FI80279B - FOERFARANDE FOER FRAMSTAELLNING AV PAPPER, KARTONG OCH PAPP MED STOR TORR- OCH VAOTBESTAENDIGHET SAMT LUTBESTAENDIGHET. - Google Patents

Abstract

1. A process for the production of paper, cardboard and board having high dry strength, wet strength and alkali resistance by adding an aqueous polymer solution to the paper stock in an amount of from 0.1 to 5% by weight, based in each case on the solids, and draining the paper stock on a screen to form sheets, wherein the aqueous polymer solution used is a reaction product obtained by reacting (1) a homopolymer of a vinylimidazole of the formula I see diagramm : EP0146000,P6,F1 where R**1 , R**2 and R**3 are each H or CH3 , and R**1 may furthermore be C2 H5 , C3 H7 or C4 H9 , or (2) a water-soluble copolymer of a) at least 5% by weight of a vinylimidazole of the formula I, b) up to 95% by weight of acrylamide and/or methacrylamide and, if desired, c) up to 30% by weight of acrylonitrile, methylenically unsaturated C3 -C5 - carboxylic acid or one of its esters, with epichlorhydrin in a ratio of from 0.02 to 2.9 moles of epichlorhydrin per molar equivalent of basic nitrogen in the homopolymer or copolymer, in the absence of a polyalkyleneimine.

Description

Process for the production of paper, board and paperboard with high dry and wet strength and alkali resistance 1 80279 5 For the production of wet-strength paper, in the neutral or weakly alkaline pH range, almost exclusively resins prepared by reacting epichlorohydrin with long chain are practically added to the pulp. with polyamidoamines, cf. U.S. Pat. No. 2,926,116. Because the polyamide chains underlying the resins are relatively easily hydrolytically degraded, these resins have the disadvantage that they have only relatively low storage stability. There is a need for improvement in the alkali resistance of papers treated with these resins.

U.S. Patent No. 3,700,623 discloses resins prepared by reacting epichlorohydrin with polymers of diallylamines. Such products enable the production of papers with high dry and wet strength as well as lye resistance. However, resins are quite expensive and as a result have not achieved favorable reception in practice. One disadvantage of these resins is that they must first be activated with lye in a paper mill to achieve an optimal effect. In addition, resins have the disadvantage that they cause a strong darkening of the whiteness of the papers treated with them.

It is an object of the invention to prepare for use such resins which, when added to the pulp in a neutral or weakly alkaline pH range, improve the dry and wet strength as well as the resistance of the paper thus produced. The resins should be directly usable without activation and, moreover, should not cause the whiteness of the paper to darken.

According to the invention, this object is achieved by a method 2 80279 for producing paper, board and cardboard with high dry and wet strength and alkali resistance, adding aqueous polymer solutions in an amount of 0.1-5% by weight, based on the amount of solids, and removing water from the 5 sheets by wire forming. in connection with.

The invention is characterized in that the polymeric aqueous solutions used are reaction products prepared by reacting (1) homopolymers of vinylimidazole of the formula I, 10 R3 \ J'r1 (I1 CH = CH.> 15 2 where R *, R2, R3 = H, CH 3, and further means C 2 H 5, C 3 H 7, C 1 H 9 or (2) water-soluble copolymers consisting of 20 (a) at least 5% by weight of vinylimidazole of formula I, (b) not more than 90% by weight acrylamide and / or methacrylamide and optionally (c) up to 30% by weight of acrylonitrile, methacrylic nitrile, vinyl acetate, vinylpyrrolidone, C3-C5 ethylenically unsaturated carboxylic acid and its ester, epichloride; imines are present in a ratio of 0.02 to 2.9 moles of epichlorohydrin per mole of basic nitrogen equivalent of the homo- or copolymer.

Homopolymers and copolymers of vinylimidazole are known. They are obtained, for example, by polymerizing vinylimidazoles of the formula I 35 r2

-OF

r3-C (^ -R1 "r ch = ch2 3 80279 12 3 1 wherein R, R, R = H, CH2; and R, moreover, represents C 40 to 100, preferably 60 to 100. R 1 may, in the case of C 1-4 alkyl, be n- or isopropyl, and in the case of C 1-4 alkyl may be n-, iso- or tertiary butyl .

