C=O]2 (IX) where R2 is a hydrocarbon radical, such as alkyl having at least 8 carbon atoms, cycloalkyl having at least 6 carbon atoms, aryl, aralkyl and alkaryl. In naming ketene dimers, the radical "R2" is named followed by "ketene dimer". Thus, phenyl ketene dimer is [ ~ `CH=C=O ]
benzyl ketene dimer is:
CH2 CH=C=O ]
:'`
and decyl ketene dimer is: ~CloH21-CH=C=O]2. Examples of ketene dimers include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octa-decyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl beta-naphthyl and cyclohexyl ketene dimers, as well as the ketene dimers pre-pared from montamic acid, naphthenic acid, ~9,10-decylenic acid, ~9,10-decylenic acid, ~9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid and eleostearic acid, as well as ketene dimers prepared from naturally occurring mixtures of fatty acids, such as those mixtures in coco-10 nut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanutoil, rape oil, beef tallow, lard (leaf) and whale blubber. Mix-tures of any of the above-named fatty acids with each other may also be used.
The following examples show the preparation of ketene dimer emulsions.
Example_4 An emulsion of an alkyl ketene dimer prepared from a mixture of palmitic and stearic acids was prepared by admixing 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium 20 lignin sulfonate. The mixture was adjusted to pH of about 3.5 with 98% sulfuric acid. The resulting mixture was heated at 90-95C. for about one hour. Water was then added to the mixture in an amount sufficient to provide a mixture of 1750 parts (total weight). About 240 parts of the ketene dimer was stirred into the mixture together with 2.4 parts of thiadiazine. The thiadiazine was used as a preservative. The resulting premix (at 65C.) was homogenized in one pass through an homogenizer at 4000 p.s.i. The homogenized product was diluted with water to a ketene dimer solids content of about 6%.
Example 5 Example 4 was repeated with the exception that the alkyl ketene dimer of oleic acid was used in place of the alkyl ketene dimer prepared from a mixture of palmitic and stearic acids.
1~0~264 Example 6 A portion of the emulsion of Example 4 was diluted, with water, to a ketene dimer solids content of 0.10%.
Example 7 A portion of the emulsion of Example 5 was diluted, with water, to a ketene dimer solids content of 0.10~.
Example 8 Products prepared in accordance with Example 1 and Example 4 were combined, with addition of water as required, to provide an-10 aqueous sizing composition comprised of 0.10% ketene dimer and 0.20% resin.
Example 9 Products prepared in accordance with Example 1 and Example 4 were combined, with addition of water as required, to provide an aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% resin.
Example 10 Products prepared in accordance with Example 2 and Example 4 were combined, with addition of water as required, to provide an 20 aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% acid stabilized resin.
Example 11 Products prepared in accordance with ~xample 3 and Example 4 were combined, with addition of water as required, to provide an aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% modified resin.
Example 12 Products prepared in accordance with Example 1 and Example 5 were combined, with addition of water as required, to provide an 30 aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% resin.
The above sizing compositions were applied to the surface of a sheet of 40 lb./3000 ft.2 waterleaf paper. The sheet was made from a 50:50 hardwood:softwood pulp blend on a pilot paper machine. Each sizing composition was adjusted to pH 7 before ap-plication to the sheet in the nip of a horizontal size press. The size press ran at 40 ft./min. and the wet pick up was 70%. Reten-tion of the ketene dimer size was the same in all of these runs.
The sized sheets were dried at 200F. for 20 sec. on a laboratory drum drier to 4% moisture. The sizing was measured by the Hercules - Size Test with test solution No. 2 to the indicated reflectance.
The off-machine data were obtained within two minutes of drying and the natural and aged data after at least 3 days storage at room 10 temperature. It is known in the art that ketene dimer size devel-ops substantially all its sizing properties in the ~aper in 3 days.
After this time the size properties of the paper remain essentially the same.
Size results are set forth in Table I below.
