DE1231103B - Process for the production of sized paper - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int CL:

D21d

D 21h
German KL: 55 c - 2

Number: 1231103

File number: A 40270 VI b / 55 c

Filing date: May 22, 1962

Opened on: December 22nd, 1966

The invention relates to a method for producing sized paper.

US Pat. No. 1996 707 describes that a well sized paper is obtained when a hydrophobic organic acid anhydride, for example stearic anhydride

CH ₈ (CH ₁ OmCO - O - OC (CHJ ₁₈ CH ₈ ,

is added as an anionic dispersion to the cellulose paper stock.

However, the process did not achieve technical success, mainly because of 3 to 6 hour heating 80 ° C to 110 ° C is required to develop the glue properties of the anhydride. Today's industrial practice requires faster development of final sizing for paper sizing agents, and it is generally preferred that the size develop fully while the paper is on the Machine dries, d. i.e. before it is formed into rolls. According to today's machine programs the drying stage is completed in this temperature range or slightly above in Va up to 3 minutes.

British patent specification 804 504 describes a faster development of the sizing, with as Holländerzusatz a dispersion of stearic anhydride and bentonite is used. The dispersion however, it is anionic and has apparently not been satisfactory for industrial purposes.

The process according to the invention for producing sized paper consists in adding a hydrophobic organic paper sizing anhydride and at least as much of a water-soluble cellulose-substantive cationic compound to a suspension of cellulose paper stock separately or as a mixture to make the anhydride after emulsification in water cellulose-substantive, a paper web is made from this in a manner known per se and this is dried at an elevated temperature. Drying is usually carried out at a temperature between 85 and 125 ° C., for which a time between ¹ _{and 2} and 5 minutes is required for most papers.

According to the invention, the cationic agents used are cellulose substances, normally water-soluble compounds used, which can be monomeric or polymeric. A sufficient amount is used to make the dispersed anhydride particles cellulosic substantive so that they are directly on the Fibers are absorbed.

Suitable monomeric compounds include octadecylamine acetate, octadecylpyridinium chloride, Process for the production of sized paper

Applicant:

American Cyanamid Company,

Township of Wayne, N.J. (V. St. A.)

Representative:

Dr. I. M. Maas and Dr. W. G. Pfeiffer,

Patent Attorneys, Munich 23, Ungererstr. 25th

Named as inventor:

Proboscis Joseph Kulick, Port Chester, N. Y .;

Edward Strazdins, Stamford, Conn. (V. St. A.)

Claimed priority:
V. St. ν. America May 26, 1961 (112 781,
112 959)

N- (2-aminoethyl) stearamide acetate, the solubilized one described in U.S. Patent 2,772,969 Fatty acid amide amine product and stearamidotrimethylene dimethyl 2-hydroxyethylammonium dihydrogen phosphate

, CHpCH ₂ OH

CH ₃ (CH ₂ ) _ie CONH (CH ₂ ) ₃ - N ς - CH ₃

CH ₃

H ₈ PO ₄

Suitable cationic polymers include polyethylene amine and other water soluble linear polymers containing a significant proportion of - CH ₂ - CH ₂ - NH bonds, water soluble cationic starch, water soluble cationic melamine-formaldehyde and urea-formaldehyde wet strength paper such as them for example, in U.S. Patents 2,345,543, 2,554,475 and 2,885,318, casein, glue, and water-soluble vinyl polymers made cationic by reacting with alum. The latter group of these agents is made by adding alum to an aqueous solution of the casein, glue or polymer, the reaction going on rapidly.

The listed cationic starch is water-soluble starch that is sufficiently cationic amino, quaternary Has ammonium or other cationic groups to make the starch total cellulosic substance close.

609 748/217

In general, better results are obtained when using polymers than with monomers, and obviously the more cationic the polymer, the better the results. The cationic Charge of any cationic compound can be easily determined according to standard laboratory tests can be determined in an electrophoresis cell.