To prepare the copolymers of vinylimidazole, at least 5% by weight of vinylimidazole of the formula 10 I is used as component (a), while at most 95% by weight of acrylamide and / or methacrylamide is used as component (b) of the copolymer. For the preparation of wet-strength resins, it is preferable to use a copolymer as the starting polymer.

compounds consisting of (a) 15-30% by weight of formula I

12 3 15, wherein R, R and R are H or R and R are H and R is methyl, or a mixture of monomers, and (b) 85-70% by weight of acyl. acrylamides.

The copolymers can be modified, e.g., so that et-20. as component (c) they contain up to 30% by weight of acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyrrolidone, a C 1 -C 4 ethylenically unsaturated carboxylic acid or an ester thereof. The monomers of component (c) are added in such an amount that the resulting copolymers are still water-soluble. Therefore, for example, only up to about 5% by weight of long chain esters of ethylenically unsaturated C 1 -C 4 carboxylic acids are polymerized, while up to 30% by weight of acrylic acid methyl ester or acrylonitrile may be present in the copolymer structure. Several monomers mentioned in (c) can also be used simultaneously in the polymerization to modify the copolymer, e.g. acrylonitrile and acrylic acid, acrylonitrile, vinyl acetate and vinylpyrrolidone or acrylic acid and acrylic acid ester.

4 80279

K-values for vinylimidazole homo- and copolymers are between 30-150, preferably between 60-120 (determined according to H. Fikentscher as 0.1% polymer solution in 5% aqueous salt solution at 20 ° C) . They are reacted in aqueous medium with epichlorohydrin to form resins. 0.02-2.9, preferably 1.0-2.5 moles of epichlorohydrin are used per mole of basic nitrogen equivalent in the polymer. The resins are preferably prepared by adding epichlorohydrin to an aqueous solution of the homo- or copo-2Q lymer of formula I and allowing the components of the mixture to react with each other until no more epoxide is detectable. In order to properly control the reaction, epichlorohydrin is added continuously or in portions. The reaction temperature is in the range of 0 to 100 ° C, preferably 20 to 80 ° C. Reaction times are about 2-6 hours. Condensation takes place in the pH range of 5-10. To obtain stable resin solutions, the pH of the aqueous solution is adjusted to a value between 2-4 before or after the end of the condensation. For this pH-20, sulfuric acid or formic acid is preferably used. Ready-to-use aqueous resin solutions have a dry matter content of 10-20% by weight and a viscosity of 100-5000 mPas (determined as a 10% solution according to Brookfield, 20 rpm, 20 ° C).

Aqueous resin solutions can be used in papermaking directly or possibly with water after further dilution, as they can be diluted with water in any ratio. They are added to the pulp before sheeting in an amount which in each case is between 0.1 and 5, preferably between 0.25 and 1% by weight, based on the dry matter. If aqueous solutions of the resin are added in an amount of between 0.005 and 0.1%, in each case based on dry fiber and 100% resin, to the pulp just before it is fed to the paper machine, these resins become excellent creping aids, e.g. for hygienic papers .

Il 5 80279

The resin solutions used according to the invention are added to the fibrous slurry under conventional papermaking conditions. Resins are effective in all known grades of paper, cardboard and board, e.g. in the manufacture of writing, printing and packaging papers. Papers, paperboards and cartons can be made from a variety of fibrous materials, for example, sulphite or sulphate cellulose (bleached or unbleached, ground or waste paper or mixtures of said fibers). The pH of the pulp suspension is between 4-9, preferably between 6-8. It is also possible to apply the resin solutions to the surface of the already formed paper, e.g. in an adhesive press.

In the following examples, the parts reported are 15 parts by weight, the percentages given refer to the weight of the substances.

The sheets were prepared in a Rapid-Köthen laboratory sheet instrument. The dry break length was determined according to DIN 53 112, sheet 1 and the wet break length according to DIN 53 112, sheet 2.

The liquor resistance was determined in the same way as the wet strength, using 1% sodium hydroxide solution (5 minutes at 50 ° C) instead of water to dip the papers.

