FI67735B - FOERFARANDE FOER LIMNING AV PAPPER ELLER LIKNANDE PRODUKT - Google Patents

Description

67735

The present invention relates to a method for gluing paper or the like with a hydrophobic glue.

The purpose of hydrophobic sizing of paper is to prevent or slow down the penetration of aqueous liquids into the paper and thus to make it water-repellent, i.e. hydrophobic. The paper can be glued either by adding adhesive chemicals containing hydrophobic groups to the pulp prior to sheet-10 or web formation together with a retention aid (hydrophobic pulp sizing) or by simultaneously adding similar sizing chemicals to the web already formed during pulp sizing, usually together with surface sizing starch. Although hydrophobic surface sizing can be performed under laboratory conditions without sizing chemicals added to the pulp, such a sizing process is not possible with a full-size paper machine because the poor water retention of the paper web to the surface sizing press causes the paper web to break.

A particular object of the invention is therefore a method by which paper can be glued using already known hydrophobic surface sizing chemicals to be added only with a surface sizing press, i.e. without using any hydrophobic sizing agents to be added to the pulp.

The process according to the invention is able to replace or substantially reduce the adhesives currently used in paper sizing, such as rosin acid, reinforced rosin acid and synthetic sizing agents, such as ketene dimer-based sizing agents, carbamoyl chloride-based sizing agents, carbamoyl chloride-based sizing agents, formaldehyde-based adhesives, alkyl, alkenyl, aryl, alkylalkenyl, alkylaryl, alkenylaryl, arylaryl, oleic acid, oleic acid succinic anhydride-based adhesives and hydrophobic starches. It is also possible to replace, in whole or in part, the adhesives used in connection with the abovementioned adhesives, such as aluminum sulphate, i.e. alum and aluminate, which are generally used in connection with resin sizing. It is also possible to replace retention aids used with synthetic adhesives, such as cationic starch, as well as various synthetic polymeric retention aids.

A particular advantage of the invention is that it is now possible to obtain a glued paper product without using the above-mentioned sizing chemicals to be added to the pulp, the sizing effect of which depends on the pH of the pulp, other additives added to the pulp, such as fillers and the pulp quality itself. depending on the quality of the wood used as a material, the content of waste pulp, the content of groundwood, etc., these variables important for papermaking can be chosen freely without adversely affecting the sizing of the paper.

The gluing method according to the invention also enables so-called "acid gluing" without the need to use resin glue and alum and aluminate which reduce the quality of the paper used as its retention aid.

The sizing method of the present invention significantly reduces paper sizing costs because hydrophobic sizing chemicals for sizing paper can be dispensed exclusively with a surface sizing press, causing them to adhere to the paper 100% without the addition of sizing and retention chemicals used in hydrophobic pulp sizing.

The term "paper" as used herein means sheet-like, web-like or molded articles made from fibrous cellulosic materials. They also include similar blends of cellulose 35 and other fibrous material, such as synthetic and mineral fiber.

It has now been found that by adding to the fiber mass before web formation a retention binder combination, (K +) n - (A-) m, which together with the fiber forms the formula: (KT) n ---- (A ") m ---- β θ Θ0ΘΘΘ

FIBER

5, a paper web having such a wet strength that a hydrophobic surface sizing can be performed without hydrophobic pulp sizing agents added to the pulp. In the above formula, the term "(K +) n" means 10 cationic polymeric retention aid compounds such as cationic starch, cationic mannogalactan, polyethyleneimine, polyamine, polyamidamine, polyacrylamide, polyacrylamide, polyamine amide epichlorohydrin (melamine) , such as polysilicates, carboxymethylcellulose, carboxylated polyacrylamide or bentonite.

It is essential that the combination of substances forms an agglomerate, i.e. a molecular aggregation, which adheres to the fiber as effectively as possible. Most preferably, this is achieved so that the total charge of the formed agglomerate remains positive, so that the ratio of cationic to anionic polymer is kept within certain limits. It is most preferred for the invention to keep the ratio of cationic to anionic polymer in the range of 1: 1 to 30: 1, preferably 1.5: 1 to 25: 1, with the resulting agglomerate having the most favorable overall charge in terms of retention.

