FI57279C - AEMNE OCH FOERFARANDE FOER NEUTRALLIMNING AV KRITFYLLT PAPPER PAPP OCH ANDRA CELLULOSAHALTIGA MATERIAL - Google Patents

Description

RSF ^ I [B] (11) KUULUTUSjgUCA.SU r797o ffiTp l J ^ 'utlAggningsskrift b / Zfy C (45) Fatentti -sySr.n: tty 10 07 1900 (51) Ky.lk. * / Lnt.CI. · D 21 D 3/00 D 21 H 3/08 FINLAND —FINLAND (21) fw «ittlh« k.imi.-p «« nt * n ^ knln | 2568/73 (22) Hukumhpilvt - Ameknlngidag l6.08.73 ^ '(23) Alkupilvft — GUtighKadif l6.08.73 (41) Tullut JulkMal - Blfvlt offantllg 18.02.7 ^ p »t« nttl- I »rekirterlhellltus (+4) Nlhtiv | * date of the month. - -

Patent- oeh ragiatarttyralaan '' AmMom utltgd oeh utUkrft «n puWicend 31.03.80 (32) (33) (31) Requested privilege-Β« «Μ prlorltet 17.08.72

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 22 ^ 0396.9- ^ 5 (71) Oiulini Chemie GmbH, Postfach 123, 67 Ludwigshafen / Rhein 15, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Ervin Hechler, Mannheim, Otto Helmboldt, Ludvigshafen / Rhein, Federal Republic of Germany - Förbundsrepubliken Tyskland (DE) (7 * 0 Oy Kolster Ab (5 * 0 Substance and method for the neutral gluing of chalk-filled paper, cardboard and other cellulosic materials Been - Ämne och förfarande för kritfyllt papper, Papp och andra cellulosahaltiga material

When gluing paper, cardboard or cardboard, their moisture absorption or permeability is known to decrease. This makes the paper printable and prevents ink from penetrating too quickly. Bonding still plays an important role in the use of paper as a printing medium, especially in offset printing.

In many cases, weakly or strongly saponified rosin resins are used for gluing. The precipitation and attachment of the resins to the cellulose fibers usually takes place by means of aluminum sulphate in the pH range 1 +, 0-5.0. As a result, the resulting papers and cellulosic suspensions contain free acids and react acidically. For this reason, a substance of particular economic interest, chalk, cannot be used as a filler in gluing because it decomposes. Below pH 6.5.

There are still other drawbacks to the acidification method using rosin resins. Due to the acid content novelty, the aging resistance and mechanical strength of the paper decrease. The receptivity of inks also slows down in many cases. In addition, corrosive phenomena occur in screens and machine parts due to the acidic mode of use.

2 57279 For this reason, attempts have been made to find substances and methods by which cellulosic materials can be glued in a neutral region. For example, plastics based on maleic acid copolymers or styrene copolymers have been proposed for this purpose. Ketene dimers have also been proposed for use as sizing agents, which are activated only during the drying of the fibrous webs and are thus rendered effective. Although all of these known methods have certain advantages, they can only be used to a limited extent. Thus, for example, neither woody papers nor waste paper can be treated with ketene dimers. In addition, metal salts, such as alum, have a very detrimental effect on their potency.

Thus, the object is to find a substance which can be used to glue chalk-filled papers and other cellulosic materials, e.g. fibrous preparations, in a neutral manner and which can avoid the above-mentioned disadvantages.

The solution of the set task is based on the fact that the sizing agent consists of an aqueous dispersion containing 50-95% by weight of fully or at least 50-% of soaped fatty acid containing carbon atoms and 50-5% by weight of a compound containing 50-5% by weight of polymeric carboxyl groups. The fatty acids used according to the invention can be either straight-chain or also branched. They can also be up to 20% by weight, based on fatty acids, of a saturated nature. It is irrelevant to the subject matter of the invention whether naturally occurring or synthetically prepared fatty acids are used. Thus, for example, it may be very advantageous to use naturally occurring liquid oleic acids, such as rapeseed oil fatty acid, for economic reasons.

