DE1281831B - Process for the production of felted, fibrous cellulose products - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

JR M Jk

GERMAN #m PATENT OFFICE Int. CL:

D21h

EDITORIAL

German class: 55 f-11/01

Number: 1281831

File number: P 12 81 831.4-45 (G 36885)

Filing date: January 23, 1963

Opening day: October 31, 1968

The invention relates to a process for the production of felted, fibrous cellulose products with the use of modified polysaccharides, which is characterized in that one the cellulose-containing pulp about 0.1 to 10%, based on the dry weight of the cellulose fiber, admits a mixture that consists of

A. about 15 to 85 percent by weight of a modified polysaccharide, in particular an oxy- ₀ dated polygalactomannan gum or an oxidized starch, and

B. about 85 to 15 percent by weight of an aminoamide or aminoimidazoline of a monomeric, an epoxidized or a polymeric fatty acid with an amine number of about 50 to 700

consists.

A particular embodiment of the method according to the invention is characterized in that adding a mixture in which the modified polysaccharide from a by treatment with 0.01 up to 0.4 moles of periodate per mole of anhydrous hexose moiety of modified polygalactomannan gum consists.

Another embodiment of the method according to the invention is characterized in that that one adds a mixture in which the modified polysaccharide from a substantially completely oxidized dialdehyde starch.

Wet strength is important in two major papermaking products. Wet strength that not at the expense of absorbency is used in the manufacture of paper towels and paper towels required for single use. In general, the natural gums and Starches, especially their oxidized dialdehyde or periodate compounds, used to make this To impart wet strength to materials. On the other hand, in the production of materials such as. B. Beverage crates, cardboard boxes, cardboard boxes and the like, a completely different type of wet strength required. There, where the subject can withstand a constant or repeated encounter with water or in a very Moist atmosphere must be used, is a more or less permanent wet strength necessary. A pumping speed is not required.

In the art, formaldehyde-based resins such as. B. melamine-formaldehyde and urea-formaldehyde resins. used to give the paper objects produced a permanent wet strength to rent.

Process for the production of matted,
fibrous cellulosic products

Applicant:

Schering Aktiengesellschaft,

Berlin and Bergkamen,

1000 Berlin 65, Müllerstr. 170-172

Named as inventor:

Don E. Floyd, Robbinsdale;

Richard J. Ess, Minneapolis;

James L. Keen, New Brighton;

Joseph W. Opie, Minneapolis (V. St. A.)

Claimed priority:

V. St. v. America January 26, 1962 (169 100)

The mixtures according to the invention belong to the type of preparations which have permanent wet strength lend, such as is required for cardboard, carbon paper, wrapping paper, etc.

Two disadvantages are encountered with the commercially available resin preparations such as e.g. B. melamine formaldehyde and Urea-Formaldehyde Resins, attributed. The use of these types of resins is generally open acidic pH values are limited, which often promote corrosion of the system, and alkaline or neutral Paper stocks cannot be used. In addition, to achieve the desired permanent wet strength Second, when formaldehyde resins are used, there is usually a certain amount of post-curing of paper products required to achieve optimal wet strength. This post-curing is usually achieved by using elevated drying temperatures, the finished

809 629/1365

Product heated or stored for relatively long periods of time to harden at room temperature to allow. Additional treatment stages, such as B. the above, lead at additional cost; either in the form of Steam consumption, time, labor and / or storage costs.