The cationic polymeric component of the combination of substances of the invention may be derived from a natural polymer or a synthetic one. The former are cationic starches, the starch of which may be derived from barley, wheat, potatoes, corn, rice, etc. The starch is made into cation-5 in known ways by means of ammonium compounds; most commonly, quaternary ammonium compounds such as 3-chloro-2-hydroxypropyl-trimethylammonium chloride are used. The degree of substitution may be 0.01 to 0.05.

Another natural polymer that can be used to make the cationic subcomponent of the invention is a mannogalactan polymer known as guar gum. Said polymer is obtained from a guar plant cultivated in Southeast Asia and is chemically a straight chain of mannose units with individual galactose branches. Guar gum can be made cationic in a known manner, as can starches. The degree of substitution may be 0.1 to 0.03.

Synthetic cationic polymers used in accordance with the invention include polyacrylamides, polyethyleneimines, polyamines and polyamideamines. Their cationic groups 20 are amino or amide groups. Melamine-formaldehyde polymers can also be used; they are prepared by polymerizing water-soluble methylol melamine salts. The polyacrylamides 6 to 7 have a molecular weight of 10 to 10, and the other synthetic cationic polymers mentioned have a molecular weight of 10 to 3 '10. Synthetic polymers are chemically active in the pH range of 4 to 8. They are known to be manufactured and are manufactured by Allied Colloids Ltd., BASF AG and Kemira Oy, among others. The longer the polymer chain, the greater the efficiency of the cationic component.

As the anionic component of the combination of substances according to the invention, colloidal silica can be advantageously used, which can be in various forms, such as polymeric silica or colloidal silica sol. The best results are obtained using a silica sol with a SiO 2 content of 35 to 60%, preferably 4 to 30%. The colloidal silica of the sol should have a specific surface area of 200 to 1000 m / g, and the best results are obtained with a specific surface area of 300 to 700 m / g, with an average colloidal silica particle size of 1 to 10 nm. The silica sol is stabilized with an alkaline solution so that the molar ratio of SiO 2: ββ 2 = 10: 1 to 300: 1, preferably 15: 1 to 100: 1, where Me can be Na, K, Li or NH 4. Eligible silicon sols are manufactured by Nalco Chemical Company, Du Pont & de Nemours Corporation and EKA Ab, among others.

Some other silicon compounds may completely or partially replace colloidal silicic acid as an anionic component of the composition of the invention. Such is mainly clay-mineral bentonite, which can also be suspended in water. Bentonite is known in the art above all as an absorbent. Also suitable as the anionic component are water-soluble cellulose derivatives such as carboxymethylcellulose and synthetic polymers such as anionic polyacrylamide made anionic by attaching carboxyl groups.

The retention aid binder combination is added to the pulp suspension prior to paper web formation. Both subcomponents of the retention binder system can be mixed together before being added to the pulp suspension. However, such a procedure does not give an optimal result. It is more preferred to form the combination of substances according to the invention in a pulp suspension so that the retention binder components are added separately, suitably diluted, to the fiber suspension maintained in sufficient agitation. Of the retention binder components, it is preferred to add the anionic component suitably diluted 30 before the cation. It is also possible to add both components at the same point in the fiber suspension, however, so that the dosages are made separately. The dosage amounts of the anionic component based on the dry weight of the paper may vary in the range of 0.01 to 0.6%, suitably 0.1 to 0.5%, and the dosage amounts of the cationic component in the range of 0.01 to 2%, suitably 0.2 to 0, 9%.

The surface adhesives used in the process of the invention may be those already known, such as resin acid-based adhesives, reinforced adhesives containing reinforced acid, styrene-maleic acid copolymer-based adhesive-based adhesives, maleic acid polymer-based adhesives, maleic acid polymer-based adhesives, maleic acid polymer-based adhesives, , polyurethane-based adhesives, malemic formaldehyde-based adhesives, fatty anhydride-based adhesives, PVC-based adhesives, PVAC-based adhesives, latex-based adhesives, carbamoyl chloride-based adhesives, ketene dimer-based adhesives, alkyl, alkenyl, alkyl, aryl, aryl , oleic acid, oleic acid succinic anhydride and their ammonium salt-based adhesives, wax emulsions, calcium and magnesium salt-based adhesive emulsions, CMC-based adhesives, starch-containing adhesives and mixtures of all the foregoing.

