FI63084C - FOER FARING FOR MATERIAL BANDNING FOR FRAMSTAELLNING AV SLUTFOERT PAPPER - Google Patents

Description

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JwA B UTLÄGGNINCSSKRIFT 6 3084 55¾¾ C Fatortti mySnncity 11 04 1933 ($ 4) Patent r.cidt-lat <51) K * .ik? /IBt.cu3 D 21 H 3/36 FINLAND — FINLAND (H) PfottWwfcnw — HfntindHmtn » TT0596 (22) HakwniapUvt — AnaBlinlngadac 23.02.77 '' (23) AfkupOvt— CIUghMadaf 23.02.77 (41) Tullut {ulkMcalMtvtt offamHg 09 09 77! - “*> * rthltte-. ,, hrtwit · och rtlsfntyrd — n '' AmMcm uttafd och etc. * krtfUn puMkwvd 31.12.82 ¢ 12) (33) (31) Requested · * μοΑ · ιι * —Begird prlorltM 08.03.76 United States ) Hercules Incorporated, 910 Market Street, Wilmington, 19899 Delaware, USA (72) David Howard Dumas, Newark, Delaware, USA (7I +) Oy Heinänen Ab (5I +) Method and mixture for the production of finished paper - Förfarande och This invention relates to the manufacture of finished paper and finished paperboard.

The invention relates in particular to the production of a finished paper and a finished board in which the finishing agent used is a hydrophobic, cellulose-reactive finishing agent such as a ketene dimer finishing agent and is used according to the invention with a new finishing agent accelerator for a substantially larger off-machine finish than cellulose-reactive finishing agent. the finishing agent would be used exclusively.

U.S. Patent No. 3,840,486 discloses water-soluble, thermosetting plastic-containing compositions prepared by the reaction of dicyanamide, ammonium salt, formaldehyde, and a reaction of a water-soluble aminopolyamide, such as a water-soluble aminopolyamide, with a dip of an amine polyamide. The plastic-containing compositions disclosed in U.S. Pat. No. 3,840,486 accelerate the paper finishing process by the action of cellulose-reactive finishes such as ketene dehydrates, acid anhydrides and isocyanates 2,63084. The use of the plastic-containing compositions of U.S. Pat. No. 3,840,486 in conjunction with the aforementioned paper finishes provides a greater off-machine finish than the use of screen equivalent amounts of finisher alone.

UK Patent 1,373,788 discloses the use of dicyandiamide-formaldehyde condensates as finishing accelerators for ketene dimer finishes.

U.S. Patent No. 3,409,500 discloses a process for making finished paper comprising separately adding hydrophobic organic cellulose-reactive paper finishing carboxylic anhydrin particles as an aqueous anionic dispersion to an aqueous suspension of polyulosic polyulosic fibers used in papermaking. 1000, wherein the amount of this polyamine is at least sufficient to deposit the above anhydride particles on the above fibers and to increase the rate at which the anhydride imparts its finishing properties to the cellulose fibers at a temperature in the range of 89-122 ° C, after which the suspension is formed aqueous web and this web is dried in a temperature range of 89-122 ° q.

U.S. Pat. No. 3,409,500, column 3, lines 61-70, discloses that the most effective cationic polymers are adipic acid-polyalkylene-polyamide-epichlorohydrin polymers prepared by condensing adipic acid with a polyalkylene polyamine to form a polyamide polyamine. has been reacted with epichlorohydrin. Methods for introducing this type of material are disclosed in U.S. Pat. No. 2,926,116, U.S. Pat. No. 2,926,154 and U.S. Pat. No. 3,329,657.

The cationic polymers of U.S. Pat. No. 2,926,116 and U.S. Pat. No. 2,926,154 are described in U.S. Pat. No. 3,483,077, where they have been found to be useful adhesives for ketene dimer wire finishes, where the finish can be improved compared to cationic starch-based binders.