On the other hand, the preparations according to the invention impart wet strength within a wide pH range, which leads from a high acid value to well into the alkaline range. Through this they are very versatile in terms of their use in acidic, alkaline or neutral paper pulps. The risk of corrosion is reduced because acidic containers are used to achieve optimal results

conditions are no longer necessary. Second, lend _I5 net

merer fat residue «refers to hydrocarbon residues a polymerized fatty acid and applies to both divalent, trivalent and other polyvalent Hydrocarbon residues from dimerized fatty acids, trimerized fatty acids and higher polymers of fatty acids. The divalent and trivalent hydrocarbon radicals are referred to above as "Dimeric fat residue" and "trimeric fat residue". The saturated, ethylenically unsaturated and Acetylenically unsaturated fatty acids are generally produced according to somewhat different processes polymerized, however, because of the functional The equality of the polymerization products is generally all referred to as "polymeric fatty acids"

the compounds according to the invention wet strength without the paper product being post-cured got to. The permanent wet strength becomes immediately after application of the wet strength according to the invention

Saturated fatty acids are difficult to polymerize, but the polymerization can take place at elevated levels Temperatures and a peroxide catalyst, such as z. B. di-t-butyl peroxide can be achieved. Because of the

Added to the paper product. This has ₂₀ generally low yields of polymeric

In technology, these materials are generally of no importance to products. Suitable saturated fatty acids are e.g. B. ' straight and branched chain acids as described above.
. The ethylenically unsaturated acids are much easier to polymerize. Catalytic or non-catalytic polymerization processes can be used. The non-catalytic polymerization generally requires a higher one

the obvious advantage that time, material and Manpower can be saved.

The amino-containing compounds derived from the fatty acids according to the invention relate to on a variety of substances. This includes the Aminoamides and aminoimidazolines, which are used in the reactions of long-chain carboxylic acids and Alkylenepolyamines are obtained, such as. B. fatty acid aminoamides, Fatty acid aminoimidazolines,

Aminoamides and aminoimidazolines at epoxy- ₃₀ temperature. Suitable catalysts for the polymerized fatty acids and the aminoamides and amino merization are z. B. acidic or alkaline clays, imidazolines of polymeric fatty acids. A valuable di-t-butyl peroxide, boron trifluoride and other Lewis characteristics of this group of compounds are the acids, anthroquinone, sulfur dioxide and the like. B. the branched-chain ones which correspond to the amine groups in 1 g of the product and do not speak of straight-chain poly- and mono-ethylene glycol. The amine number of a particular compound of saturated acids, which have been described above, indicates the amine groups required for the reaction. The acetylenically unsaturated fatty acids may be available and serve as an indication of simply heating the acids to polymerize the particular structure. Generally became. The polymerization of these highly reactive found that amino compounds that are suitable for the presentable materials takes place in the absence of any present invention, amine numbers of the catalyst. The acetylenically unsaturated 50 to 700 have. Acids occur only rarely in nature and ~ --BgiU expression »Fettsäureri« .iiegight = look at ver are only synthetic with great effort,
different saturated and ethylenically unsaturated. They are therefore commonly found in the '^'
acetylenically unsaturated, naturally occurring _{45 of} no concern. Acetylenically unsaturated ~ VFei: £. and synthetic monobasic aliphatic acids with acids, both straight and
8 to ■ 24 carbon atoms. Suitable saturated
Fatty acids are branched and straight-chain acids,
such as B. caprylic acid, pelargonic acid, caphic acid,
Lauric acid, myristic acid, palmitic acid, isopal- ₅ q te'r ¹
"fiiflatue / stearic acid, arachidonic acid, behen-> ~ ^ci ™. .-" -

fex. si **, ipceric acid. Another GrangJ β ΐβΜ8 & Μ ^

—-- ^ Sfe »Sill«

poxidation level ooer in
known procedures using

ι m

Acid resins and hydrogen peroxide and acetic acid are produced. The epoxidation can can also be achieved by using formic acid and hydrogen peroxide. The epoxies Körtrien also by adding hypochlorous acid to the carbon-carbon double bond and then Dehydrochlorination can be achieved according to the following equation:

-CH = CH-

HOCl

CH-GH-

OH Cl - HCl

CH

The Pohamines that are used in the production of the amino-containing interlocking connections are used are the Alkvlenpolvamme like / B. Athvlendiamin, Dialhvlentruiiniii, letraalhvlenpentamin, Di-M-propanefiamine, di-1,2-piopanetriamine u like The Polvaminc can duieh the lying general 1 formula