Table I
Sizing Composition Hercules Size Test of Off-the-~achine to 80% Natural Aged to 85%
Example _ Reflectance (Seconds) P~eflectance(Seconds) 6 ) 2 separate 0 331 6 ) tests 0 400 8 ) 2 separate 310 350 8 ) tests 305 9 ) 2 separate 335 450 9 ) tests 160 436 The following examples show the improvement in off-the-30 machine sizing when the sizing compositions of this invention areused in internal sizing.
Handsheets of 40 lb./3000 ft.2 were made on a Noble and Wood handsheet apparatus using a pulp consisting of 30% waste news, 35%
- Rayonier bleached softwood, and 35% Weyerhauser bleached kraft hardwood. Sheets were dried for 45-50 sec. at 215F. The size accelerator resin, in aqueous solution, was adaed to the aliquot where the pulp consistency was about 0.275% and stirred for 15 seconds and then the ketene dimer size emulsion was added followed by stirring for another 15 seconds This was then diluted, with water, to a pulp consistency of about 0.025% in the deckle box prior to sheet formation. The amounts of accelerator resin used and ketene dimer used are shown in Table II below and are based on the dry weight of the pulp.
Test results are shown in Table II below.
Table II
Hercules Size Test ~ccelerator Ketene Dimer to 80% Reflectance Resin of Emulsion of Off-the- Natural 10 Example No.Exam~le 1Example 4Machine Aged 13 none 0.15% ketene 0 300-dimer 14 .15% " 16 303 - 15 .30% " 78 464 16 .45% " 154 594 In examples 13, 14, 15 and 16 the accelerator resin and the sizing agent were added separately. It is to be understood that they can be admixed to pro~ide a sizing composition, as in surface sizing, prior to addition ~o a pulp slurry, and sized sheets pre-20 pared from the thus treated slurry.
Example 17 An aqueous emulsion of octadecyl isocyanate (stearyl iso-cyanate) sizing agent wa~ used in the internal sizing of a hand-sheet using a furnish of 50% hardwood kraft:50% softwood kraft with 10% clay and 10% calcium carbonate as fillers. Cationic starch (Stalok 400), 35% based on the dry weight of the pulp, was added as a retention aid for the fillers. The amount of octadecyl isocyanate used as sizing agent was 0.2% based on the dry weight of the fibers.
Example 18 Example 17 was repeated with the exception that resin pre-pared in accordance with Example 1, in a~ueous solution, was also added to the pulp slurry prior to sheet formation in an amount equal to .125% of the dry weight of the pulp. Test results are shown in Table III below.
``` il~264 Table III
Hercules Size Test to 80~ Reflectance Handsheets Off-the- Natural of Example Machine A~ed It is to be understood that the above description and work-ing examples are illustrative of this invention and not in limita-tion thereof.
~ (VII) Rl C~
o where Rl is a saturated or unsaturated hydrocarbon radical, the 20 hydrocarbon radical being a straight or branched chain alkyl radi-cal, an aromatic substituted alkyl radical or an alkyl substituted aromatic radical so long as the hydrocarbon radical contains a total of from about 14 to 36 carbon atoms; and (C) cyclic dicar-boxylic acid anhydrides having the structure Il ,C (VIII) \ C/
Io 30 where R" represents a dimethylene or trimethylene radical and where R" ' is a hydrocarbon radical containing more than 7 carbon a~oms which are selected from the group consisting of alkyl, alkenyl, aralkyl or aralkenyl. Substituted cyclic dicarboxylic acid anhyd-rides falling within the above formula (VIII) are substituted suc-cinic and glutaric anhydrides. In formula (VII) above each Rl can 11t)~264 be the same hydrocarbon radical or each Rl can be a different hydrocarbon radical.
Specific examples of anhydrides of formula (VII) are myris-toyl anhydride; palmitoyl anhydride; oleoyl anhydride; and stear-oyl anhydride.
Specific examples of anhydrides of formula (VIII) are iso-octadecenyl succinic acid anhydride; n~hexadecenyl succinic acid anhydride; dodecyl succinic acid anhydride; decenyl succinic acid anhydride; octenyl succinic acid anhydride; and heptyl glutaric 10 acid anhydride.
