DE1546369A1 - Process for the production of paper and similar material made from cellulose fibers and having increased wet strength - Google Patents

Description

PATENT _{LAWYERS 15Α6} 369 DR. INC.A.VAN DERWERTH _DR . _FRA NZ LEATHER

91 HAMBURG 9O. _mOn c _H EN βό

WIUTOIH ».TH. ·· - TlU ΙΘ4Ι1Ι 770 ··! lUCW-CAHN-.T «. >. - TIL. <0 · ΙΠ 440 · 4 ·

Munich, July 14, 1969 L / D

Applicant: Hercules Incorporated, 910 Market Street, Wilmington, Delaware, V.St.A.

Process for the production of cellulose fiber » manufactured paper and similar material of increased wet strength

Patent 1,177,824 relates to a process for the preparation of water-soluble condensates from polyamides and epichlorohydrin by reacting polyamides in aqueous solution with epichlorohydrin, which is characterized in that polyamides obtained by polycondensing saturated aliphatic dicarboxylic acids having 3 to 10 carbon atoms and more -valent anines of the general formula NH ₂ - (C _n H _2n NH) _x H, in which η and x are whole numbers is Vert of at least 2, in a molar ratio to the dicarboxylic acids of 0.8 t 1 to 1.4 j I have been prepared at temperatures of 110-250 ° C, reacted in a manner known per se with epichlorohydrin at temperatures of 45-100 ° C.

The cationic resins obtained in this way are for useful in a number of uses. One of these is the wetting of paper, cardboard and similar fibrous products made from cellulosic fiber. Ea has been found that a high degree of wet strength paper and paper products

"009821/1564. _2. New documents (Art. 7 ,, Ab .. ₂ u ,, β * a *. X ^ _n , ^? ™ ™ ^AL

reported when these resins are used in amounts from about 0.1 to about $ 5 (resin solids on a dry weight basis dee paper) incorporated therein or applied to it. These resins can be in the vat or through Spray applied. For example, pre-formed and partially or fully dried paper can pass through Immersion in or spraying with an aqueous solution of the resin are impregnated, whereupon the paper for about 0.5 to 30 minutes at temperatures between 90 and 100 ° C or higher can be heated to dry and harden the resin in a water-insoluble state. The received Paper has greatly improved wet strength and therefore this method is well suited for impregnation from paper towels, absorbent tissue, etc., but also from heavier material, e.g. wrapping paper, Sackcloth, and the like. To give these fabrics good wet strength to communicate.

The preferred method of incorporating these haze into Paper is, however, by addition in the interior before the sheet formation, whereby in advantageous wines the substantivity the resins for hydrated cellulose fiber »is exploited. When performing this procedure, an aqueous solution is used of the resin in its uncured and hydrophilic state to form an aqueous suspension of the paper pulp in the Hollander, Storage box (stock ehest), Jordan machine, vane pump, head box, or any other added to a suitable place before the leaf formation. The sheet is then formed and dried in the usual way, where » cured by the resin to its polymerize and water-insoluble state and imparted wet strength to the paper.

The uncured cationic thermosetting resins of the invention incorporated in paper can be made from acidic, neutral or cured in alkaline conditions, i.e. at pH values of about 4-10, by placing the paper in a heat

009821/1564 - 3 -

Treatment is subjected to about 0.5 to 30 minutes at a temperature of about 90-100 ° C. However, better results are obtained under alkaline conditions. In view of this and the relatively strong Corrosion of the plant at pH values below about 6.0 is preferred to hardening at a pH of about 6.0 to 9.0 carried out.

The cationic resins obtained in this way can be used in processes to make water-soluble or to apply water-insoluble coating or impregnating agents to fibrous organic and inorganic materials such as paper fibers, textile fibers, glass fibers, etc. It it is particularly advantageous to use these resins in processes which include the addition of coating or impregnating agents to paper and the like in its interior, such means being added to an aqueous pulp suspension, e.g. added to a paper-making plant in the Hollander, in the vane pump and the like, the fibers are then converted into sheets or webs and dried in the usual way.

For example, in a porous, fibrous cellulosic material in suspension along with about 0.25-10 $ of a water-soluble carboxyl-containing compound, the presence of relatively small amounts, e.g., from about 0.1 to about 5 %, improves On the dry weight of the fiber, these resins not only flocculate and deposit the water-soluble carboxyl-containing compound on the fibers, but also serve to keep them on the fibers by the formation of a direct bond between the cationic resin and the water-soluble carboxyl-containing compound and by the affinity of the cationic resin to anchor the fiber. When these resins are used in the same quantity in connection with each other. With unsolvable coating or impregnating agents, improved retention of such agents by the fiber is also achieved, moreover

00982 1/1564 _ k -

BATH

In any case, the products obtained have improved properties, e.g. improved wet and dry strength, etc.