U.S. Pat. No. 3,575,797 discloses a process for finishing paper and board products, which method comprises effectively mixing 3,63084 into an aqueous pulp or applying to an prepared paper web an aqueous emulsion of an N-substituted aziridine compound prepared by reacting a carbonyl-substituted Λ-ethylenically unsaturated compound such as alkyleneimine such as ethyleneimine, with each other. The finishing agent can be uniformly dispersed in a cationic emulsifier such as cationic starch to better adhere the agent to the fibers. Columns 1-44 of U.S. Pat. No. 3,575,796, column 4, disclose other cationic agents for use in facilitating the attachment of a finishing agent in accordance with the invention, such as cationic, thermosetting plastics such as the reaction products of two basic acids, polyalkylene polyamines and epihalohydrins. Lines 45-62 of column 4 of this publication also indicate that cationic agents are also useful emulsifiers for finishing agents.

U.S. Pat. No. 3,666,512 discloses compositions having a hydrophobic, cellulose-reactive carboxylic anhydrin as a paper finishing agent and a catalyst that accelerates the rate at which anhydride develops its finishing properties when deposited on a surface of a cellulose medium and aqueous. The catalyst or accelerator of the anhydride-based finishing agent is a cellulose-associated, water-soluble cationic salt of water-soluble polyamine. Suitable cationic substances are listed in the table in column 7 of this publication. The cationic substances are aminopolyamide-epichlorohydrin resin, whereby the aminopolyamide is prepared by the reaction between diethylenetriamine and adipic acid.

U.S. Pat.

U.S. Pat. No. 3,046,186 discloses the preparation of finished paper by the addition of an abutment treatment in which an aqueous cationic dispersion of a hydrophobic ketene diether is added to an aqueous suspension of 4,630,84 cellulosic fibers. The finished paper is prepared by forming an aqueous suspension of cellulosic fibers used in papermaking, to which is added an emulsion of a hydrophobic ketene dimer in an aqueous medium containing a cationic dispersant, which may be a monomeric or high molecular weight hydrophilic or water-soluble basic nitrogen. Dispersants are described in columns 3 and 4 of U.S. Pat. No. 3,046,186.

U.S. Patent 3,006,806 discloses the use of an organic cationic polymer with a ketene dimer in paper finishing. The cationic polymers disclosed therein are melamine-formaldehyde plastics (as disclosed in U.S. Patent Nos. 2,345,543 and 2,559,220), urea-formaldehyde plastics (as disclosed in U.S. Patent 2,657,132), cationic cereal starch, guanitine-foraldehyde plastics U.S. Patent No. 2,745,744), alkylene-polyamine halohydrin plastics (U.S. Patent No. 2,601,597) and cationic urea-formaldehyde plastics (as described in English Patent Publications (675,477 and 677,184)).

U.S. Patent No. 1,084,092 discloses a paper made using the simultaneous use of an amino resin and a hydrophobic organic isocyanate. The plastics described in U.S. Patent 3,084,092 are the polyfunctional halohydrin plastics described in U.S. Patent No. 2,595,934; the dicyandiamide-formaldehyde-amine polymers described in U.S. Patent No. 2,596,014; -substituted urea plastics described in U.S. Pat. No. 2,698,787; linear polyamine-polyamide polymers described in U.S. Pat. are described in U.S. Patent No. 2,582,840, and the aminosulfuric acid-melamine-formaldehyde plastics described in U.S. Patent No. 2,688,607.

According to the present invention, novel finishing process accelerators have been found which are suitable for use with hydrophobic, cellulose-reactive finishing agents such as ketene dimers, acid anhydrides and organic isocyanates.

5,63084

The finishing charge accelerators used in accordance with this invention are poly (diallylamine) epichlorohydrin resins proposed and described in U.S. Patent 3,700,623.

The facts set forth in this patent publication are incorporated herein by reference.

The poly (diallylamide) epihalohydrin plastics used according to the present invention are (A) plastic reaction products of a linear olymer containing units of formula I (I) R *, wherein R is hydrogen or lower alkyl and R * is hydrogen, alkyl or a substituted alkyl group and (B) is epihalohydrin.