The effective amount of the cationic agent is that which makes the dispersed phase cellulosic power. This amount is also most easily found in laboratory tests, with the the optimum amount is that with which the best sizing results can be achieved.

It is also within the scope of the present Invention of using a nonionic emulsifier together with the cationic agent, either to obtain a finer-grained dispersion or to reduce the amount of the otherwise required cationic By means of belittling.

A convenient way to acid anhydrides be tested for suitability for sizing paper, is to form them from 0.2 ° / ₀ by weight solutions in a volatile organic solvent and apply the solution on filter paper. The filter paper is impregnated with the solution and then held at 107 ⁰ C (225 ° F) for 1 hour. The formation of water resistance shows that the compound is an anhydride for paper sizing.

The anhydrides that can be used as paper glue include the dianhydrides, which are made up of hydrophobic organic acids with more than 12 carbon atoms are formed, e.g. B. myristic, palmitic, Oleic and stearic anhydride, the corresponding polymeric anhydrides, formed from dicarboxylic acids are, for example from 1,12-dodecanedicarboxylic acid, and the mixed anhydrides, for example Stearic acid acetic anhydride.

The present invention is independent of the particular manner in which the dispersions are made will. In general, it is advantageous to use a two-step process, the Acid anhydride (or a mixture of acid anhydrides) is emulsified in water, which is an effective Amount of a highly effective, nonionic emulsifying agent, and then the cationic Means is added. This process eliminates the consumption of the normally expensive cationic Ingredient kept to a minimum and a finer grain emulsion formed.

The organic acid anhydrides for paper sizing generally have melting points below 95 ° C 'and can therefore be made using hot water or water that has a suitable emulsifier contains, are emulsified. The higher melting agents can be produced by high pressure emulsification emulsified above 100 ° C or by using solvents.

It is usually advantageous to pass the emulsion through a homogenizer in order to reduce the dimensions to reduce the emulsified droplets as far as practicable; after that the Emulsion immediately and rapidly cooled to form a dispersion of a dye in a liquid to build. The emulsion is a microscopically heterogeneous mixture of the acid anhydride droplets for sizing paper in a continuous aqueous phase. Most of the droplets have one Diameter of less than 1 μ, and it was found that the sizing effect is all the greater is, the finer the droplets are. The rapid cooling converts the liquid droplets into solid particles without any significant change in dimensions.

The cationic agent can be added before, during or after the emulsification step, and if it is added after emulsification, it can be added to the glue dispersion before or after cooling will.

ίο It is particularly beneficial if the anhydride and the cationic compound can only be added after a conventional pulp a web was formed in a known manner and then the web at a temperature between 95 and 125 ° C is dried.

The pH of the fiber suspension is advantageously maintained during the addition of the paper sizing agent between 5 and 8. The solids content of the glue dispersion is a matter of expediency.

The dispersions are advantageously diluted before use to a solids content of ¹ Z ₂ to 5 ° / ₀ to produce a uniform distribution to ensure the glue.

The dispersions are stable over a wide pH range and appear to be most stable in the pH range to be from 4 to 6.

The glue is effective in a small amount, and between 0.1 and 0.5 ° / ₀ of sizing agent, based on the dry weight of the fibers, are generally sufficient.

Polymeric cationic agents with molecular weights above about 1000 generally give better results Results as monomeric agents at the same weight ratios. In this context, was found that some amount of alum, up to about 5% of the dry weight of the fibers, when used these polymeric agents can advantageously be added. The alum appears to be an extender for the cationic polymer to act and the extent of sizing that would otherwise be achieved by the glue would increase. The alum can be added after, with or before the cationic dispersion, so that the fibers have an adsorbed content of alum before the cationic polymer and the Anhydride glue are adsorbed thereon.

The alum is added as a dilute aqueous solution separately from the glue composition. A procedure in which the water-soluble, cellulose substance is cationic is particularly advantageous Compound has a molecular weight over 1000 and a small amount of alum, up to 5% of the Dry weight of the fibers.