II ₂ N (RNH) ,,! I.

where R is an alkylene number and / ι a whole range from 2 to 6, while the alkylene is in general ι''new at least, but also up to 6 carbon atoms are needed are p) is generally easier eiLiltln.li and bevoizugte \ usgangsin.iienalien / ui Heisti Settin g dei e ^r tindungsgemaßen amipolialtiper compounds

The. "Minohaltigen compounds d ι voiliegend <'s invention graze duieh 1 mset / ung a *"' AIkV ¹ Ci poKamins ium voi ^ tchcnddi 'Vt nut de' Saun, odn the I-art de. \ v p-telicnd touched carboxylic acid, obtained from cue: I etKaino st < ^ir nim, under conditions the / ι n'Jit umgi. set / ten ^ mipogii'ppen drove

The eitii'dun ^^ einj'i; !! i strange Amijnoimui a / without iirid the f m> ct / iiiigipiodrfcle of the presented '\ thj, Lonpolvamii c jnd the saturated or uri ^ csaliig'teii I M- acidic tip wesjn'lielvn, equivalent of the fatty acid only 1 mol of the PoIvamiJs unigybct / t I) .g I'm setting wnd "under usual conditions, üic i'ur eincp s.olelien /, Wy <; k migi ^ cpJa waves, made ie at b". -nua 3 ⁽ >> ί vvahrend meliere. Hours Choosing Jie-.u ι mseUung takes place / uer ^ 4ie peli.yiirieru.it du »Monuarnkts utul mb (hlu: äend the further delivdiieiung / U den» imidazoiinrir-fe instead of Üahe- i is> e.bst b ^ i the simplest alk> lenpplyanViu, d 'Athvlenediamine, C ^ n.' Vpibipdung zu cihdlten, <iie irneiice An.mogruppe 'ie, hi.t Jedeiüi it will generally νυι a, u < against one of the holier "Alkvlenpulyamme, like / B D'aih ^ Icntuamip Tw- ■ ithylentetianun retraathvl"npeaunii'i ihv * / u ve _r w ^ nden to that you have Veibjndurgen with a fistieu primary ^ mn.eruppe *) wic cnei iuc ii ^ ahperen secondary ammgruppen what i) ie, irhaksnep Aminoimidij / ») hne Λ.ΐιΐΛ / ihle'i \ on about χ to ei, wa 50i )

Pn? tsttsaure Aininoamu'e gein.'i? the invention graze if) dhnlidu.1 way like that

ie, hiig (: "tellt ha essential" η wyrd 1 it Fettsauic with ^T Mi \ H: ι ^% ηροΐ ^υ «-ηι ι> ι · ι

₄ o

_{4 <;}

Jedoeh wild, made the AmidifikaUon generally at a lower temperature, usually about I ⁷ OC, while several £ tu ligand This leads to Fettsaurf-aminoamides, the free primary amino groups irt all cases and have both free primary, Amjnpgruppen and a odef mehreie se! tindary amino groups where the alkylene polyamine used is a D \ äfn> lentuamin or a higher Wlyamiii

The ammo-polyamides and aminopolyamides of the present invention, which are obtained from the synthesis of alkali amines and polymeric formulations, are described in a manner similar to that of the ntonoamides and monoimidazolines 'etge ^ ellt. ie _(the .n reduction is usually performed at 700 C or wciiigei during several hours aurrV ^ fuhii to form only Ojer in v.ese ^ fbchen nui_ \ nndbindungi ο If it's on the anderqn SeUe e rwun ^ ht, Jnjida / ormbinvlungen so ^ ir ^ dip ^ Jmsetzun ^ at about Iflu C dialing mebiercr $ tuiiidvl