The whiteness of the paper sheets was determined using a reflection photometer (Elrefo instrument) according to DIN 53 145.

The K-value of the polymer was determined according to H. Finkentscher by Cellulosechemie 13, 58-64 and 71-74 (1932), at 20 ° C in 5% aqueous table salt; then means K = k'lO'5.

Preparation of Resin Solutions 3Q Resin 1 (a) Preparation of an aqueous solution of N-vinylimidazole homopolymer.

To the polymerization vessel were placed 500 parts of vinyl iridate sol and 450 parts of water, and while nitrogen was passed through the vessel at 100 ° C for one hour, 8 parts of tert-butyl perethylhexanoate in 40 parts of 6,80279 parts of methanol were added thereto. After the addition of the polymerization initiator was complete, the reaction mixture was post-polymerized for 7 hours at 91 ° C and then diluted by adding water to a dry matter content of 30.3%.

This gave a brown, slightly turbid, highly viscous polymer solution. The K-value of the pleasure polymer was 86.

(b) Reaction of the homopolymer with epichlorohydrin.

A 30.3% aqueous solution of 10,878 g of the poly-N-vinylimidazole obtained in (a) (corresponding to 2.7 equivalents of basic nitrogen) was diluted with 1630 g of water and 677 g (7.3 moles) were added. ) epichlorohydrin at room temperature. This again increased the viscosity of the solution hi-15. After 30 minutes, 193 g of sulfuric acid (2 moles) were added, after which the pH became 2. The reaction mixture was heated to 80 ° C and stirred for 4 hours at this temperature, whereby 2100 g of water were added portionwise. An aqueous solution of resin 1 having a dry-2Q content of 17.2% and a pH of 1.7 was obtained. The viscosity of the aqueous solution was 380 mPas.

Resin 2 (a) Preparation of aqueous copolymer solution.

250 parts of water were placed in the polymerization vessel and, while stirring and passing nitrogen through the vessel, substance I and II, fed simultaneously from two separate feeding vessels, were added at a temperature of 90 ° C for one hour. Feedstock I comprised 150 parts of acrylamide, 150 parts of vinylimidazole and 150 parts of water, while feedstock II consisted of a solution of 3 parts of 2,21-azobis (2-amidinopropane) di-hydrochloride in 47 parts of water. The reaction mixture was then post-polymerized at 90 ° C for 4 hours and its dry matter content was adjusted to 30.3 ° by adding water.

35 The K value of the copolymer was 68.

Il 7 80279 (b) Reaction of the copolymer with epichlorohydrin.

233 g (corresponding to 0.4 equivalents of basic nitrogen) of a 30.3% aqueous solution of the copolymer of (a) were diluted with 286.5 g of water, and 41.6 g (0.45 mol) of epichlorohydrin were added to the mixture at room temperature. The reaction mixture was then slowly warmed to 75 ° C.

After 60 minutes, the viscosity of the reaction mixture had clearly increased. It was then adjusted to pH 44 with 44 g: 0.8 m 3 of less than 85% formic acid and the mixture was further stirred at 75 ° C for 2 hours. After this time, the reaction was complete. The dry matter content of the reaction mixture was adjusted to 15 by adding 200 g of water. The viscosity of the aqueous solution of resin 2 was 230 mPas and the pH was 15.

Resin 3 (a) Preparation of aqueous copolymer solution

125 parts of water were placed in the polymerization vessel and, while stirring and passing nitrogen through the vessel, it was heated to 80 ° C. As soon as the temperature of 80 ° C was reached, two separate feeds were continuously added to the vessel within one hour. Feedstock I comprised a solution of 225 parts acrylamide and 75 parts N-vinylimidazole in 225 parts hydrogen, while feedstock II was a solution of 3 parts 2,2'-azobis (2-amidinopropane). ) dihydrochloride in 47 parts of water. After the addition of monomers and initiator was complete, the reaction mixture was post-polymerized for a further 4 hours at 80 ° C and then adjusted to a dry matter content of 10.1% by adding water. The K value of the copolymer was 84.

(b) Reaction of the copolymer (a) with epichlorohydrin.