Hydrophobic organic isocyanates used as sizing agents for paper are well known in the art. Best results are obtained when the hydrocarbon chains of the isocyanates contain at least 12 car-bon atoms, preferably from 14 to 36 carbon atoms. Such isocyan-ates include rosin isocyanate; dodecyl isocyanate; octadecyl iso-cyanate; tetradecyl isocyanate; hexadecyl isocyanate; eicosyl iso--` cyanate; docosyl isocyanate; 6-ethyldecyl isocyanate; 6-phenyl-decyl isocyanate; and polyisocyanates such as 1,18-octadecyl di-isocyanate and 1,12-dodecyl diisocyanate, wherein one long chain 20 alkyl group serves two isocyanate radicals and imparts hydrophobic properties to the molecule as a whole.
Ketene dimers used as cellulose reactive sizing agents are well known in the art and are dimers having the formula [R2CH=C=O]2 (IX) where R2 is a hydrocarbon radical, such as alkyl having at least 8 carbon atoms, cycloalkyl having at least 6 carbon atoms, aryl, aralkyl and alkaryl. In naming ketene dimers, the radical "R2" is named followed by "ketene dimer". Thus, phenyl ketene dimer is [ ~ `CH=C=O ]
benzyl ketene dimer is:
CH2 CH=C=O ]
:'`
and decyl ketene dimer is: ~CloH21-CH=C=O]2. Examples of ketene dimers include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octa-decyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl beta-naphthyl and cyclohexyl ketene dimers, as well as the ketene dimers pre-pared from montamic acid, naphthenic acid, ~9,10-decylenic acid, ~9,10-decylenic acid, ~9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid and eleostearic acid, as well as ketene dimers prepared from naturally occurring mixtures of fatty acids, such as those mixtures in coco-10 nut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanutoil, rape oil, beef tallow, lard (leaf) and whale blubber. Mix-tures of any of the above-named fatty acids with each other may also be used.
The following examples show the preparation of ketene dimer emulsions.
Example_4 An emulsion of an alkyl ketene dimer prepared from a mixture of palmitic and stearic acids was prepared by admixing 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium 20 lignin sulfonate. The mixture was adjusted to pH of about 3.5 with 98% sulfuric acid. The resulting mixture was heated at 90-95C. for about one hour. Water was then added to the mixture in an amount sufficient to provide a mixture of 1750 parts (total weight). About 240 parts of the ketene dimer was stirred into the mixture together with 2.4 parts of thiadiazine. The thiadiazine was used as a preservative. The resulting premix (at 65C.) was homogenized in one pass through an homogenizer at 4000 p.s.i. The homogenized product was diluted with water to a ketene dimer solids content of about 6%.
Example 5 Example 4 was repeated with the exception that the alkyl ketene dimer of oleic acid was used in place of the alkyl ketene dimer prepared from a mixture of palmitic and stearic acids.
1~0~264 Example 6 A portion of the emulsion of Example 4 was diluted, with water, to a ketene dimer solids content of 0.10%.
Example 7 A portion of the emulsion of Example 5 was diluted, with water, to a ketene dimer solids content of 0.10~.
Example 8 Products prepared in accordance with Example 1 and Example 4 were combined, with addition of water as required, to provide an-10 aqueous sizing composition comprised of 0.10% ketene dimer and 0.20% resin.
Example 9 Products prepared in accordance with Example 1 and Example 4 were combined, with addition of water as required, to provide an aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% resin.
Example 10 Products prepared in accordance with Example 2 and Example 4 were combined, with addition of water as required, to provide an 20 aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% acid stabilized resin.
Example 11 Products prepared in accordance with ~xample 3 and Example 4 were combined, with addition of water as required, to provide an aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% modified resin.
Example 12 Products prepared in accordance with Example 1 and Example 5 were combined, with addition of water as required, to provide an 30 aqueous sizing composition comprised of 0.10% ketene dimer and 0.10% resin.