In the above formula, each R may be the same or different and, as indicated above, may be hydrogen or lower alkyl. Alkyl groups contain 1 to 6 carbon atoms and are most preferably methyl, ethyl, isopropyl or n-butyl. R 'represented by the formula is hydrogen, alkyl or a substituted alkyl group. R'-alkyl groups may contain 1 to 18 carbon atoms (suitably 1 to 6 carbon atoms), which groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl tetradecyl and octa-decyl. R 'may also be a substituted alkyl group. Suitable substituents are generally all groups which do not interfere with the polymerization to the vinyl double bond. Typically, the substituent may be a carboxylate, cyano, ether, amino (primary, secondary or tertiary), amide, hydroxide and hydroxyl.

Polymers having units of the above formula can be prepared by polymerizing a hydrohalide salt of diallylamine ch2 ψ2 Ry fR (II) CH / CH2 A »6 63084, in which R and R 'have the same meaning as above, either alone or mixed with other copolymerized materials, free radicals after which the salt is neutralized to give an olymeric free base.

Specific hydrohalide salts of diallylamines that can be polymerized to prepare the polymeric units of this invention include diallylamine hydrochloride, N-methyldiallylamine hydropromo-di, 2,2, -dimethyl-N-diidylminide, di-isidiamine, dialylamine hydrochloride, N-ethyl-diallyl tert-butyylidiallyyliamiini hydrochloride, n, n-heksyylidiallyyliamiinihydrokloridi, n-octadecyl-diallyyliaminihydrokloridi, asetamidodiallyyliamiinihydrokloridi n, n-cyano ^ methyldiallylamine hydrochloride, n-β - propionamidodial-lyyliamiinihydrokromidi, n-karboetoksimetyylidiallyydiamiinihydroklo chloride, N- f - metoksietyylidiallyyliamiinihydrokromidi, Ν-β -aminoethyl diallylamine hydrochloride, N-hydroxyethyldiallylamine hydrochloride and N-acetohydrazide-substituted diallylamine hydrochloride.

In preparing homo polymers and gecapolymers for use in accordance with this invention, the reaction may be initiated with a redox catalyst system. In the retoxic system, the catalyst is activated using a reducing agent to generate free radicals without the use of heat. Commonly used reducing agents include sodium metamabis sulfite and potassium metabisulfite. Other reducing agents include water-soluble thiosulfates and bisulfites, hydrosulfites, and reducing salts such as sulfate of a metal that may be present at more than one valence, such as cobalt, iron, manganese, and copper. Stylish examples of such sulfates are ferrous sulfate. The use of a redox initiator system has several advantages, the most important of which is efficient polymerization at lower temperatures. Conventional peroxide catalysts such as tertiary butyl hydroperoxide, potassium persulfate, hydrogen peroxide and ammonium persulfate can be used in combination with the above-mentioned reducing agents or metal activators.

As mentioned above, the linear polymers of diallylamines may contain various units of formula (i) and / or contain units of one or more of the 6,63084 or more copolymerizable monomers. Typically! is a comonomer other than diallylamine, a monoethylenically unsaturated compound containing a simple vinyl or vinylidene group, or sulfur dioxide, and is present in an amount of 0 to 95 mol% of polymer. Thus, diallylamine polymers are linear polymers of which 5-100% of the reversible units are of formula I and 0-95% of the reversible units are monomeric units derived from formula I, vinyl or vinylidene monomers and / or (2) sulfur dioxide are preferred. -hanpo, methacrylic acid, methyl and other alkyl acrylates and methacrylates, acrylamides, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers, vinyl ethers, vinyl ethers, vinyl ethers, according to formula (II) above ..

Specific copolymers that can be reacted with epihalohydrin include copolymers of N-methyldiallylamine and sulfur dioxide, a copolymer of N-methyldiallylamine and diallylamine, a copolymer of diallylamine and acrylamide methylamide, a copolymer of allylamine and acrylamide, diallylamine diallylamine and acrylonitrile, copolymers of n-methyldiallylamine and vinyl acetate copolymers, diallylamine and metyylifinyyli ether copolymers, n-metyylidiallyyliaminin and finyyliasetaatin copolymers of diallylamine and metyylifinyylieetterin copolymers of n-methyldiallylamine and finyylisulfonamiidin copolymers of n-raetyylidiallyyli amine and metyylifinyyliketönin copolymers of diallylamine, sulfur dioxide and terpolymers of acrylamide and terpolymers of N-methyldiallylamine, acrylic acid and acrylamide.