The surface sizing of the paper can be performed by applying the surface sizing chemical or the surface sizing chemical mixture either to the surface of the paper web directly formed by a separate surface sizing press or a similar application method. Such drops, surface-size press hydrophobic surface 20 of adhesive chemicals can be synthetic compounds, such as styrene-maleic anhydride copolymer, maleinised olefins, maleinised oil acids, maleinised of oleic acid, of the esters, a copolymer of styrene-maleiinibutadieeni, maleii-nibutadieenikopolymeeri, maleiinihappopolymeeri both the previous and 25 of ammonium akryylistyreenikopolymeerit, maleic acid ester copolymers, polyurethanes, alkyl ketene dimers, carbamoyl chlorides, melamine-formaldehyde resins, fatty acid anhydrides, wax emulsions, rosin acid, fortified rosin acid and hydrophobic starches, and mixtures thereof. The aforementioned hydrophobic surface adhesive chemicals can be dispensed as such with a surface adhesive press diluted in water. Most preferably, however, the surface sizing can be performed with these chemicals by first adding them to the cooked starch solution. Either crude starch or modified starches such as starch ethers, anionic starch such as carboxymemyl starch, sulfated starch or cationic starch such as tertiary nitrogen-containing starch or quaternary nitrogen-containing starch or quaternary starch can be used in the surface adhesive composition 35. 5 However, the most favorable gluing result is obtained using quaternary lightly cationized, oxidized starch (e.g. "Raisastarch 265" Raisio Tehtaat SF 21200 Raisio). Instead of or in addition to starch, PVA, PVC, carboxymethylcellulose-10, etc. can be added to this surface adhesive mixture. The most preferred sizing result is obtained when the viscosity of the surface adhesive mixture is less than 100 cp and the pH is in the range 6-9. Depending on the quality of the paper to be glued in each case, the ratio of starch to hydrophobic surface sizing agent can be changed, but the most advantageous sizing result is generally obtained when the amount of hydrophobic sizing agent is 0.5 to 5% of dry starch and the starch solution is 1 5%.

The invention is further illustrated by the following examples, which illustrate various embodiments of the invention without limiting the scope of the invention. The percentages given are percentages by weight unless otherwise indicated.

Example 1:

A sizing test was performed on a miniature paper machine with a capacity of 120 kg of paper per hour and a speed of 60 m / min, using the sizing method according to the invention.

The paper grade to be glued was a filler-containing fine paper. Surface weight 60 g / m and ash 17 - 18%. A talc carbonate mixture was used as the filler, with talc accounting for 75% and carbonate for 25%. This filler mixture was dispensed in water dispersed in a pulp container of a paper machine in an amount of 20% of the dry fiber. The pulp used consisted of bleached birch and pine sulphite cellulose, with birch accounting for 60% and pine for 40%. Both pulps were ground simultaneously to a degree of grinding ° SR22.

As the anionic retention binder component, 8,67735 colloidal silica sols with a specific surface area of 2,430 m / dry gram were used. The silica sol in question was metered into the riser of the paper machine just before the headbox. The dosage amount of the silica sol was 0.15% dry matter by weight of the finished paper-5 product.

As the cationic retention binder component, cationic potato starch containing 0.042 molar parts of quaternary ammonium groups per mole of anhydroglucose was used. The cationic starch was boiled to 5.2% aqueous solution with a steam cooker at a cooking temperature of 130-135 ° C. This cooking solution was diluted with hot (+ 70 ° C) water to a 1% solution before being dispensed into a paper machine leveling box. The starch solution was dispensed so that the proportion of dry starch in the finished Paper Product was 0.30%.

A mixture containing 3.5% of 0.022 molar parts of cationic oxidized wheat starch containing quaternary ammonium groups and 0.05% of dry ammonium salt of a styrene maleic anhydride copolymer was used as the surface adhesive.

(SMA_ nh3) '20 This surface adhesive mixture was applied to the surface of the paper web formed by the adhesive press section of the paper machine.