If desired, the glue dispersion can also be used according to the "tub" glue process, wherein a water-scooped cellulose web is impregnated with the glue dispersion and then the web is dried. The presence of cationic material in the dispersion gives a faster one Development of water resistance when drying than would otherwise be the case.

According to the invention, dry mixes which contain one or more anhydrides for paper sizing can also be used and a water-soluble, cellulose-substantive cationic agent can be used, which according to make the anhydride cellulose noun after emulsifying in water.

The mixtures can contain one or more nonionic dispersants to aid in the Emulsification, protective colloids to stabilize the

5 6

Emulsion, hydrophobic pigments, such as titanium dioxide suspension of cellulose fibers these fibers with

or ultramarine, to improve the appearance of a positive charge provided by the

Mixture, emulsion and paper as well as olfactory behavior of the fibers in an electrophoresis cell

substances to mask any odor that may be present. Preferably a sufficiently large one

contain. 5 Amount of the cationic compound (or mixture

The mixtures form glue emulsions when added to the cationic compounds)

be stirred quickly with water that has a sufficient negative charge on the fibers (the electrokinetic

is hot, around the contained anhydride material or "zeta" potential of the fibers) to about zero

to melt. The emulsion obtained will usually degrade.

advantageously homogenized and can be the io cationic polymers with a molecular weight

Dutch porridge can be added while hot. above 1000 are preferred because they are generally

The agents will mean the fibrous paper stock suspension are more effective per unit weight and there

most convenient than dilute, aqueous solutions by the presence of alum (up to about

added to make measuring easier and the 5% by weight of the dry weight of the fibers)

uniform distribution through the suspension to 15 are favored in their effect on this

guarantee. Way acts as a reinforcing agent or extender

It has further been found that anionic dispersants and often a substantial reduction in amount

Sions of hydrophobic acid anhydrides their of the required cationic agent allowed to

Sizing properties to achieve a given degree of sizing in the production of ge

sized paper develop very quickly if it improves 20 or the otherwise obtained sizing,

in connection with a separately added, water- The alum can be before, with or after the cationic

soluble, cellulose-substantive, cationic polymer can be added. The effect of alum

binding can be used. In preferred cases it is most evident when the amount of cationic

more than half of the final sizing would see polymers being relatively small. The means

obtained in 3 minutes at 121 ° C, which are most conveniently supplied to the machine as dilute solutions.

drying is equivalent, and the numbers obtained are set to facilitate measuring and the

Roman sizing values were very high. uniform distribution through the suspension

According to this part of the invention, an aqueous one will be ensured.

Anionic Dispersion of Hydrophobic Organic The following examples serve to better understand the invention without limiting it, paper size particles to an aqueous suspension.
of cellulose pulp added, a water-soluble cellulose-substantive cationic compound
separates added, the suspension formed into webs

and the web at a temperature between 85 and The following is the production of a cationic

122 ° C dried. 35 see dispersion of an organic anhydride for

In general, somewhat better sizing paper sizes according to the present invention are obtained, if the cationic compound according to the wrote, being a nonionic dispersant anionic glue emulsion is added. So it is practically impossible to form an initial one Generally best, the glue dispersion in ionic dispersion is used by ZuHolländer or to add in the storage chest and 40 would add a water-soluble cationic resin to the the cationic agent in the vicinity of the sieve, by-cationic cellulosic substantive form for example at the head end. will.

The pH of the fiber suspension during and after the 50 ml to water at 8O ⁰ C, the 2-polyoxy g addition of the treating agents is not critical. Ethylene sorbitol oleate laurate, a non-ionic dispersion that has been found to contain the best sizing agents, will result in properties with rapid stirring if the pH value of the suspension is added to 10 g of molten distearic anhydride, sion after the treatment in the range from pH 5 to a liquid, creamy, practically non-pH 8 is formed. ionic dispersion.