To 297.6 g (corresponding to 0.1 equivalent of basic nitrogen) of a 10.1 L aqueous solution of copolymer (a) was added 150 g of water, 16.7 g (0.18 moles) of epichlorohydrin and 9, 7 g (0.18 mol) of 85% formic acid and the mixture was heated to 75 ° C. After a reaction time of 4 hours at 75 ° C, an 8.4% aqueous solution of resin 3 with a viscosity of 3800 mPas and a pH of 3.6 was obtained.

Resin 4 (a) Preparation of aqueous copolymer solution.

145 parts of water were added to the polymerization vessel, and while water was stirred and 10 ° C nitrogen was passed through the vessel, it was heated to 80 ° C. After the water in the vessel had warmed to 80 ° C, substances I and II were added simultaneously within one hour. Feedstock I comprised a solution of 255 parts acrylamide and 45 parts N-vinyl-15 imidazole in 255 parts water, while feedstock II comprised a solution containing 1.5 g of 2,2'-azobis (2-amidinopropane) - dihydrochloride in 48.5 parts of water. After the addition of monomers and initiator, the reaction mixture was post-polymerized for a further 4 hours at 80 ° C and then diluted with water to a dry matter content of 5%. The K value of the copolymer was 113.

(b) Reaction of copolymer (a) with epichlorohydrin.

To 894.6 g (corresponding to 0.08 equivalents of basic nitrogen) of the 5% aqueous solution of copolymer (a) described above at room temperature were added 6.9 g (0.13 mol) of 85% formic acid and 11, 8 g (0.13 moles) of epichlorohydrin. The reaction mixture was heated to 80 ° C and stirred for 5 hours at this temperature.

3Q An aqueous solution of resin 4 having a dry matter content of 6.0% and a pH of 3.6 was obtained. The viscosity was 600 mPas.

Example 1 A 0.5% pulp suspension was prepared from 100% spruce sulfite cellulose in water. The pH of the suspension was 7.5, the degree of grinding was 35 ° SR. The pulp suspension was divided into equal portions, and sheets with a basis weight of 80 g / m 2 were prepared from each under the following conditions: (a) Nothing was added to the pulp suspension.

5 (b) A 1% aqueous solution of a commercially available neutral wet strength resin based on the reaction product of epichlorohydrin and a polyamidoamine consisting of diethylenetriamine and adipic acid was added to the pulp suspension, calculated in each case on a dry weight basis. A neutral wet strength resin was prepared according to Example 1 of U.S. Patent No. 2,926,116.

(c) 1% of the above-mentioned resin 3, in each case calculated as dry matter, was added to the pulp suspension.

Of the three sheets obtained according to (a) to (c), 15 had a dry break length, a wet break length, a lye resistance and whiteness. The results are shown in Table 1.

Table 1 (a) (b) (c) 2Q Breaking length when dry (m) 4450 5340 5990

Breaking length when wet (m) 0 1120 1190

Paper out of date:

Breaking length when wet (m) 120 1520 1450

Paper aging 5 min 110 ° C: 25 Alkali resistance 0 725 980

1% Sodium Liquor for 5 min at 50 ° C

Paper out of date:

Durability of the lye 0 1020 1090

1% Sodium Liquor for 5 min at 50 ° C

Paper aging 5 min 50 ° C: 30 Whiteness 80.5 59.0 73.5% degree of reflection

Example 2 An aqueous suspension of 0.5% pulp was prepared from 100% mixed waste paper. The pH of the suspension was 7.2, the degree of grinding was 50 ° SR. The pulp suspension was then divided into five equal parts, and sheets weighing 80 g / m 2 were prepared from each under the following conditions: (a) nothing else was added to the pulp suspension, 5 (b) 0.5% of dry fiber was added, the neutral wet strength resin shown in Example Ib), (c) added 1.0% based on dry fiber, the neutral wet strength resin shown in Example Ib), (d) adding 0.5% in each case based on fiber 10 resin 4 and (e) added 1, 0% in each case, calculated on the fiber content, resin 4.

From all sheets of paper thus prepared, the breaking length was measured dry and wet. The results are presented in Table 2.