The epihalohydrin which is reacted with the polymer of diallylamine may be an epihalohydrin, i. epichlorohydrin, epi-chromohydrin, epichlorohydrin or epiodihydrin and is most preferably epichlorohydrin. Generally, epihalohydrin is used in an amount of about 0.5 to about 1.5 moles, and most preferably about 1 mole to about 1.5 moles per mole of secondary as well as tertiary amine in the polymer.

8 63084

The poly (diallylamine) epihalohydrin plastic can be prepared by reacting the dialylamine homopolymer or copolymer described above with epihalohydrin at a temperature of about 30 ° C to about 80 ° C, and preferably about 40 ° C to about 60 ° C, until 20 to 30 ° C. The viscosity of the solution containing solids has reached a range of AE at 25 ° C and preferably about CD on the Gardner-Holdt scale. The reaction is preferably carried out in aqueous solution to keep the reaction rate reasonable and in the pH range of about 7 to about 9.5.

When the desired viscosity is reached, an amount of water is added such that the solids content of the plastic solution is adjusted to about $ 15 or less, after which the product is cooled to room temperature at about 25 ° C.

The plastic solution can be stabilized against gelation by adding sufficient water-soluble acid (such as hydrochloric acid and sulfuric acid) to its aqueous solution to bring the pH of the mixture to about 2. The resulting stabilized plastic solution can be used to practice the present invention or reactivated by known methods before use. Such gap-stabilized plastic solutions and agents for reactivating it are disclosed and described in U.S. Patent No. 3,833,531. The considerations set forth in this patent are incorporated herein by reference.

Prior to stabilization against gelation, the plastic in solution in its active, i.e., easily crosslinkable, form can be represented by the following formula: '-HpC ^ C \ C-H2C \ ® / CH2 ^ CH-CHCHo 2W 2 o

Upon stabilization against gelation, for example with hydrogen chloride, the group -CH 2 CHCH 2 of formula (IIi) is converted into the group -CH 2 CHCH 2 (IV), in which

V OH X

X is halogen such as chlorine. Upon reactivation of the plastic by the addition of 9,63084 aqueous NaOH to the plastic solution, for example, ('IV) is converted to the epoxide represented by formula (XII).

The group -CH2GHCH2 of formula (IIi) may be modified if desired

V

to the group -CH 2 CHCH 2 (V) by adding sodium bicarbo-OH OH

to a solution of a compound of formula (III) and heating the resulting solution to about 100 ° C and maintaining it there for about 1.5 hours. The compound of formula (V) cannot form crosslinks or change to form (lii) it is in the glycol form and is an inert cationic polymer.

All forms of the above plastics can be used in accordance with the present invention, and the phrase poly (diallylamine) epihalohydrin used in this context and in the claims includes all plastics in which the epihalohydrin group is of formula (III), (IIId and (V Thus, the plastic of the present invention can be represented as follows:

R / R

-h2 ^ X 'ke- / H2c ^ ^ ^ iH2 (vi) wherein E is -CHpCHCHo, -CH5CH CH- or -CH <CH GH-.

\ / Il 2l I 2

o OH Cl OH OH

The following examples illustrate the preparation of poly (diallylamine) epichlorohydrin plastics for use in this invention.

Example 1

A solution of 69.1 parts of N-methylallylamine and 197 parts of 20 ° C Be hydrochloric acid in 111.7 parts of salted water was purged with nitrogen to remove air, after which the solution was treated with 0.55 parts of tertiary butyl hydroberoxide and a solution of 0.0036 parts. parts of ferrous sulphate in 0.5 parts of water. The resulting solution was allowed to polymerize at 60-69 ° C for 24 hours to give a polymer solution containing about 52.1 g of kittens with an RSV of 10,63084 0.22. 122 parts of the above solution were adjusted to pH 8.5 by adding 95 parts of 3.8% sodium hydroxide, followed by diluting the solution with 211 parts of water and adding 60 parts of epichlorohydrin. The mixture was maintained at 45-55 ° C for 1.35 hours until its Gardner-Holdt viscosity, taken from a sample cooled to 25 ° C, reached B +. The resulting solution was acidified with 25 parts of 20 ° C Be hydrochloric acid and maintained at 60 ° C until the pH reached a constant value of 2.0. The resulting plastic solution had a solids content of 20.8 μm and a Brookfield viscosity of 77 cps. (Measurement was performed using a Brookfield Model LVF Viscometer No. 1 with a bore speed of 60 times per hour using the same controller).