The invention does not depend on which one this is slowly with rapid stirring to

hydrophobic anhydride or which mixture of 50 930 ml of water at 8O ⁰ C added, the 10 g of des

Anhydrides is used. Contains suitable anhydrides of water-soluble resin, which is

are set in the USA.-patent mentioned at the beginning of 0.2MoI tetraethylene pentamine with 0.6MoI

font 1 996 707 as well as in the British patent epichlorohydrin up to a Gardner-Holt viscosity R

Papers 451 300 and 804 504. They are according to that in Example 1 of the USA patent

water-insoluble, water-repellent anhydrides obtained from the process shown in 55 2 595 935. The received

When heated with cellulose it becomes irreversible so that the emulsion is homogenized hot and then rapidly

realize. cooled to room temperature. The product is a

There should be at least enough kationische.Verbindung cationic cellulose substantive dispersion with 1.0 ° / ₀

be added to the uniform distribution of distearic anhydride, which is stable for more than 2 days

dispersed particles of anhydride glue on the 60 remains.

To effect paper pulp fibers. The quantity changes example 2
vary from case to case, especially depending on the type of

used cationic compound, its molecule- In the following the production of a cellulose-

lar weight and the pH of the suspension and nouns dispersion of an acid anhydride to the

in any case, the most convenient way to do this is to glue the paper with the help of a cationic agent,

Laboratory test found. which serves as its own emulsifier.

Suitable cationic compounds are 20 g in 600 ml of water at 80 ° C

those which after addition to an aqueous water-soluble cationic starch (starch, the

- CH ₂ - CH ₂ - N (CHg) ₂ - has substituents [s. USA. Patent 2,935,436]) and 10 g of melted distearic anhydride were slowly added with vigorous stirring. The emulsion obtained with 1.6 percent by weight distearic anhydride is homogenized hot in a laboratory homogenizer and then rapidly cooled to room temperature.

Example 3

The procedure of Example 2 is repeated, but using instead of cationic starch 0.5 g stearoylamidotrimethylene dimethyl 2-hydroxyethyl ammonium dihydrogen phosphate

. CH ₂ CH ₂ OH

aiCH ^ CONHCCH ^ -N ζ- CH ₃ · H ₂ PO ₄

CH ₃

A similar dispersion is obtained.

Example 4

Here the production of a cationic dispersion of an organic anhydride is used for paper sizing using a water-dispersible hydrophobic amidoamine for paper sizing described as both a cationic agent and a dispersing agent.

To 10 g of melted distearic anhydride is added at 80 ° Cig by reacting 1 mol Tetraethylene pentamine with 3.5 moles of stearic acid at 175 ° C until 2.5 moles of water are developed converted amidoamine, which by adding

1 mole of acetic acid is solubilized, added. The liquid melt is obtained with intensive stirring into 600 ml of water at 80 ⁰ C in a Waring blender allowed to enter. A creamy emulsion forms, which is quickly cooled.

Example 5

The procedure of Example 1 is repeated, but in place of the amine-epichlorohydrin resin used therein 20 g of the urea-formaldehyde-triethylenetetramine resin of the USA patent

2 657132 used. You get a similar one Emulsion.

Example 6

The procedure of Example 1 is repeated, but 10 g of des is used as the cationic agent water-soluble diethylenetriamine-adipic acid-epichlorohydrin resin according to the United States patent 2,926,154. A similar dispersion is obtained.

Example 7

The procedure of Example 1 is repeated, except that stearic acid acetic acid hydride is used as the sizing agent

[CHa (CHj) ₁₆ CO-O-OCCH ₃ ].

The agent is prepared by reacting stearoyl chloride and glacial acetic acid in Diäthylätherlösung at 10 ⁰ C in the presence of Pyredin as an acid acceptor. A similar dispersion is obtained.

Example 8
5

The following is the preparation of a cationic Emulsion shown, which gives excellent sizing values and which chemically and physically for a long time remains stable.