The above sizing compositions were applied to the surface of a sheet of 40 lb./3000 ft.2 waterleaf paper. The sheet was made from a 50:50 hardwood:softwood pulp blend on a pilot paper machine. Each sizing composition was adjusted to pH 7 before ap-plication to the sheet in the nip of a horizontal size press. The size press ran at 40 ft./min. and the wet pick up was 70%. Reten-tion of the ketene dimer size was the same in all of these runs.
The sized sheets were dried at 200F. for 20 sec. on a laboratory drum drier to 4% moisture. The sizing was measured by the Hercules - Size Test with test solution No. 2 to the indicated reflectance.
The off-machine data were obtained within two minutes of drying and the natural and aged data after at least 3 days storage at room 10 temperature. It is known in the art that ketene dimer size devel-ops substantially all its sizing properties in the ~aper in 3 days.
After this time the size properties of the paper remain essentially the same.
Size results are set forth in Table I below.
Table I
Sizing Composition Hercules Size Test of Off-the-~achine to 80% Natural Aged to 85%
Example _ Reflectance (Seconds) P~eflectance(Seconds) 6 ) 2 separate 0 331 6 ) tests 0 400 8 ) 2 separate 310 350 8 ) tests 305 9 ) 2 separate 335 450 9 ) tests 160 436 The following examples show the improvement in off-the-30 machine sizing when the sizing compositions of this invention areused in internal sizing.
Handsheets of 40 lb./3000 ft.2 were made on a Noble and Wood handsheet apparatus using a pulp consisting of 30% waste news, 35%
- Rayonier bleached softwood, and 35% Weyerhauser bleached kraft hardwood. Sheets were dried for 45-50 sec. at 215F. The size accelerator resin, in aqueous solution, was adaed to the aliquot where the pulp consistency was about 0.275% and stirred for 15 seconds and then the ketene dimer size emulsion was added followed by stirring for another 15 seconds This was then diluted, with water, to a pulp consistency of about 0.025% in the deckle box prior to sheet formation. The amounts of accelerator resin used and ketene dimer used are shown in Table II below and are based on the dry weight of the pulp.
Test results are shown in Table II below.
Table II
Hercules Size Test ~ccelerator Ketene Dimer to 80% Reflectance Resin of Emulsion of Off-the- Natural 10 Example No.Exam~le 1Example 4Machine Aged 13 none 0.15% ketene 0 300-dimer 14 .15% " 16 303 - 15 .30% " 78 464 16 .45% " 154 594 In examples 13, 14, 15 and 16 the accelerator resin and the sizing agent were added separately. It is to be understood that they can be admixed to pro~ide a sizing composition, as in surface sizing, prior to addition ~o a pulp slurry, and sized sheets pre-20 pared from the thus treated slurry.
Example 17 An aqueous emulsion of octadecyl isocyanate (stearyl iso-cyanate) sizing agent wa~ used in the internal sizing of a hand-sheet using a furnish of 50% hardwood kraft:50% softwood kraft with 10% clay and 10% calcium carbonate as fillers. Cationic starch (Stalok 400), 35% based on the dry weight of the pulp, was added as a retention aid for the fillers. The amount of octadecyl isocyanate used as sizing agent was 0.2% based on the dry weight of the fibers.
Example 18 Example 17 was repeated with the exception that resin pre-pared in accordance with Example 1, in a~ueous solution, was also added to the pulp slurry prior to sheet formation in an amount equal to .125% of the dry weight of the pulp. Test results are shown in Table III below.
``` il~264 Table III
Hercules Size Test to 80~ Reflectance Handsheets Off-the- Natural of Example Machine A~ed It is to be understood that the above description and work-ing examples are illustrative of this invention and not in limita-tion thereof.
Claims (12)
1. In the method of producing sized paper wherein there is employed an aqueous emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides, and organic isocyanates, the improvement wherein there is employed in combination with the sizing agent a sizing accelerator, said accelerator being a poly(diallylamine)-epihalo-hydrin resin in an amount sufficient to increase the off-the-machine sizing effect of the sizing agent.
2. The method of claim 1 wherein the sizing agent is a ketene dimer and the sizing accelerator is poly(N-methyldiallyl-amine)-epichlorohydrin resin.