F wide of the ep, 'Wvditfr'tta fatty acids ode · used their Tiler, complexes are ammQh _v \ l, lnimogebunderje term' F ^ ^ öljianiidpplyirriid / oiine erKaUciu The X.'njbct / clothes with "remote PoJvamih kf" nn so ^r c & üi- π wildest'i) a \ S PrQdjuJite'erh'ilt, en wirdq, dje iujit. h Ainidjgrüppea or ,, jra wesepüich ^ i ^ .i, ngruppen ^ aer ueB ^ isjjlie this' pjyppui entiiaUqn Di ^ ₁ feewigmtgen * upter to whom this; 'Vodukte' hergebe]] !, vvcrdep, sc, Wank \ en wpH gehtUvl, eat ^ be ^ on ^ ere, <U als ^ ußgangsmaterwl Un wese ^ t punch every ep9 \> 4th. PetaiiUre, pder im wcotnt hej) eft everyone h ^ <r hup oeniisch, ^ this ^ teiiaJlea d will tcounen. Woda ^ Auj ^ angsmateU'U tin i ^ ter φΙ ± steps djf implementation im

g -i? ijt derp PolyanMA * ehr sthnell fo.t, and

Atr> .dgfuapen wprfipn at .1 (X) C unj Irruda / olin gcuppcn even at ^ UftfC frinaUen WßBjije4ocb das Auigangsmuternl voi ^ iegeod, <n i-on »der fiei £? I Acid provisionally sia4r the dehydration step Doors much higher, namheh 200 to 300 (around convert all Iimda'olia groups ι

The inventive passport modified poly acrh »- nd <; lie in, wftRptjichia} m form vt. «i two Ty |) cn ddfi Guar-04er l.ocqsti

ty to
oJJeiE ^ nJ> «i? n
Pdd

wur ^ (i | tt, and , at

De
as is proven by the OxydaMon eiifr

anhydrous hexose unit to a dialdehyde according to the following conversion scheme:

CH ₂ OH

+ HIO ₄

In the case of periodate-oxidized starches, which essentially consist of anhydroglucose units, does the oxidation take place more or less accidentally within the chain, and so does the degree of oxidation depends almost entirely on the amount of oxidizing agent used. On the other hand is the periodate oxidation slightly different from polygalactomannan gum. The anhydrogalactose units are preferably attacked before the anhydromannose units are attacked. Hence the Oxidation of a polygalactomannan gum is not accidental, but at low degrees of oxidation for the anhydrogalactose units selectively.

The partially oxidized polygalactomannan gums of the present invention are conveniently made by treatment with less than stoichiometric amounts of the periodate (usually 0.01 to 0.4 moles per mole of anhydrous hexose unit) under which conditions the anhydrogalactose units are preferably attacked before the anhydromannose units. This reaction can be carried out in solution in aqueous systems, in suspension in aqueous systems which contain an organic solvent such as. An alcohol or ketone, or can be made under substantially dry conditions by mixing the reactants. In this reaction, the degree of oxidation of the anhydrogalactose units is determined by the conditions and the molar ratio of the periodate. The ratio of anhydrous galactose units to anhydrous mannose units will vary with the particular polygalactomannan gum in question. The percentage of galactose units. which are oxidized can range from as low as on the order of 15 to 20 ^° O to substantially all of the oxidized galactose units. A typical product of this composition is the aldehyde locust bean gum used as the standard material in the examples of the present invention. This product is oxidized to 10%. That is, one in 10 hexose units is converted. Since locust bean gum consists roughly of four mannose units per galactose unit and since the galactose units are preferentially oxidized, this gum is a material in which about 50 "<> of the available galactose units have been converted. These partially oxidized galactomannan gums are the preferred polysaccharides for the preparations according to the invention .

Use higher concentrations of periodate (0.4 to 1.0 moles per mole of anhydrosehexose unit) used for the oxidation of polygalactomannan gum, then both the anhydrogalactose units as well as oxidizing the anhydromannose units. This results in a product with a large number of dialdehyde groups, very similar in nature to high starches.