ίο To 908 ml of water at 80 ° C, the 30 g of the dissolved contains cationic starch according to Example 2, 1.5 g of sodium lignosulfonate are added. To be 30 g of molten stearic anhydride are run in with vigorous stirring. The emulsion obtained is homogenized hot and quickly cooled. 0.4 g of sodium hydroxide are then added to the dispersion obtained. dissolved in a little water, added.

Example 9
20th

The procedure of Example 1 is repeated, but using stearic anhydride instead of stearic anhydride 10 g of naphthenic anhydride (made from petroleum naphthenic acids). A similar dispersion is obtained.

Example 10

The procedure of Example 1 is repeated,

however, a water-soluble copolymer of acrylamide and diallyldimethylammonium chloride is used 89: 1 weight ratio as a cationic agent.

Example 11

The following is the rate of development of the sizing properties of the present invention Dispersions shown.

An aqueous suspension of geholländerter 50 ° / o bleached sulfite, 50 ° / ₀ of bleached hardwood pulp at 0.6% consistency is divided into aliquots and added to a small amount of one of the dispersions described to each part as shown in the following table will be shown. The pH of the aliquots is then adjusted to 7, the aliquots are stirred gently for a few minutes to allow adsorption of the anhydride glue, and then the aliquots are made into hand-scooped sheets of approximately 281 g basis weight on a Noble & Wood hand operated paper machine / m ² shaped. The hand sheets are at 121 ⁰ C in a laboratory drum drier determined (two passages of 1.5 minutes) dried and the lactic acid resistance of the arc, with 20% lactic acid solution by means of Peneskop under a 30.48-cm-head at 37.8 ° C is applied.

The penescope is a testing device that keeps a piece of paper in contact with an acid until the Acid erodes the paper. The device contains a small metal test chamber on the open side the piece of paper, which is kept in contact with lactic acid, is clamped to reduce the rate of penetration of the acid through the coated or uncoated paper. The chamber can handle changing amounts of acid when changing Temperatures are filled to measure the relative penetration rates.

The results show the extent of the sizing effect exerted by the paper in the paper machine is being developed.

The sheets are then cured in a drying cabinet for 1 hour at 104 ° C and their lactic acid resistance determined once again in order to

10

to determine valid sizing, which was effected in each case by the acid anhydride. The results are as follows:

Ver
search
No. ¹ ) Sizing
anhydride
description Glue
7o ^a ) spersion
Cationic agent ⁸ )
description V) Developed L
dry
at 121 ° C
3 minutes solution according to ⁴ )
Oven hardening
at 101 ⁰ C
1 hour % of the final
Gluing on the
Dryer ent
wraps ⁶ ) 1 Distearic 0.3 TEPA epi resin 0.3 3600 3600 100 2 Distearic 0.3 Cationic starch 0.6 2500 3600 70 3 Distearic 0.5 SDHA 0.025 360 380 95 4th Distearic 0.5 TEPA stearic acid
condensate 0.05 150 250 60 5 Distearic 0.5 U-F-TETA resin 2.0 240 320 75 6th Distearic 0.3 DETA-adipic acid-Epi 0.3 3600 3600 100 7th Stearic acid
Acetic acid- 0.3 TEPA Epi 0.2 420 600 70 8th Distearic 0.2 Cationic starch 0.8 3600 ^B ) 3600 100 9 Naphthenic 0.5 TEPA Epi 0.2 410 550 68 10 Distearic 0.2 AM-DADM resin 0.75 3600 3600 100

Explanation

² ) Number of the experimental example, details in the text.

^a ) Based on the dry weight of the fibers.

") TEPA = tetraethylene pentamine; Epi = epichlorohydrin;
SDHA = stearoylamidotrimethy] dimethyl-2-hydroxyethylammonium dihydrogen phosphate; UF-TETA = urea-formaldehyde-triethylenetetramine; DETA = diethylenetriamine; AM-DADM = acrylamide diallyldimethyl ammonium chloride.

*) Seconds when using 20% lactic acid solution under 12 inches head.

⁶ ) The sizing developed after 1.5 minutes of drying corresponds to 510 seconds.