Although the use of partially saponified unsaturated fatty acids in sizing agents is already known from German application 2090, it has been shown that the above-mentioned agent is not suitable for gluing in the neutral zone. As has been found, such sizing agents can only be satisfactorily precipitated in the neutral range and attached to the cellulosic fibers when they have a higher degree of saponification and when added in admixture with polymeric carboxyl group-containing compounds. When used in admixture with polymers containing carboxyl groups, their surprisingly improved adhesion to the fibers considerably, especially when they are precipitated with cationically active substances, for example aluminum sulphate.

Polymeric compounds containing carboxyl groups, like fatty acids, can be of natural origin or they can also be synthetic. Particularly suitable are water-soluble salts of strongly etherified carboxymethylcelluloses. Other compounds may be used, for example the sodium salt of alginic acid. According to a particularly preferred embodiment of the invention, the dispersion contains from 10 to 35% by weight of a compound containing polymeric carboxyl groups.

3 57279

As already mentioned, in order to achieve good neutral sizing efficiency, the degree of saponification of oil fatty acids must be quite high. According to the invention it is at least 50% and preferably 70-90%. The saponification of the fatty acids is carried out with alkali hydroxides or ammonium hydroxide. It can take place both at room temperature, for example ammonium hydroxide, and also at temperatures between T0 and 80 ° C, for example with alkali metal hydroxides. As stated above, the oleic acids are preferably saponified with potassium liquor, since this gives a very good flow property for the adhesive dispersion. If necessary, the flow property can also be improved in a manner known per se by adding viscosity-lowering agents, such as urea or dicyandiamide.

It should also be mentioned that saponified fatty acids can of course also be used as mixtures, for example as mixtures of oleic fatty acids having 16 to 20 carbon atoms. Some of the fatty acids can also be replaced by other hydrophobically active substances, for example paraffin or waxes. The aqueous dispersion may also contain other excipients conventionally used in the paper industry, for example starch, methylcellulose, colorants, fungicides, etc.

The following example illustrates the invention in more detail. The numerical ratios of the examples refer to weight ratios, unless otherwise stated.

Example 1

Prepare a batch containing 1U5 parts of distilled rapeseed oil fatty acid 35 parts of commercial carboxymethylcellulose (lyiose CBS 30) 20 parts of potassium hydroxide 800 parts of hot water at about 80 °

Stir vigorously at 70-80 ° C for one hour. In this case, the carboxymethylcellulose dissolves as its sodium salt, and the fatty acid is saponified.

The dispersion is then placed in containers and allowed to cool.

Example 2

Mix the following ingredients: 150 parts of distilled rapeseed oil fatty acid 20 parts of alginate (Erotacell) 22 parts of potassium hydroxide 8 parts of urea 800 parts of hot water at 80 ° C

Mixing, dissolving and saponification again take place at 70-80 ° C in about an hour. The dispersion is then placed in a storage vessel and allowed to cool.

11 57279

Example 3

The following batch is prepared: 100 parts of distilled rapeseed oil fatty acid 35 parts of commercial carboxymethylcellulose U5 parts of paraffin (softening point 5U / 56 ° C) 15 parts of potassium hydroxide 5 parts of urea 100 parts of about 80 ° C hot water Dispersion takes place as above.

Example U

Mix 10 parts of distilled rapeseed oleic acid n 30 parts of commercial carboxymethylcellulose (Tylose CBS 70) 15 parts of potassium hydroxide 10 parts of triethanolamine 5 parts of dicyandiamide 800 parts of hot water at about 80 ° C The treatment is carried out as described above.

The sizing agents prepared according to the examples are flowable and are excellent for the production of chalk-filled papers, especially when the pulp contains a lot of wood-containing ingredients and a high filler-binding capacity is required.

Example 5 Starting materials: 150 parts of rapeseed oil fatty acid 35 parts of commercial carboxymethylcellulose (Tylose CBS 30) 5 parts of urea are mixed with 775 parts of cold water. After thorough mixing, 35 parts of ammonia (25 .mu.l) are added portionwise and stirring is continued until a readily flowing dispersion is formed.

Example 6

In the experimental laboratory, wood-containing chalk-filled paper was produced on a paper machine. The fibrous material contained 50 parts of bleached spruce sulfite cellulose (35 S.R.) and 50 parts of bleached wood chips (treated as spotless).

20 parts of commercial chalk were added as fillers.

After thorough mixing, 1.5 parts of the neutral adhesive of Example 1, 1.0 part of aluminum sulfate, both as a 10% aqueous solution, were added.