For comparison, a gluing test was performed in which the above-mentioned surface adhesive mixture was used under otherwise the same conditions, but now without the retention-bond-25 substance combination according to the invention.

In connection with the same gluing test, a third gluing test was performed, the purpose of which was to compare this new gluing method with conventional hydrophobic pulp and hydrophobic surface gluing. In this sizing test 30, a ketene dimer-based emulsion glue (Aquapel 3100 Hercules Inc.) was used as the hydrophobic pulp sizing agent, which was metered into the riser of the paper machine instead of the anionic retention binder component together with the polyacrylamide used as a retention aid. (Percol 455).

35 The above gluing test runs lasted one hour each, during which time the machine was runable (break frequency), the water retention capacity of the finished paper was measured by the so-called Cobb® assay (cf. methods Scan 26:76 and Scan M 5:76) and the finished wet strength of the paper (cf. method Scan P 5 20:67).

The table below shows the results obtained from these sizing tests.

t! ί ίο

i I

2 I ^ o I o c. 67735 ^ 'nZ «y · co co ro - -j ----— I ----------: -----------! _____________ 2 ° aj ί -π

:; is i ?, I Μ -H

, ι-o + -1 .e ω 3 i — I

„C 3 (0 (0 o i, 1 5 7-; 7 s e +>

Lf).;, - i O m its.— S, r | S *, ro: ro -Η -Η · Ή • 5, <- OJ I i— o ·. I— oo -H r — I Qj

° C 00 | CVI, CX1, Ur-r-H ID

-? B - 1 --------- 4 -------- 1 ------------- H _ X 4-1: (0 (/ > -S <T3 C> .7; 'i hd .o o3 · J "" i. Ί: <oo ro Ή 0 (Λ!

El, i! ui (+ - 4-) (1) H

r- C 5

(/> CD + -> ί 'E.? Ή CX

, C -o; ! ; ! rn rn -H: (0

° C * °: 00 I-O i -§j? £ Aii04J

'! ! - ^ o n-p% ω «: ¾ ί: § 7 Ό e -rj« ro S -: ro 1! 1 '21 -2 G> ^ - Ξ i:! 1: m ^^ 2 G Φ Ί- G - γ- ------------ {—----------- f ---------- - -JI— 4-) O '0 & :( 0

r ij! ,. ! - O)> β rt H

S c ·. <.; r i: 2 * -> c a φ

C S i '1: E (/, T -H -H

- C in | j i 'Z £ “> • ° g-:; . <u>, 5 <y g g E E p = °, I c> /), * -H m Ξ. 5 9 I I, CD c O ao ro - «ί ί e ω r-: (C * *

r- OJ! - ί 7 .f: Ξ -g G -H

σ -r- I 7 .. -P: (0 W

s ^ e 5 ti j - «ω e 3 ί ° ω £ 5 s *. ί - · ο I „T £ 0 cd + -> 4-> cc | ° 2 0): td

E C (/) O O O ^ Ui> -H

OI -r- -r- CLCO + | ,, ™ ™ -n! (0 <D

LTI + J T3 4-> E * 7 7 '.2 -H 4-> ϋ 5S ° (D (D ^ g4J (0 (Λ 1Λ O) H -rl cl

O 'III ό £ Ή · Η -H

V ^ D Li (Tl 5 3 ε y,> 1 ί4 ^ Ε τ-: (0 β · Η 5 · <~ τ- X (0 C4 <° V> c 1 Ε (0 φ ί m: ° * § ft ω om 1 E JO rt ίο (0 .C r-Γ "! ί - ie (Λ r4 (¾ α <2 ° °° ί (/) ε: ο (0 ω? 1 ι -4>, Ε C «Β (Ο 1 I Ο) ΙΟ Ε Bj id, ¾ m Ε ι / ι! 'I-vII-COröAJ (0 r + + I 1 I +: ro <υ ^«, Ξ £ ΓΓ, + j ι / jc a ^ m ffl - + ^ ¾ j 4 -> .. Γ- (0> 0) .2 eu -42: <oc <rtl o 4-> ai c