") All values above 3600 seconds are considered the same.

The results are as follows:

Example 12

The following is the effect of changes in the amounts of pulp applied Sizing anhydride and the cationic resin on the sizing explained.

To 500 ml of water at 80 ° C., 0.3 g of Ghatti gum and 1.5 g of the naphthalenesulfonic acid-formaldehyde emulsifier are added with vigorous stirring and 3 grams of technical grade fused distearic anhydride with 6% unreacted stearic acid was added. the The emulsion obtained is homogenized while hot and immediately cooled rapidly.

From a well-healed 50:50 from bleached Sulphite pulp and bleached hardwood pulp are taken from aliphote parts and first with the sizing dispersion and then with an aqueous solution of the tetraethylene pentamine epichlorohydrin resin of Example 1 in the amounts shown in the table below.

The aliquots are formed into hand sheets of 140.6 g / m ² paper weight, dried for 3 minutes at 121 ° C., and their resistance to lactic acid is determined, all the processes being carried out as described in Example 1.

Attempt
number %
Added
cationic
resin "I.
Io
Added
Distearic acid
anhydride ¹ ) After 3 minutes
Drying at
121 ° C ent
wrapped
Lactic acid
strength ² ) control none 0.3 immediately 1 0.05 0.3 1000 2 0.1 0.3 2000 3 0.3 0.3 3500 4th 0.6 0.3 700 5 1.0 0.3 500 7th 0.3 0.1 immediately 8th 0.3 0.2 700 9 0.3 0.3 3500 10 0.3 0.5 7200

Explanation:

¹ ) based on dry fiber weight.

² ) seconds.

The sizing obtained in Experiment 10 shows that fatty acid anhydrides are present in paper sizing allow significant amounts of free higher fatty acids.

Example 13

The following describes the production of a practically anhydrous self-dispersing sizing mixture described which an organic anhydride for paper sizing and a water-soluble cationic dispersant contains. The dispersant is the amidoamine from Example 4. A dry one is formed Mixture of 10 g of this material in flake form, 200 g of a water-soluble cationic starch and 100 g of crushed stearic anhydride. The Mi

609 748/217

The mixture is powdered and forms a stable dispersion when 8 g are slowly added to 200 cm ^{3 of} vigorously stirred boiling water. The resulting dispersion is immediately cooled to room temperature and used in the manufacture of sized paper as described in Example 1, with similar results being obtained.

Example 14

IO

This shows the apparent wet strength of paper according to the present invention.

A strip 2.54 cm in width and 12.7 cm length is cut from paper according to the invention having a content of 0.3 ° / ₀ and I ⁰ I ₀ Distearinsäureanhydrid cationic starch. The paper is suspended in water with a pH of 8.4 (sodium bicarbonate buffer) at a temperature of 20 ^° C. under 1 kg of tensile stress.

The paper was visibly not corroded after a test duration of 24 hours. A paper control strip of I ⁰ I ₀ deposited with alum reinforced CoIophonium had as sizing, pulled under tension in 30 minutes.

Example 15

This shows the effectiveness of the cationic constituents of the acid anhydride dispersions for sizing according to the present invention in the treatment of paper by means of the pan sizing process. The sizing dispersion used here is that from Example 8, but only 15 g of cationic starch are used. The dispersion is diluted by adding water to 0.38 ° / ₀ Stearinsäureanhydridgehalt.

An unskilled paper sheet is made by scooping an untreated, but good geholländerten Stoffbreies of 50 ° / o bleached sulphate pulp and 50 ° / ₀ bleached hardwood pulp, with a weight of 281 g / m ^2, dried for 3 minutes at 100 ⁰ C and then Immersed in the sizing dispersion for 2 seconds. The sheet is passed through the press to remove excess (unabsorbed) dispersion. It is found that it has absorbed 79% of its weight in dispersion and therefore contains 0.3% by weight of anhydride glue and half that amount of cationic starch.