Oxidized starches, which are commercially available as dialdehyde starches, are used in the oxidation of Strengths such as B. corn starch, wheat starch, tapioca starch, etc., obtained with periodate under conditions.

in which the anhydroglucose units are converted into units carrying dialdehyde groups. The degree of oxidation achieved in these reactions depends to a large extent on the time and the amount of the oxidizing agent used. The conversion conditions can be essentially identical with the conditions described for the preparation of oxidized polygalactomannan gums be. The degree of conversion can vary from a relatively low value of 10 to 20% extend to substantially complete oxidation of 90% or greater.

The aminoamid-, aminoimidazoline-oxidized polysaccharides of fatty acids according to the invention can in the case of a large number of fibrous, cellulosic materials, e.g. B. the commonly called Sulphite, sodium, sulphate cellulose and wood pulp called materials, or used for fibers that come from rags, cotton, bast, flax and straw or from ground scrap come here.

The preparations according to the invention can be applied to the matted cellulose-containing products by processes in which the partially dried products are immersed in an aqueous solution or dispersion of the modified polysaccharide-amino mixture and with about 1 to 10 ° _{() of the} same, based on the dry weight of the Paper, to be impregnated. The paper is then treated in a conventional manner. It is also possible to spray the paper product obtained with an aqueous and / or alcohol solution or dispersion of the mixture.

However, the preferred inventive method consists in the addition of an alcohol and or Water solution or dispersion of the preparations to the ground and preferably cleaned cellulose fiber. The preparations are in the grinding device, the storage container or the dispensing vessel on a

added at any point before the actual paper-forming process. The conditions are regulated so that a concentration of about 0.1 to 10%, based on the dry weight of the Fibers. The concentration of that consisting of the polysaccharide and the amino compound Mixture in the grinding device is, for example, 0.1 to 1%, based on the ground mixture.

The preparations according to the invention can be used alone or together with other additives, as are customary used in the manufacture of paper products. The combination can be as a solution or as a dispersion in water, in water and alcohol or another suitable solvents are added. The individual components can be separately integrated into the Paper pulp mixture are introduced.

In the examples below, unless otherwise specified, the parts and percentages are based on weight.

example 1

Additives that lead to wet strength can be determined using known laboratory methods, a hand-made sheet is made to have the desired concentration of additive (or no addition) under carefully elaborated, established and strictly adhered to procedures, whereupon the hand sheets under the desired conditions and with determination of the Wet burst pressure of the sheet (and usually dry burst pressure). It will a comparison is made with a control sample, with a control sample often being a known conventional additive for imparting wet strength was used.

The following standard procedure was used to make the additives of the invention testing:

360 g of bleached kraft pulp was added to 24 liters of tap water and vigorously for 2 hours touched. The mixture was whipped in a Valley laboratory whipper for 35 minutes and then diluted with 241 tap water. The pulp could now be used to produce Hand sheets with various additives introduced into the whipping device are used will.

The additives were added to the pulp mixture as a 1% aqueous solution or emulsions Except for some additives that do not form aqueous solutions or emulsions, and

The following data were obtained:

these exceptions were added as a 5% solution in isopropanol. In each case, 0.4 g of the additive is added to 21 of the pulp mixture, and this added amount corresponds to about 2.5 g of the dry pulp mix. One sheet was obtained from each liter of the pulp mixture so that the result obtained with each addition is the average burst pressure of two wet strength sheets represents. In a number of experiments, the pH of the mixture of substances was determined by adding concentrated HCl or 30% NaOH solution before adding the chemicals to be tested. the Additives were mixed with the pulp mix for 10 minutes before the handsheets were received became.

The hand sheets were formed with a sheet-forming according to Noble and Wood, conditioned overnight at 23 ° C and 50 ⁰ / o relative humidity, immersed for exactly 15 minutes in tap water, and the values for the Naßberstdruck were. measured by a Mullen test device. The value measured on the handsheets was the wet burst pressure and this value is expressed in kilograms per 45.4 kg of ream weight, 40.2 x 64.4 cm x 500 sheets.