- i to I. .7¾ 7 ^ Ή G

Q-uot-; ; ι Eg_7 ^ :( 0W4J

ι— 0 1-0 + 1 ^

------------------ ’r- >> QJ E> 1 QJ <D

~ __l £ ε ^ d «ι h

j, r ~ U1 · Η I — I

-Λ TO C (Λ I> 4 P Q)., Λ: τ ω ίο i1 5 tf cm I -j ± j & m e

CM Ο! Γ— 7 · C 4-1 -H

o o! i äo, -: <ö - + -> 4-1 n. ° °; TO Ο Γ- o. rH -H U1 c - I + J (/) 'rH Μ Ή • I- b I 2 1 ° E ® «o n * OW -v7.77SC3g

'e: H2; ! T-r33Qj'-itfiCD

200 ^ '(D ο IB ΙΛ ¢) ID

. = ^ ^, E E E - 4-1 C 2 ι— CD Ο ι '' r "S CD d> (0 r- Q. S I 'G W g IB ffl C. i! J U. ^ r- 0-

(/) 3 CD

t / ι era 1 I

H3 C '1 ΣΙ = + ι;

! 1 I

j! ι! I r- j CM Λ I Ä: -L__1 _ ^ ____! ___ ί_ 11 67735

Example 2:

The gluing test mentioned in Example 1 was performed by the gluing method according to the invention. The same miniature paper machine as in Example 1 was used in this gluing test.

Resin gluing at pH 5.2 was now used as a reference. In connection with the resin gluing, only talc was used as a filler, which was dosed at 20% of the dry weight of the pulp. Aluminate and alum were used as the resin adhesive retention agent. Both resin and alum 10 were dispensed into the pulp container at 0.60% alum and aluminate dosage and 0.40% resin by weight of the finished paper.

The gluing test according to the invention was carried out under the same conditions as the resin gluing, but omitting the dosing of the resin and the alum. The pH of the pulp was adjusted to the pH conditions of the resin adhesive with dilute sulfuric acid. Otherwise, the dosage amounts and sites for the retention-binder combination were the same as in Example 1.

In the same gluing test, in addition to the surface adhesive mixture used in Example 1, surface adhesive mixtures were tested in which the ammonium salt (SMA- + mu) of the 20 styrene maleic copolymer was alternatively replaced by maleic-butadiene copolymer, polyurethane and polyacrylate.

The results obtained from these gluing tests are shown in the table below.

! [ί 1; 12 I ί! ! 1 and 1 67735! ϊ

, I

j! S ί ι Ο \ ο 1 JD ιί, _Q ί ι ^ Ο 'ι ^ Ο' .ί '! ™ —Λ ™ '-ι' Ζ ι.

σ> o tr eri! r. e ·, r— c \ j CM · - j cm - ----- 4 ------- t--; £ 'α>! ! .¾ i-? ‘T- -i— i lp1 0 co I u CO! + -> C I! ΐ «3 OI I -i ^ ______o__o <- | o J_ o> 4->! '00 + ->! ; 1 ro li] i O) ro I; - • s 1; 5 ro r— ι— ι%, <ϋ · Γ- <U I ^ '- "Ό c /> _äi i ir,

Cd -r->,. * ^.

co: ro i— s_ - p • r- ι E o; ro 'ί c -äi O r- Q. + -> J, ^ Jäi -r- (U ι i Ί: - s- fi + j Si : * = ^ O) C CO I 'E Oi-r-mo ι, ι,> ^ · <- -4-> Ό <- CO I + + I + 1 + "~ o

co (Ux: «. T T _ P

ϋ “! ; ί S k 1 - * ---—--- 1 -------- j --— η ---- C (S) S s “ae a-Ϊ I ^ e

$ 00 _ * · LO

~ en LO en ι o 1 3, “o • '• i—" co J co = Ξ to "ro eo>,>, i' r- 3 oa> <- co r— e a- ° e ro · · OJ ω o <u oi! : o> ^ -o -äi-ι- -äi "Jäi e co ι e e '' · - * Ji -O -r- -äi O -äi -r- o! cc e ro t. ι ee ro" ι - co .ro ι: ro e di: ro · -—: ro ä o 'co e, "' ^ I + ·> 3 O + J e ne! j φ

rö 00 i -QE! ro O -r- 0J CL

p * F e ι e · γ-. e ro cq.L-1 _i ro. 2J Si * 111. (Dei—; (D n cj-i-o »! Cl,‘ Ζ c o c ro e · - o; e oj e ι— o |: ro