Example 2 25 parts of a 9.58 # solids plastic solution prepared according to Example 1 were mixed with a solution of 1.62 parts of 10 N sodium hydroxide in 11.25 parts of water, and the mixture was allowed to age for 0.5 hours.

Example 3 150 parts of a 20% solids plastic solution prepared according to Example 1 were diluted with 172.5 parts of water. A solution of 7.2 parts of NaOH in 160 parts of water was then added to the solution. The resulting solution was allowed to stand for 5 minutes, after which 10.5 parts of NaHCO 3 were added. The solution was then heated to the onset of boiling point and heated under a condenser for 1.5 hours, after which it was cooled to room temperature. The resulting solution had a solids content (modified plastic) of 9.2 μm and a Brookfield viscosity of 77 cps. (measured using a Brookfield-model LVP viscometer, No. 1 spindle, 60 rpm using a shield).

The finishing process accelerators of this invention are used in combination with hydrophobic, cellulose-reactive finishing agents such as ketene dimers, acid anhydrides and isocyanates. Such finishing agents are known per se in the art and are usually used as aqueous emulsions. As used herein, the phrase "emulsion" 1, which is conventional in the art, means either a liquid-liquid type dispersion of 11,63084 or a solid-liquid type dispersion.

Hydrophobic acid anhydrides useful as cellulose-reactive finishes in the papermaking process include (A) plastic anhydride (see U.S. Patent No. 3,582,464) and (B) anhydrides of formula R1-C / 1 (O) (VII). wherein R 1 is a saturated or unsaturated hydrocarbon radical, wherein the hydrocarbon radical is a straight or branched chain alkyl radical, an aromatic substituted alkyl radical or an alkyl substituted aromatic radical, wherein the hydrocarbon radical contains a total of about 14 to 36 carbon atoms, the formula is °,

. C

/ \ R ,,, - R "^^ 0 (VIII)

C

II

0 wherein R "represents a dimethylene or trimethylene radical and wherein R ** 'is a hydrocarbon radical having more than 7 carbon atoms and prepared from the group consisting of alkyls, alkenyls, aralkyls or aralkenyls. Substituted cyclic dicarboxylic anhydrides of formula ( In formula (VII) above, each R 1 may be the same attached radical or each R 1 may be a different hydrocarbon radical.

Typical examples of anhydrides of formula (VII) are myristoyl anhydrides, palmitoyl anhydride, oleoyl anhydride and stearoyl anhydride.

12 63084

Typical examples of anhydrides of formula (VIII) are iso-octadecenyl succinic anhydride, n-hexadecenyl succinic anhydride, dodecyl succinic anhydride, dececyl succinic anhydride, octenyl succinic anhydride, octenyl

Hydrophobic organic isocyanates used as paper finishes are known per se in the art. The best results are obtained when the hydrocarbon chains of the isocyanates contain at least 12 carbon atoms and preferably 14 to 36 carbon atoms. Such isocyanates include resin isocyanate, dodecyl isocyanate, octadecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, eicyl isocyanate, docosyl isocyanate, 6-ethyldecyanate, 6-ethyldecyanate. polyisocyanates such as 1,8-octa-decyl diisocyanates and 1,12 dodecyl isocyanate in which one long chain alkyl group contains two isocyanate radicals and gives the molecule as a whole hydrophobic properties.