The sheet is then dried ^{at 105 ° C. for 3 minutes.} The lactic acid resistance of the sheet treated in this way is over 3600 seconds.

In the following the production of sized paper according to the present invention is shown, being anionic dispersions of hydrophobic acid anhydrides with separately added cationic Funds are used.

Example 16

An anionic emulsion of a hydrophobic organic anhydride for paper sizing is prepared by slowly pouring 60 g of molten distearic anhydride into 930 cm ^{3 of} water containing 6 g of gummy gum and 3 g of anionic emulsifier dissolved by reacting with vigorous stirring

1 mole of naphthalenesulfonic acid is formed with 2 moles of formaldehyde. A creamy emulsion forms, which is homogenized hot and then rapidly cooled in order to allow the dispersed phase to flow together avoid.

Samples of sized paper to be prepared by an aqueous suspension of well geholländertem pulp (50% bleached sulphite and 50 ° / ₀ deciduous wood pulp) prepared at 0.6% consistency, divides the material into aliquots and the quantities given in the table below is added to the above emulsion and the cationic agent. (The cationic agent used is tetraethylene pentamine epichlorohydrin resin according to Example 1 of the USA patent

2,595,935 used.) The cationic agent is added after the anionic emulsion. The suspensions are stirred about 1 minute after each addition and hand sheets with a paper weight of 141 g / m ^{2 are} formed from the swatches according to the standard laboratory procedure.

The hand-made sheets are 3 minutes on a rotary laboratory drum drier at 121 ° C dried (two passages of 1.5 minutes) and the lactic acid resistance of the sheets by means of Peneskop using 20 ° / ₀ strength lactic acid solution at 37.8 ° C under a 30 , 48 cm head and then cured the sheets at 93.3 ° C for 1 hour in order to develop their practically final size.

The results are as follows:

Vprinphsnnmmpr %
Added / 0
Added Developed glue, seconds 104 ⁰ C %
the final gluing V wXoUwllollUlllUXGl anionic cationic 121 ° C 1 hour during drying Emulsion ¹ ) Medium ¹ ) 3 minutes _ developed 1 0.1 0.1 immediately > 3900 _ 2 0.2 0.1 > 3900 > 3900 100 3 0.3 0.1 > 3900 3200 100 4th 0.2 0.05 3000 > 3900 100 5 0.2 0.1 > 3900 > 3900 100 6th 0.2 0.3 > 3900 2560 100 7th 0.2 0.6 2040 100

Explanation:

^x ) Based on dry fiber weight.

B e i s ρ i e 1 17

It is known from other laboratory experiments that 65 The following describes the production of glued that similar results are obtained when illustrating the paper according to the present invention cationic agents in front of the anionic agent and a number of the usable cationic admixtures will. bindings are shown.

The procedure of Example 16 is repeated, except that the tetraethylene pentamine epichlorohydrin resin is used in place of the resin the resins given in the table below. If alum is used, will

he added after the sizing agent and the polymer. The sheets are produced with a paper weight of 140.7 g / m ² and dried for 3 minutes on a laboratory drum dryer at 121 ° C.

Experimental /O
Added Cationic agent ⁰ L Lactic acid resistance number anionic / 0
added ¹ ) dry after 3 minutes at 121 ° C Emulsion ¹ ) description none 1 0.3 Polyethylene amine 0.03 immediately 2 0.3 Polyethyleneimine 0.05 1800 3 0.3 Polyethyleneimine 0.075 3000 4th 0.3 Polyethyleneimine 0.1 1350 5 0.3 Adipic acid-DETA-Epi ² ) 0.3 1320 6th 0.3 Adipic acid-DETA-Epi ² ) 1.0 5400 7th 0.3 Adipic acid-DETA-Epi ² ) 0.5 5000 8th 0.3 DADM-AM copolymer ³ ) 0.75 900 9 0.3 DADM-AM copolymer ³ ) 1.0 1020 10 0.3 DADM-AM copolymer ³ ) 0.8 1020 11 0.3 Cationic starch ⁴ ) 1.1 1140 12th 0.3 Cationic starch *) 1.4 1800 13th 0.3 Cationic starch ⁴ ) 0.6 1040 14th 0.3 Polycrylamide oxime resin ⁶ ) with alum ⁶ ) 2000

Explanation

*) Based on dry fiber weight.