The cationic resin and the coating or impregnating agent are preferably added to the aqueous stock suspension in the form of aqueous solutions or, in the case of water-insoluble coating or impregnating agents, in the form of an aqueous emulsion or dispensation. The order of the cationic resin and the coating or impregnating agent is not critical, but is important to achieve the best results. Thus, for best results in the case of water-soluble coating or impregnating agents, for example largest Z _u nahtne in the dry and wet strength obtained when the cationic resin is added first to the aqueous pulp suspension and is thoroughly mixed before; Addition of the water-soluble coating and impregnating agent. In the case of water-insoluble coating or impregnating agents, the order in which they are added depends to a large extent on the amount of cationic resin used. Thus, when less than about 0.5 to about 0.6 $ of the cationic resin is employed, best results are obtained when the water-insoluble coating or impregnating agent is added first and thoroughly mixed with the fabric before the cationic resin is added. If more than 0.5 to about 0.6 # resin is used, it is better to add the resin first.

A wide variety of water-soluble or water-insoluble Coating or impregnating agents can be more advantageous Manner using the cationic resins of the invention. So can any water soluble or water-dispersible carboxyl-containing compound therein Way to be applied. Examples of compounds of this type are polymers and copolymers of acrylic acid and methacrylic acid, such as acrylamide-acrylic acid, methacrylamide-acrylic acid, Acrylonitrile ~ acrylic acid, methacrylonitrile acrylic acid, Mixed polymers, which one or more alkyl acrylates and acrylic acid, copolymers of one or

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BATH ORIGINAL

several alkyl methacrylates and acrylic acid, mixed polymers from one or more alkyl vinyl ethers and acrylic acid, and the same copolymers in which methacrylic acid is used instead of acrylic acid is used in the above examples, water-soluble cellulose ethers such as carboxymethyl cellulose, Carbox3Tnethylhydroxyäthylcellulose etc., the alkali and Ammonium salts of water-soluble cellulose ethers, the alkali salts of resin including gum rosin, resin gums and Tall oil resin, the alkali salts of modified resin such as disproportionated, polymerized and partially hydrogenated Resin, the alkali salts of adducts of resin with substances such as maleic acid, fumaric acid, itaconic acid or the anhydrides of these acids, and the alkali salts of various saturated or unsaturated fatty acids with about 10-22 Carbon atoms.

Examples of acrylic acid polymers and copolymers, with which the resins of the invention can be used; are those according to the American patent specification 2,661 and Canadian Patent 597 013.

The water-soluble or water-dispersible compounds, with which the resins described here can also be used with advantage, also include lower condensates Alk ;, lenoxyde with polymers of acrylic acid, methacrylic acid and itaconic acid one having average molecular weights of about 1000 and condensates of lower alkylene oxides with copolymers of acrylic acid, methacrylic acid and itaconic acid with a content of at least 35 Mo1 $, and preferably at least about 50 moles. $, of one or several of these acids as the monomer units to be used. Polymerizable compounds, which with one or several of these acids or copolymerized with salts of such acids include the esters of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and citraconic acid, and monohydric alcohols such as methyl » Butyl, octyl, dodecyl, cyclohydric alcohol, etc., vinyl and

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Vinyloxyalkyl esters of carboxylic acids such as sa »iff · (tare, Propionic acid and the like., Vin> lather such as Xthylvinyläther and Butyl vinyl ether. Acrylamides, methacrylamides, etc. The preparation of these carboxyl-containing polymers and copolymers and their condensation with alkylene oxides can be carried out according to known procedures are carried out. In the latter reaction, the ratio of the introduced alkylene oxide from about $ 1 Mo1 to $ 250 Mq1, and preferably between 10 and about 95 mol $, of the carboxyl-containing units of Polymers fluctuate.

The water-insoluble coating and impregnating agents, which advantageously use the cationic Resins of the invention can be applied, close Substances such as resins, precipitated or insoluble glues, elastomers, waxes, pitches, bitumens and oils, as well as the various clays and / or pigments used in the production of filled and / or coated papers will. Typical water-insoluble substances of this type that can be applied are in US U.S. Patent 2,601,598. The cationic resins of the invention can also be used advantageously in the Application of Ketendiaieran on paper and the like. Used will. These can sometimes be dispersed directly in the aqueous pulp suspension. You can also use the In the form of aqueous dispersions, for example as mentioned in US Pat. No. 2,627,77, or in any other suitable manner, e.g. in the form of aqueous dispersions of ketene dimer compositions which are finely divided on particles of a inorganic material such as clay, silicic acid and the like. Contain carried ketene dimer. Ketendimer assemblies of the latter type are disclosed in U.S. Patent Specification (Serial No. 6 * 6 020). In addition, this can be «resins can be used advantageously to non-ionic marriage and to apply anionic wax emulsions.