Ketene dimers used as cellulose-reactive finishing agents are known per se in the art, and the formula of the diraers is

Lr2ch = c = o] 2 (IX) wherein R2 is a hydrocarbon radical such as alkyl of at least 8 carbon atoms, cycloalkyl of at least 6 carbon atoms, aryl, aralkyl and alkaryl. In the definition of ketene dimers, the radicals “R2M are hereinafter referred to as“ ketene dimer. ”Thus, the phenyl ketene dimer is ^ ^ -CH = C = O

O

J 2 13 63084 and the decyl ketene dimer is O'10O 2 '^ ^ ^ g · Examples of ketene dimers are octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl , phenyl, benzyl-β-naphthyl and cyclohexyl ketene dimers as well as ketene dimers prepared from montamic acid, naphthenic acid, β9,10-decylenic acid, Δ 9,10-decylenic acid, 99-10 dodecylene acid, palmitic oleic acid, palmitic acid, palmitic acid, palmitic acid leucic acid, linoleic acid, linolenic acid and eleostearic acid, as well as ketene dimers prepared from naturally occurring fatty acid mixtures such as those found in coconut oil, babassu oil, rapeseed oil, palm kernel oil, palm kernel oil, palm oil, olive oil, olive oil. Mixtures of all the above fatty acids with all others can also be used.

The following examples illustrate the preparation of ketene dimer emulsions.

Example 4

An alkyl ketene dimer emulsion prepared from a mixture of palmitic and stearic acids was prepared by mixing 880 parts of water, 60 parts of cationic cereal starch and 10 parts of sodium limon sulfonate. The pH of the mixture was adjusted to about 3.5 by the addition of 98 L of sulfuric acid. The resulting mixture was heated to 90 ° -95 ° C and held for one hour. Water was then added to the mixture in such an amount that the total amount of the mixture became 1750 parts (total weight). About 240 parts of ketene dimer were added to the mixture together with 2.4 parts of thiadiazine. Thiadiazine was used as a preservative. The resulting premix (at 65 ° C) was homogenized in a single treatment in a homogenizer using a pressure of 28 bar. 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 an alkyl ketene dimer of oleic acid was used instead of an alkyl ketene dimer prepared from a mixture of palmetic and stearic acids.

14 63084

Example 6 t

The emulsion dose of Example 4 was diluted with water to a solids content of 0.10 in ketene dimers.

Example 7

The dose of the emulsion according to Example 5 was diluted with water so that the solids content of the ketene dihydrate was 0.10.

Example 8

The products prepared according to Example 1 and Example 4 were combined by adding the required amount of water to give an aqueous finishing mixture of 0.10% ketene dimer and $ 0.20 resin.

Example 9

The products prepared according to Example 1 and Example 4 were combined by adding the required amount of water to give an aqueous finishing agent containing $ 0.10> ketene dimer and $ 0.10> resin.

Example 10

The products prepared according to Example 2 and Example 4 were combined by adding the required amount of water to give an aqueous finishing agent mixture containing 0.10 L of ketene dimer and 0.10 L of acid stabilized resin.

Example 11

The products prepared according to Example 3 and Example 4 were combined by adding the required amount of water to give an aqueous finishing mixture containing $ 0.10 of ketene dimer and 0.10% of modified resin.

Example 12

The product prepared according to Example 1 and Example 5 was combined by adding the required amount of water to give an aqueous finishing mixture containing $ 0.10> ketene dimer and $ 0.10> resin.

The above finishing compositions were applied to an 18.4 kg / 320 m strip of water-leaf paper. The strip was made from a 50:50 mixture of hardwood softwood pulp in a miniature paper machine. The pH of all finishing agent mixtures was adjusted to 7 before applying the agent to the strip at the horizontal finishing press nip. The finishing press operates at a speed of 13 m / min and the moisture content was 70 ia. The adhesion of the ketene dimer finishing agent was the same in all different experiments. The finished strips were dried at 94 ° C for 20 seconds in a laboratory tumble dryer to 4 L humidity. The degree of finishing was measured on a Hercules finishing test apparatus using test solution No. 2 up to the indicated reflectivity. The values obtained outside the machine were obtained within a drying time of two minutes and the natural and aged values were obtained after storage for at least three days at room temperature. It is known in the art that a ketene dimer finisher develops substantially all of its finishing properties on paper within three days. After this time, the finishing properties that came to the paper remain essentially unchanged.

The results obtained in the finishing process are shown in Table I below.

TABLE I

Finishing mixture according to Hercules finishing machine outside the machine natural 80 ia reflectivity (s) aging 85 i ___________hei .reflective (s) 6) 2 separate 0 331 6) tests 0 400 7 0 554 8) 2 separate 310 350 8) tests 305 - 9) 2 separate tests 335 450 9) tests 160 436 10 437 590 11 250 500 12 315 500 16 63084

The following examples demonstrate the superiority of off-machine finishing when the finishing compositions of this invention were used for internal finishing.