^a ) Adipic acid - DETA - Epi = adipic acid - diethylenetriaminepichlorohydrin, manufactured according to US Pat. No. 2,926,154.

") DADM-AM copolymer = copolymer of diallyldimethylammonium chloride and acrylamide (11:89 weight ratio).

⁴ ) Manufactured according to USA patent 2,935,436.

^δ ) An amphoteric polymer made according to U.S. Patent 2,959,574.

") 0.5% alum (based on dry fiber weight) then added to the cationic resin.

Example 18

The following describes the production of sized paper using the by converting Cationic polymer formed by casein (ammonium caseinate) is shown.

The procedure of Example 17 is repeated, but ammonium caseinate and alum (subsequently added) are used in place of the cationic polymer from Example 2, and the fibers are converted into a paper weight of 281 g / m ² per sheet with a sheet size of 63.5 x 101.6 cm shaped. Electrophoretic studies show that the alum reacts with the caseinate immediately after addition to form a cationic compound or complex.
The results are as follows:

Trial number %
Added
more anionic
Emulsifier ¹ ) %
Added
Caseinate ¹ ) %
Added
Alum ¹ ) pH
Setting ² ) Lactic acid
resistance
Seconds Control A
Control B
Control C
1
2
3 0.3
0.3
0.3
0.3
0.3
0.3 none
none
1.0
1.0
1.0
1.0 none
0.9
none
0.9
0.9
0.9 4.8
4.8
4.8
4.3
4.8
6.0 immediately
immediately
immediately
3300
1200
1310

Remarks

^x ) Based on dry fiber weight.

² ) After adding alum.

Example 19

The following shows the manufacture of sized paper according to the present invention using a normally anionic polymer which is made cationic by reaction with alum. The procedure of Example 18 is followed and sheets with a paper weight of 281 g / m ^{2 are} formed.

The polymer used is a copolymer of 90 percent by weight acrylamide and 10 percent by weight Acrylic acid, which is made cationic by the subsequent addition of alum.

The results are as follows:

Trial number O/
/ 0
Added
more anionic
Emulsifier ¹ ) %
Added
Polymer ¹ ) %
Added
Alum ¹ ) pH
Setting ² ) Lactic acid
resistance
Seconds Control A
Control B
Control C
1
2
3
4th
5 0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3 none
1.0
none
1.0
1.0
1.0
1.0
1.0 none
none
1.5
1.5
1.5
1.5
1.5
1.5 4.8
4.9
4.6
4.7
5.2
6.0
6.5
7.0 immediately
immediately
immediately
185
220
340
305
300

Remarks

*) Based on dry fiber weight.

^a ) After adding alum.

Claims (4)

Patent claims: •1. Process for the production of sized paper, characterized in that a hydrophobic organic paper sizing anhydride is added to a suspension of cellulose paper stock and at least as much of a water-soluble cellulose-substantive cationic compound as to make the anhydride cellulosic substance after emulsification in water, separately or as a mixture adds to each other, then a paper web is manufactured in a manner known per se and this at increased Temperature dries. 2. The method according to claim 1, characterized in that the anhydride and the cationic Compound can only be added after a conventional pulp in known Way a web was formed and then the web at a temperature between 95 and 125 ° C is dried. 3. The method according to claim 1 or 2, characterized in that the pH of the fiber suspension is between 5 and 8 during the addition of the paper sizing agent. 4. The method according to any one of the preceding claims, characterized in that the water-soluble cellulose-substantive cationic compound has a molecular weight above 1000 and a small amount of alum, up to 5% by dry weight of the fibers, is added. 609 748/217 12. 66 © Bundesdruckerei Berlin