^ · - r- -r- Π! 'r— * i— CL · <- C -r-> - f = + - * C

ro £ ® £ + == £ ω> o | e 3; c ^ s, ero 5, Λ ° * ί $ I ° 'o r— r- ι O>. OC * - dJ ro "C ΰ -o- -äi Ί- CC -I- ro O -r- r— O!> C9i" tf1- -MiECLi-t-iO -j-> ro Cl -110 * 5 · Ό Roco ro o: ro Q. Roo '-ie M ^ 8 "- OO * 1! ^ _ I ι ro

r- li: -ro CO

e> i ι; ^ 1/1 ® I 1 · '; e te e I ί ί S o ro es ti Z 2-

ro e <- + i i ι ET

E ro +! ι I! uj o • r “« r- i

‘R- r— + I! I

r— · (- '1 I I

ra 1/5 ro I I I

* S \ + -> e I I

</ 1 S- 3 | 1 f0 dr- ί Σ n: <! ä I, j | co j co i u ~> | ^ j j j i 13 67735

Example 3: A gluing test was performed on a full-scale offset fine paper machine by the gluing method according to the invention. The gluing-5 procedure mentioned in Example 1 was used in this gluing experiment.

The current production capacity of the machine was about 10 tons of wood-containing offset paper per hour. The current speed of the paper machine ranged from 500 to 600 m / min. The basis weight of the paper driven by the paper machine was 60 to 75 g / m. The cellulose portion of the Pa-10 rootstock consisted in part of bleached birch sulfate cellulose and in part of bleached pine sulfate cellulose. The filler content of the paper to be glued varied in the range of 19 to 23%.

The same colloidal silica sol as in Example 1 was still used as the cationic component 15 of the retention-binder combination, but now it had a specific surface area of 610 m / g and its dosage ranged from 0.7 to 2.0%.

A 3.5% starch solution supplemented with 0.08 to 0.10% maleic acid polymer was used as the surface adhesive mixture. The pre-test situation was used to compare the runnability and the gluing level of the paper machine, in which a ketene dimer-based glue (Aquapel 3100) was used as the hydrophobic pulp glue and cationic polyacrylamide (Percol 455) was used as the retention agent.

25 The table below shows the results obtained from this gluing test using the situation prior to the gluing test as a reference.

v, to [I,.

(Λ j j lii 1 • r- LO I i ^! ^ T * O; ΓΟ j r— CO C-i E CVJ CV CVJ OO OJ C \ J '- I—! 1

ro 3! I

> · S ~ · I

—3 - ^ - 1 - <-! ------ '67735 o c' I '5! '-Q C <0 LO .— -r- Ojr ^! Q.! O J e T 't Ο- ΙΛ I! :, o LO;

u £ i:; r0 I,,: <Τ3 I

«A ·! i 15 5 _> ____ I_ _I; : oo c ^ I 1 r i ~ ~ i H TftJ! I 1 ‘S aj fi; ; I! - J E j j 2: 5 *>] 1 I c; r

C! I! O rT

2J-2U! - «J

• 4- o a: i 0 S- lx * 3- «tf ·! ro! · Σ * - 0- I>. r- 4-1 fO! 1 LO £ .IS *; ! : >> 7: ----- rrr-- £ ----- i ---—----------------------- ·, · - * ->, >>! , 'o :, - LX r— LX LX LT) I—:! F = .r- "O - - O ', /! ._ 1 ro CL ro CO ro Q. OI I—

JO. LX 1 + J

t LO lo x: lo to lox -! cj c:, r *> V "Z>) i>) · Γ- ro j C · <- • r- '- r— <_ l C« - f—! I— Γ r C! O i- * - <u <d · <- α> <υ! <D -r-.! C φ fO LO 00 * r- ^ L *:; CO · <- j *: 1 00 Cl + -> oo J *: * O <D -a * o <DI Z3 <V, CO i-CO S- * r- J *. I roc.