The leaves were stressed several times. Ten burst pressure values were obtained for each sheet.

A comparative sample was obtained by making 0.4 g of dialdehyde locust bean gum, the to the cellulose blend had been added (previously adjusted to a pH of about 3.6 had been), and checked each time an additive was evaluated.

Two amino-containing compounds have been tested for effectiveness in conferring the Wet strength compared. The first of these compounds (Resin A in the table below) was the amino amide reaction product of polymeric fatty acids, triethylene tetramine and tetraethylene pentamine and had an amine number of 305. The second product (Resin B in the table below) was the aminoimidazoline reaction product of polymeric fatty acids and triethylenetetramine and had an amine number of 375.

Using the standard procedures outlined above, aldehyde locust bean gum was made with mixtures compared that made from 3 parts of aldehyde locust bean gum and one part of the amino-containing Connection established. The wet strength additives were added to the pulp in one Concentration of 0.4 g per 2000 ecm of pulp or about 2.5% additive, based on the dry weight of the pulp.

Aldehyde- G Resin A *) Resin B *) G Amine number Wet burst pressure **) attempt Locust bean gum - (Aminoamide) (Aminoimidazoline) - - G 0.1 - - 20.9 1-1 0.4 0.1 - - 30.0 1-2 0.3 - 0.1 375 30.5 J-5 0.3 0.4 - - 32.0 1-4 0.3 - 0.4 375 0 1-5 --- 0 1-6 - Amine number - 305 305 - 305 -

* l See description above.
** 1 kilogram per 45.4 kg of ream weight, average data for double sheets (average of 10 tests per sheet).

809 629/1365

Examples

The dry and wet burst pressure associated with the combinations of polymeric fatty acid and amidoimidazoline obtained in Examples 1 to 4 (amine number 350 to 400) and aldehyde locust bean gum was, as a function of pH, the

The following data were obtained:

The concentration of the additive and the ratio of the two components are determined. It was there the procedure described above was applied. Bleached soda pulp was used. the The serve time was 35 minutes.

Polymer fat Aldehyde PH value
the leaf mass 0 Composition of the additive 1.0 2.5 5.0 0 Wet burst pressure **)
Additive***), % 1.0 2.5 5.0 acid aminoimide
azoline after
Examples 1 to 4 Locust
bean gum 70 Dry burst pressure **)
Additive***), % 49 48 46 0 0.5 0. 0 0 % % 8.0 to 8.5 70 0.5 62 68 72 0 0 6th 12th 22nd 100 0 8.0 to 8.5 70 50 71 75 , 78 0 3 9 19th 28 70 30th 8.0 to 8.5 69 59 70 77 84 Q 3 8th 20th 32 50 50 8.0 to 8.5 70 67 74 81 82 0 .3 11 25th 35 40 60 8.0 to 8.5 68 65 78 80 -81 0 4th 7th 18th 25th 30th 70 8.0 to 8.5 68 72 78 81 80 0 4th 4th 9 ' 11 20th 80 8.0 to 8.5 71 73 79 82 82 0 (0.4) *) 4th 5 7th 10 90 8.0 to 8.5 69 72 56 54 45 0 4th 0 0 0 0 100 4.0 to 4.5 68 79 69 71 73 0 0 5 10 17th 100 0 4.0 to 4.5 69 59 69 74 80 0 2 9 18th 27 70. 30th 4.0 to 4.5 69 66 71 80 80 0 4th 13th 23 31 50 50 4.0 to 4.5 66 69 73 80 82 0 6th • 15th 26th 35 , 40 60 4.0 to 4.5 66 71 78 84 87 0 8th 17, 29 38 30th 70 4.0 to 4.5 69 71 82 87 87 0 9 18th 28 • 32 20th 80 4.0 to 4.5 69 71 80 82 83 0 10 14th 24 25th 10 90 4.0 to 4.5 77 10 0 100 78

*): (0.4) = very weak wet burst pressure.
**) Each value is the average value of the average burst pressure values of three sheets produced as hand samples in

Kilograms per 45.4 kg of the ream weight of 40.2 ■ 64.4 cm ■ 500 sheets.
***) Addition based on the dry pulp weight.