3. The method of claim 1 wherein the sizing agent is an acid anhydride and the sizing accelerator is poly(N-methyldiallylamine)-epichlorohydrin resin.
4. The method of claim 1 wherein the sizing agent is an or-ganic isocyanate and the sizing accelerator is poly(N-methyldi-allylamine)-epichlorohydrin resin.
5. A sizing composition for cellulose fibers consisting essentially of an aqueous emulsion of a hydrophobic cellulose re-active sizing agent selected from the group consisting of ketene dimers, acid anhydrides and organic isocyanate containing a sizing accelerator, said sizing accelerator being a poly(diallylamine)-epihalohydrin resin and being present in an amount sufficient to increase the off-the-machine sizing properties of the sizing agent.
6. The sizing composition of claim 5 wherein the sizing agent is a ketene dimer and the sizing accelerator is poly(N-methyldiallylamine)-epichlorohydrin resin.
7. The sizing composition of claim 5 wherein the sizing agent is an acid anhydride and the sizing accelerator is poly-(N-methyldiallylamine)-epichlorohydrin resin.
8. The sizing composition of claim 5 wherein the sizing agent is an organic isocyanate and the sizing accelerator is poly(N-methyldiallylamine)-epichlorohydrin resin.
9. A sizing composition for cellulose fibers consisting essentially of an aqueous emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides, and organic isocyanates containing a sizing accelerator, said sizing accelerator being selected from a water-soluble poly(diallylamine)-epihalohydrin resin and a water-soluble poly(N-methyldiallylamine)-epihalohydrin resin, the pro-portion of accelerator to sizing agent being in the range of 1:1 to 3:1.
10. The sizing composition of claim 9 wherein the sizing agent is a ketene dimer and the sizing accelerator is poly(N-methyldiallylamine)-epichlorohydrin resin.
11. The sizing composition of claim 9 wherein the sizing agent is an acid anhydride and the sizing accelerator is poly(N-methyldiallylamine)-epichlorohydrin resin.
12. The sizing composition of claim 9 wherein the sizing agent is an organic isocyanate and the sizing accelerator is poly(N-methyldiallylamine)-epichlorohydrin resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66514076A | 1976-03-08 | 1976-03-08 | |
| US665,140 | 1976-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100264A true CA1100264A (en) | 1981-05-05 |
Family
ID=24668891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA271,958A Expired CA1100264A (en) | 1976-03-08 | 1977-02-17 | Sizing method and sizing composition for use therein |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS52110906A (en) |
| AT (1) | AT357865B (en) |
| AU (1) | AU506880B2 (en) |
| BE (1) | BE852211A (en) |
| BR (1) | BR7701377A (en) |
| CA (1) | CA1100264A (en) |
| CH (1) | CH619500A5 (en) |
| DE (1) | DE2710060A1 (en) |
| DK (1) | DK148040C (en) |
| FI (1) | FI63084C (en) |
| FR (1) | FR2343857A1 (en) |
| GB (1) | GB1549564A (en) |
| IT (1) | IT1071348B (en) |
| MX (1) | MX4301E (en) |
| NL (1) | NL7702455A (en) |
| NO (1) | NO149477C (en) |
| NZ (1) | NZ183271A (en) |
| SE (1) | SE432790B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4240935A (en) * | 1978-12-22 | 1980-12-23 | Hercules Incorporated | Ketene dimer paper sizing compositions |
| JPS5626096A (en) * | 1979-08-02 | 1981-03-13 | Dainippon Ink & Chemicals | Sizing agent for cationic paper making |