co «r- o>; ru: ioo a): ro: ro o ro: rc I e Q- i /) H" h ~ + EH— h— I— + E h— '· r— c 5! - > «- '·' --- 1 Εχ · ί £ °

w I VS

LlJoijl: lx lx lx lx! Dl lo

* C t— r— I—, -! Ό ‘X

^ · Γ- · δ-5 * «- ..! c: £> S S <° o oo ^! 2 ____: o- —J LO 1 ^ ._ <o Q- | ^ to ^ ° OOI IX LX ί ai · & «« 3- ro ro 1 ai o * "n I -mi-% ™ ° OOO + ->> ^ ro 01 - * + J 4-> j 0J C 4- 5 --- ^ 3 r- -r->

ΓΓ r— r— E> 0 fO

O 1— CD r— CD i— O)> - r— ^ 2 0.0 Cl o CL o cl O -r->, E fOO fOO <OÖ (fOO: r ai, r ~ ^ s- 3 i. Ns_] ai- -r-,

, r- σ · <υ era era Creu lacrO

i- <C a. <a <CL t et CL. JH -r- ^ I to e loss CO cu Oro iDr- | o ro: a>, a <λ oo> - o oo i— oa (O λλ r> r \ * r <«sn ^ ^ OO OOOO OO · r— o -Lt; ro ------- 1 _ I L_ · + -> -r-

r ------ \ ---- QJD L

• li E CD O

.ro 13 * r— Cl - ^ 3 lo in-Ri * ro evi ro <s> e; to * - 'r J Λ Λ * \ n * L Λ Qj ·, _ | ra32cro ojoo | «o * c \ j c \ j 03 1: 03 4->: ro _____ [4-> 4-> + ->

—- I -η ---------- 1 - <n r— + -J

Π3 l / | ί I £ g: 2 -iL CJDr-r-IrO Λ Λ 0t- -CS5 r- ι-r rr C \ j „

_t___I T .__ I T

t 1 I

O Q

££ * 1- il II

* r— (¾ 'NO Γ "r— LO r- r— Q_ CL. CD U0 .— n-, -, - --- j ------ f — rt- • t— -r- 1 rO ro

+ -> * -> I

CO L. ΓΟ ^ 3- ^

Φ v I

___>: f> I

Claims (9)

67735 15 A method for hydrophobic gluing of paper or a similar fibrous product, characterized in that a cationic polymeric compound (K +) r and an anionic polymeric binder compound (A) are added to the fibrous stock before applying the hydrophobic glue to the web, reacting with the fibers . Process according to Claim 1, characterized in that the ratio of cationic polymeric retention aid (K +) n to anionic polymeric binder (A ') m is in the range from 1: 1 to 30: 1, preferably in the range from 1.5: 1 to 10 : 1. Process according to Claim 1 or 2, characterized in that the cationic polymeric retention aid and the anionic polymeric binder are added to the fiber suspension separately. Process according to one of the preceding claims 1 to 3, characterized in that the anionic polymeric binder is added to the fiber suspension before the cationic polymeric retention aid. Cationic polymeric retention aid for carrying out the process according to one of the preceding claims 1 to 4, characterized in that it is a natural polymer, such as cationic starch or guar gum. Cationic polymeric retention aid according to Claim 5, characterized in that it is synthetic, such as polyacrylamide, polyethyleneimine, polyamine, polyamideamine or melamine-formaldehyde polymer. Anionic polymeric binder for carrying out the process according to one of the preceding claims 1 to 4, characterized in that it is colloidal silicic acid, bentonite, carboxymethylcellulose or anionic polyacrylamide. Process according to one of Claims 1 to 4, characterized in that the absolute amounts of cationic compounds mentioned in claims 5 and 6 in the paper product, based on the dry weight of the paper, vary in the range from 0.01 to 2.0%, but most preferably in the range 0.2-0.9%. Process according to one of Claims 1 to 4, characterized in that the absolute amounts of such anionic compounds in the finished paper product, based on the dry weight of the paper, vary from 0.01 to 0.6%, but most preferably from 0.1 to 0.5%.