Example 3

On the basis of the data in Example 3, a 45 ratio of 30:70 was determined as an approximate optimum mixture of the aminoimidazoline derived from a polymeric fatty acid (especially at a pH of 8.0 to 8.5) according to Examples 1 ? determined. The ratio was then within one to 4 and aldehyde locust in comparison ^'f pH range wide tested.

The following data were obtained:

0 Dry burst pressure **) Additive***), % 2.5 5.0 0. Wet burst pressure **) 0.5 1.0 2.5 5.0 PH value
the leaf mass 65 1.0 81 84 0 " Additive***), % 8th 15th 28 39 66 0.5 74 80 82 "0 8th 15 .. 26th 35 2.5 to 3.0 69 71 73 84 87 0 5. 11 24 35 4.0 to 5.0 70 71 78 81 82 0- 4th 10 25th 35 6.5 to 7.0 73 73 74 73 80 0 (0.4) *) 4th 8th 17th 8.0 to 8.5 66 71 72 60 60 0 (0.4) *) (0.4) *) (0.4) *) 2 9.5 69 66 10.2 69

*) (0.4) = very weak wet burst pressure.

**) Each value is the average of the average burst pressure values of three sheets produced as hand samples in kilograms per 45.4 kg of the base weight of 40.2 · 64.4 cm · 500 sheets.
♦ * ♦) "Addition based on the dry pulp weight.

Example 4

The retention of wet strength after soaking (compared to one in use located drinking cup cardboard) was for the mixture according to Example 3 of aminoimidazoline and Aldehyde locust bean gum determined in a ratio of 30:70. A Series of sheets produced by the method described above, wherein the in the sheet

mass measured pH was 7.0 to 8.0. The wet burst pressure of these sheets was then after method described above with the deviation determined that the paper at different pH values was maintained in water for periods of up to 9 days. Disregarding the Durability is typically 15 minutes in water when tested for wet strength. placed.

It became the following data obtain: iruck after a
4 days Population calibrate from
6 days 9 days Set pH value
des to soak
used bath 15 minutes Wet burst
ITag 6.4 6.5 2.3 19.5 - 16 17th 4th 27 19 · - 23.5 20.4 7th 25th 24 21 20.5 - 7th 23.5 - - 25th 22nd 10 25th 24.5 - 21 18.5 11 26th 22nd 13.6 13th - 12th ·. 19.5 -

Example 5

An aminoimidazoline derived from a fatty acid was obtained by reacting 65 g of tall oil fatty acids (iodine number = 135) with 4.0 equivalent (= 35 g) of triethylenetetramine. The reaction was carried out at 300 ^° C. for 3 hours, the water of hydration being removed. The product had an amine number of 345 and a viscosity of 4 poise at 25 ^° C.

The above fatty acid derived aminoimidazoline (30 parts) was used together with Aldehyde locust bean gum (70 parts) following the procedure of Example 1 to bleached soda pulp admitted. Sheets were made as hand samples and the wet burst print was carried out as in Example 1 determined. The pH of the pulp dispersion was 4.5 to 5.0. The wet burst pressure was at 25.9 kg per 45.4 kg of the basis weight of 40.2 x 64.4 cm x 500 sheets. The wet strength was continuous.

Example 6

50.5 g of a mixture of tall oil fatty acids and tall oil fatty acids with esters of an epoxide value of 2.0 (epoxidation with peracetic acid) 49.5 g of tetraethylene pentamine at 165 ⁰ C were reacted for 2 hours. The reaction product was then vacuum distilled to remove water and other volatile materials. The product obtained (mainly an imino-linked amino amide) had an amine number of 602.