Table 2

Experience Breaking length Breaking length Breaking length dry wet wet 2Q (m) (m) (m) aged

5 min at 110 ° C

i - · '-' "; a) 2420 0 0 1 b) 25 70 3 9 0 5 90 c) 2890 520 900 25 d) 2750 475 580 e) 3050 714 910

Example 3

In a test paper machine with a working width of 75 cm, 80% bleached spruce sulphite cellulose and 20% bleached beech sulphite cellulose were produced at a speed of 60 meters / minute so that the paper had a basis weight of 8Q g / m 2. The pH of the pulp suspension was 7.5, the degree of grinding was 35 ° SR. Under the following conditions (a) to (g), papers were prepared from this pulp suspension: 11 80279 (a) none added, (b) 0.25% neutral wet strength resin from Example (Ib) added, (c) 0 added , 5% resin according to (b), 5 (d) added 1.0% resin according to (b), (e) added 0.25% resin 4, (f) added 0.5% resin 4, (g ) added 1.0% resin 4.

The percentages given refer in each case to the solids, i.e. the pulp suspension as well as the solids of the resin solutions. The addition of the resin solutions according to (a) to (g) was carried out in an area where the pulp had already thickened. From the papers thus prepared, the wet breaking length and the alkali resistance were determined. The measurement results 15 are averages in the longitudinal and transverse direction of the paper relative to the paper machine. The following values were obtained:

Table 3

Breaking length (m) Alkali resistance 20 _1% NaOIl, 5 min 50 ° C

a) 0 0 b) 340 240 c) 550 340 d) 840 470 25 e) 405 515 f) 580 735 g) 870 940 30

Claims (2)

A process for the production of paper, board and cardboard having high dry and wet strength and alkali resistance by adding aqueous polymer solutions to the stock in an amount of 0.1 to 5% by weight, based on the amount of solids, and removing water from the stock by wire, sheet in the case of dosing, characterized in that reaction products prepared by reacting (1) homopolymers of vinylimidazole of the formula I are used as polymeric aqueous solutions, R3-Ä Jlt-R1 (!) 15 T1 ch = ch2 where R3, R2 , R3 = H, CH-j; and R 3 further represents C 2 H 5, C 3 H 7, C 2 H 9 or 20 (2) water-soluble copolymers consisting of (a) at least 5% by weight of vinyl imidazole of formula I, (b) up to 90% by weight of acrylamide, and / or methacrylamide and optionally 25 (c) up to 30% by weight of acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyrrolidone, C3-C5 ethylenically unsaturated carboxylic acid or an ester thereof; with epichlorohydrin in the absence of polyalkyleneimines 30 in a ratio of 0.02 to 2.9 moles of epichlorohydrin per mole of basic nitrogen equivalent of the homo- or copolymer. Process according to Claim 1, characterized in that reaction products prepared by reacting water-soluble copolymers consisting of (i) 15 to 30% by weight of N-vinylimidazole and (b) 85% by weight are added. -70% by weight of alkrylamide; with epichlorohydrin in the absence of polyalkyleneimines. i4 80279 1. For the production of paper, paperboard and paperboard with a maximum of 5 to 5 weeks, the genome of which has been reduced to 0.1-5% by weight, The reaction is carried out in the form of an image, the reaction is carried out by means of a wattage polymeric reaction product, which is a 10-fold genome with a variant (1) of a homopolymer of vinylimidazole with the formula I (CN r3_J) ch = ch2 color R1,, R · ^ = H, CH2; and R 2 is an intermediate C2H5, or 20 (2) water-based shampoo polymer of (a) at least 5% by weight of vinylimidazole from formula I, (b) up to 90% by weight of acrylamide and / or methacrylamide, optionally (c) 30 % acrylonitrile, methacrylonitrile, vinyl acetate-25, vinylpyrrolidone, and C3-C5 ethylene containing carboxylic acid or ester, with epichlorohydrin, with the addition of polyalkylenemines, and 0.02-2.9 mol of epichloride mol basisk kväveequivalent i homo- eller sampolymeren. 30 A preferred embodiment according to claim 1, wherein the reaction product is present in a solid genome with the presence of a water-based shampoo polymer (a) 15-30% by weight of N-vinylimidazole and 35 (b) 85-70% by weight epichlorohydrin, i fränvaro av polyalkyleniminer.