5 57279

After the addition of the substances, the pH settled at 6.9 · The solids content in the gluing chamber was 2.5% and. after addition of substances about 1%.

Neutral glued paper passed smoothly through the paper machine. A paper having a basis weight of 8U, 6 g / m 2 was obtained, which gave the following values in the gluing test: (the test was carried out according to the standards with a test ink having a pH setting of 1.8 to 0.1).

Immersion time __ S (min)

Top surface Bottom surface 32.15 25.06 From this the degree of gluing was calculated according to Zellcheming-Merkblatt V / 15/60, in which case the value f = 1-10 weak gluing f = 10-20 medium-strong gluing f => 20 strong gluing The following values were obtained from the experiment:

Glue level f

Top surface Bottom surface 35.0 30.95 Thus, a very strong gluing was achieved.

Example 7 Using a glue level tester PLG sold by Fa.K. Kchröder KG, Weinheim, was tested for the resistance of the adhesive to test inks adjusted for acidity in accordance with DIN 53 126. The paper prepared according to Example 6 was used. From the optically determined ink penetration values over time at different pH values, the following results were obtained:

Adjusted to the test ink Penetration time half- Bonding degree pH value up to f (min) (sec) 0.5 - Ui 0.1 1.0 2 30 1 *, 8 1.5 6 11 11.9 2.0> 30> 50 2.5> 30> 50 3.0> 30> 50 U, 0> 30> 50 5.0> 30> 50 6.0> 30> 50 7.0> 30> 50 6 57279

The table shows that gluing is stable on contact with liquids with a wide pH range.

Example 8

Test strips were hung on inks with different pH values for 30 minutes, and the elevation was measured. The following measurement results were obtained for the paper prepared according to Example 5;

Adjusted rise height of the test ink in the strip pH value after 30 minutes (min) 2.0 4.7 3.0 4.5 4.0 4.0 5.0 3.0 6.0 2.0

The rise height of the non-glued paper in the comparative test was 50.0 mm.

Example 9

Surface wetting and penetration were measured according to the Cobb test (Handbuch der papier- und Pappenfabrikation (Papierlexikon), Sändig-Verlag KG Wiesbaden 1962, p. 234 et seq.). Distilled water was usually used in the test, but according to the experimental procedure of Examples 7 and 8, the pH setting was again modified here.

Water pH adjustment Cobb value after 60 seconds 0.5 132 1.0 111 1.5 66 2.0 23.5 2.5 22 3.0 20 ^, 0 19.5 5.0 19 6.0 18.5 7.0 18

Even more remarkable than the results obtained above is the high alkali resistance. As the Cobb test was continued, measurements were performed with basified water. The results are shown below;

Water pH adjustment Cobb value after 60 seconds 8.0 19 9.0 19.5 10.0 23.5 11.0 30 12.0 42 12.5 6l 7 57279

As the alkalinity increases, it is observed that the values increase, but even at pH 11.0 the value corresponds to the order of magnitude, in which case we can still speak of half-life. Thus, a certain alkali stability can be achieved with this gluing method, which is particularly important when using chalk raw paper.

Claims (6)

8 57279 A substance for the neutral gluing of chalk-filled paper, cardboard and other cellulosic materials, characterized in that it consists of an aqueous dispersion containing 50-95% by weight of all or at least 50- $ saponified oleic acid containing 12-2 ^ carbon atoms and 50- 5 wt% alkali metal salt of strongly etherified carboxymethylcellulose. Substance according to Claim 1, characterized in that it contains a mixture of fatty acids, in particular a mixture of fatty acids containing ΐβ-20 carbon atoms. Substance according to Claims 1 and 2, characterized in that the saponified fatty acid is used in whole or in part as its alkali metal salt, in particular as its potassium or ammonium salt. Process for preparing an adhesive according to Claims 1 to 3, characterized in that the oleic fatty acids are dispersed in a solution of an alkali metal hydroxide or ammonium hydroxide and mixed with a polymeric aqueous solution containing a compound containing carboxyl groups. Process according to Claim 1, characterized in that the saponification of the fatty acids is carried out with an alkali metal hydroxide, in particular potassium hydroxide, at a temperature of 70 to 80 ° C. Process according to Claim 1+, characterized in that the saponification of the fatty acids is carried out with ammonium hydroxide at room temperature.