| JPS5933220Y2 (en) * | 1979-11-30 | 1984-09-17 | 三菱農機株式会社 | Pot seedling planting device in rice transplanter |
| WO1981003328A1 (en) * | 1980-05-22 | 1981-11-26 | Firmenich & Cie | Bicyclic compounds and utilization thereof as perfuming agents |
| DE3069015D1 (en) * | 1980-06-24 | 1984-09-27 | Seiko Kagaku Kogyo Co Ltd | Cellulose-treating agent and paper products sized therewith |
| DE3203189A1 (en) * | 1982-01-30 | 1983-08-04 | Bayer Ag, 5090 Leverkusen | SIZE AND ITS USE |
| JPS6059195A (en) * | 1983-09-13 | 1985-04-05 | 三菱製紙株式会社 | Neutral paper |
| US7998311B2 (en) * | 2008-07-24 | 2011-08-16 | Hercules Incorporated | Enhanced surface sizing of paper |
| HUE029313T2 (en) * | 2012-02-09 | 2017-02-28 | Omya Int Ag | A composition and method for controlling the wettability of surfaces |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA999300A (en) * | 1970-09-22 | 1976-11-02 | Rohm And Haas Company | Wet-strength resins, paper and method of making it |
| CA1045735A (en) * | 1973-08-06 | 1979-01-02 | Paul H. Aldrich | Stable rosin dispersions |
| US3923745A (en) * | 1973-08-31 | 1975-12-02 | Hercules Inc | Water-dispersible thermosettable cationic resins and paper sized therewith |
-
1977
- 1977-02-07 NZ NZ183271A patent/NZ183271A/en unknown
- 1977-02-17 CA CA271,958A patent/CA1100264A/en not_active Expired
- 1977-02-23 FI FI770596A patent/FI63084C/en not_active IP Right Cessation
- 1977-03-07 NO NO770789A patent/NO149477C/en unknown
- 1977-03-07 AU AU22975/77A patent/AU506880B2/en not_active Expired
- 1977-03-07 FR FR7706628A patent/FR2343857A1/en active Granted
- 1977-03-07 JP JP2400577A patent/JPS52110906A/en active Granted
- 1977-03-07 MX MX775513U patent/MX4301E/en unknown
- 1977-03-07 AT AT150277A patent/AT357865B/en not_active IP Right Cessation
- 1977-03-07 SE SE7702539A patent/SE432790B/en not_active IP Right Cessation
- 1977-03-07 IT IT21002/77A patent/IT1071348B/en active
- 1977-03-07 GB GB9485/77A patent/GB1549564A/en not_active Expired
- 1977-03-07 CH CH280677A patent/CH619500A5/en not_active IP Right Cessation
- 1977-03-08 NL NL7702455A patent/NL7702455A/en active Search and Examination
- 1977-03-08 DE DE19772710060 patent/DE2710060A1/en active Granted
- 1977-03-08 BE BE175581A patent/BE852211A/en not_active IP Right Cessation
- 1977-03-08 DK DK101077A patent/DK148040C/en not_active IP Right Cessation
- 1977-03-08 BR BR7701377A patent/BR7701377A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2343857A1 (en) | 1977-10-07 |
| JPS6215679B2 (en) | 1987-04-08 |
| NO770789L (en) | 1977-09-09 |
| NL7702455A (en) | 1977-09-12 |
| DK101077A (en) | 1977-09-09 |
| DK148040C (en) | 1985-10-07 |
| FI770596A (en) | 1977-09-09 |
| DE2710060C2 (en) | 1987-03-26 |
| FI63084B (en) | 1982-12-31 |
| BE852211A (en) | 1977-09-08 |
| NO149477C (en) | 1984-04-25 |
| AU2297577A (en) | 1978-09-14 |
| MX4301E (en) | 1982-03-19 |
| IT1071348B (en) | 1985-04-02 |
| FR2343857B1 (en) | 1983-01-07 |
| AU506880B2 (en) | 1980-01-24 |
| AT357865B (en) | 1980-08-11 |
| NO149477B (en) | 1984-01-16 |
| CH619500A5 (en) | 1980-09-30 |
| FI63084C (en) | 1983-04-11 |
| SE432790B (en) | 1984-04-16 |
| DK148040B (en) | 1985-02-11 |
| ATA150277A (en) | 1979-12-15 |
| SE7702539L (en) | 1977-09-09 |
| GB1549564A (en) | 1979-08-08 |
| DE2710060A1 (en) | 1977-09-22 |
| JPS52110906A (en) | 1977-09-17 |
| BR7701377A (en) | 1978-05-02 |
| NZ183271A (en) | 1979-01-11 |
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