Handmade sheets of 18.4 kg / 320 m were made in a "Noble and Wood" brand hand sheet machine using a pulp of 30 # fresh waste, 35 # 'Kayonier "bleached softwood and 35 #" Weyerhauser "bleached hardwood kraft pulp. 50 s at 102 [deg.] C. A relative amount of plastic fixing the finishing process was added as an aqueous solution such that the consistency of the pulp was about 0.275 #, after which the mixture was stirred for 15 seconds and then the ketene dimer finishing emulsion was added, followed by stirring for another 15 seconds. diluted with water so that the consistency of the pulp was about 0.025 # in the headbox before sheet formation.The amounts of fixing resin and ketene dimer used are shown in Table II below based on the weight of the pulp.

The test results are shown in Table II below.

TABLE II

Hercules viimeistelykoe

Example 80 80 for the reflectivity of Example 4

Well. natural _ _ __ nidimer emulsion of accelerator resin according to the accelerator resin aged 13 0.15 # ketene 0 300 <, · dimer 14 0.15 # "16 303 15 0.30 #" 78 464 16 0.45 # "154 594

In Examples 13, 14, 15 and 16, the accelerator resin and the finishing agent were added separately. It will be appreciated that they may be mixed together to provide a finishing composition and may also be used to finish the surface prior to addition to the pulp slurry, whereby the finished sheets were made from the thus treated slurry.

Example 17

An aqueous emulsion of octadecyl isocyanate (stearin isocyanate) was used as a finishing agent for the internal finishing of handmade sheets π '63084 using 50 l »hardwood pulp: $ 50> soft wood pulp and 10 # clay and $ 10 calcium carbonate as fillers. Cationic starch (Stalok 400), 35 l »based on the dry weight of the pulp, was added as a filler adjuvant. The amount of octadecyl isocyanate used as a finishing agent is 0.2 # based on the dry weight of the fibers.

Example 18

Example 17 was repeated with the exception that the resin prepared according to Example 1 was also added as an aqueous solution to the pulp slurry before forming the sheets in an amount of 0.125 # by dry weight of the pulp. The test results are shown in Table III below.

TABLE III

Hercules viimeistelykoe

An example of an 80? S reflectivity handmade sheet machine on the out-natural _ side ·. aging 17 18 90 18 62 75

It is clear that the above description and working examples are only intended to illustrate the inventive idea and do not limit the scope of the invention.

Claims (8)

1. A process for making finished paper using a water emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of the ketene dimers, acid anhydrides and organic isocyanates, characterized in that in combination with the sizing agent, a sizing accelerator, which is a poly (diallylamine) epihalohydrin resin, in sufficient quantity to increase the sizing effect of the sizing agent outside the machine. 2. Procedure according to. Claim 1, characterized in that the sizing agent is a ketene dimer and that the sizing accelerator is poly (N-methyldiallylamine) epichlorohydrin resin. 3. Process according to claim 1, characterized in that the sizing agent is an acid anhydride and that the sizing accelerator is poly (N-methyldiallylamine) epichlorohydrin resin. 4. A process according to claim 1, characterized in that the sizing agent is an organic isocyanate and that the sizing accelerator is poly (N-methyldiallylamine) epichlorohydrin resin. 5. Cellulose fiber sizing composition for use in a process according to any of the preceding claims, characterized in that it has as an essential constituent an aqueous emulsion of a hydrophobic cellulose reactive sizing agent selected from the group consisting of the ketene dimers, the acid anhydrides, the organic isocyanate, which emulsion contains a sizing accelerator, which is a poly (diallylamine) epihalohydrin resin, present in the composition in sufficient quantity to increase the sizing effect of the sizing agent outside the machine. 6. The sizing composition according to claim 5, characterized in that the sizing agent is a ketene dimer and that the sizing accelerator is poly (N-methyldiallylamine) epichlorohydrin resin. Sizing composition according to claim 5, characterized in that the sizing agent is an acid anhydride and that the sizing accelerator