The above amino amide (25 parts) was combined with aldehyde locust bean gum (75 parts) was added to bleached soda pulp by following the procedure of Example 1. As hand mister Sheets were made and, as in Example 1, the wet burst pressure was tested. The pH the pulp dispersion was 3.6. The wet burst pressure was 24.5 kg per 45.4 kg of the ream weight. The wet strength was permanent.

Example 7

Dialdehyde starch (90% oxidized) was combined with the aminoimidazoline derived from a polymeric fatty acid mixed according to Examples 1 to 4. The wet strength was prepared as a hand sample Leaves determined at three different pH values and an addition of 0.4 g (3 parts Dialdehyde starch, 2 parts aminoimidazoline) per 2000 ecm of the pulp mixture (2.5% of the additive, based on the dry weight of the pulp).

The following results were obtained:

attempt

7-1

Dialdehyde starch

0.24 g

Aminoimidazoline *)

of polymer

fatty acid

0.16 g

Wet burst pressure **), pH

9.8 8.6. 4.9

4.5

*) According to examples 1 to 4.
**) Kilograms per 45.4 kg of the basis weight of 40.2 x 64.4 cm x 500 sheets.

Examples

Guar gum was oxidized with periodate so that 10% oxidation was obtained; i.e. that one in ten hexose units was oxidized. Because guar gum has an average of two anhydromannose units contains per anhydrogalactose unit, leads the oxidation to the fact that three out of ten galactose units present to the dialdehyde functionality were oxidized. The product was tested for wet strength using the procedure of Example 1. Bleached soda pulp was used and was whipped for 35 minutes and its pH was adjusted to 7.5 to 8.0.

There were the following results achieved: 0% Wet
Conc initial print *) at a
ration of addition
1.0% it
**) from
2.5% test ng of the addition
'Aminoimidazoline
of polymeric fatty acid
0 /
'O 0 5 10.4 VII-I 40 0 7th 14th VII-2 35 0 5.4 11 VII-3 30th 0 7th 10 VII-4 25th 0 7th 9.5 VII-5 20th Put it together!
Aldehyde guar gum
0 /
/ 0 60 65 70 75 80

*) Kilograms per 45.4 kg of the basis weight of 40.2 · 64.4 cm · 500 sheets. **) Addition based on the dry weight of the cellulose.

From the above examples it can be seen that a large number of fatty acids derived Aminoamide or aminoimidazoline compounds effective in wetting paper when taken together with polysaccharides are either of the galactomannan gum type or as conventional Starch with different degrees of oxidation can be used. It is obvious, that it is a permanent wet strength that for cardboard boxes, drinking cup cardboard, folding box cardboard, etc. is required. This permanent wet strength was obtained by simply adding the additive to the pulp. A hardening either at elevated temperatures or for longer periods of time is not necessary.

Claims (3)

Patent claims: 1. Process for the production of felted, fibrous cellulose products with additional use modified polysaccharides, characterized in that the , cellulose-containing pulp about 0.1 to 10%, based on the dry weight of the cellulose fiber, admits a mixture that consists of A. about 15 to 85 percent by weight of a modified Polysaccharides, particularly an oxidized polygalactomannan gum or an oxidized starch, and B. about 85 to 15 percent by weight of an aminoamide or aminoimidazoline of a monomeric, an epoxidized or a polymeric fatty acid with an amine number of about 50 to 700 consists. 2. The method according to claim 1, characterized in that that one adds a mixture in which the modified polysaccharide from one by treatment with 0.01 to 0.4 moles of periodate per mole of the anhydrous hexose unit modified polygalactomannan gum. 3. The method according to claim 1, characterized in that a mixture is added in which is the modified polysaccharide from a substantially fully oxidized dialdehyde starch consists. 809 629/1365 10. 68 © Bundesdruckerei Berlin