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% A ORIGINAL

Another application in which the cationic resins of the invention can be used to advantage is in the manufacture of fibrous sheets, mats and other fiber products from mineral fibers such as glass, rock wool and asbestos fibers. It has been found that the incorporation of the resin into the mineral fiber sheets, - ■ atten and improves the like (based solid resin to the Pasergewicht) in amounts of from about Ο, Ί to 12 i "inter-fiber bonding and wet strength gives these products.. In the manufacture of such products, an aqueous solution of the resin can be added to an aqueous suspension of the fibers, and the fibers can then be converted into sheets, mats and the like and usually dried. Instead, an aqueous solution of the resin can be applied to a preformed and partially or completely dried sheet, mat or the like by spraying, dipping and the like, and the sheet, mat or the like can then be dried in any convenient manner, for example by air drying heated rollers, in heat tunnels, using lamps or in cafes, dried.

Example 1;

Bleached Tacoma kraft pulp was comminuted to a Schopper-Riegler price of 750 ecm in a Noble and Wood-Xreis-Xaufholländer. The substance was then adjusted to pH 9 to 100 NaOH and 1} 6, based on the dry weight of the substance, of the polyamide-epichlorohydrin resin, prepared according to Examples 1 - h of OAS 1 177 824, was added. The substance was deformed on a Noble and Wood handsheet machine into a sheet using a closed system wherein the white water contained 100 parts per million sulfate ion and was adjusted to pH 9.0 with 10% NaOH. Some of the calibrating hand sheets were additionally hardened for one hour at 105 °. The leaves tested for wet strength were soaked in distilled water for 2 hours. The results follow in Table I.

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BATH ORIGINAL

Table I. Basic weight
Pound per
3000
Square feet Wet dough
speed
PfuMd /
customs Wet strength
strength
tet pound /
customs Resin according to
example
the DAS
1 177 824 $ sugesetstea
Resin related
on dry
filler 40.6 6.5 8.5 1 1.0 39.2 5.9 8.6 2 1.0 40.3 6.0 8.2 3 1.0 40.8 7.4 8.7 4th 1.0 40.5 0.2 1.1 without addition 0.0 Example 2:

Bleached Tacctna power pulp was ground to a Schopper-Riegler freedom of 750 ecm in a Noble and Wood circulation Dutchman. The pH of the fabric was 7 »5-7.8. 1 % of the plyamide-epichlorohydrin dimethyl sulfate resin prepared according to Examples o-i'i of DAS 1 177 824, based on the dry weight of the substance, was added to this substance. The fabric was converted into sheet form on a Noble and Wood handsheet machine using a closed system. The white water contained 200 parts per million sulfate ion and had been adjusted to pH 7.5. The resulting hard sheets were passed through press rollers and then dried on a drum according to the .b / üXichen method. A portion of the resulting handsheets were cured for one hour at 1C-5 ° C. The leaves tested for wet strength were soaked in distilled water for 2 hours. The results follow in Table II.

Table IT

Resin according to
example
the DAS
1 177 824

* p added resin (dry matter oasis)

Wet Tensile Strength (pounds / inch width) uncured cured

7th
8th

1.0 6.4

1.0 6.4

1.0 6.5

009821/1564

8.8 11.2 11.5

bath

9 1.0 10 1.0 11 1.0

6 _t 5 5.7 5.1

8.7 9.3

■ 1) Basic weight of all sheets was 40.0 0.5 pounds per 3000 square feet. Sheets made from the same pulp gave wet tensile strengths, taken from the pilsner, of 0.8 (hardened) and 1.2 (hardened) pounds per inch of width.

Bejgpd el 3 t

In Table III are the results measured on paper sheets using other quaternization tools resins produced (Examples 12-17 of DAS I 177 824).

Table III ' Methylj © did Qwater-
never-
guessing
niittel
in g $ addition
resin
(Dry
st off base) Wet draft ^
firm
speed
Lb/
Inch width , 5 example
the DAS
1 177 824 Type of quatern
sizing agent Dietary Hydrogen Sulphate un-
här ~ här
tet tet ,1 j Ethyl bromide 20.9 1 6.0 11 , 6 J2 1-chloroglycerin 22.6 1 5.1 TO , 0 13th 1.3 "dichloroglyceri 16.0 1 6.1 10 , 5 14th Bensaylehlorid 16.2 1 5.5 10 , 2 -n 19.0 1 5.4 9 16 18.6 1 5.3 9 17th

1) Basic weight of all leaves x »ar 40.0 * 0.5 pounds per 3000 square feet. Sheets made from the same pulp gave wet pull strengths of 0.8 (uncured) and 1.2 (cured) pounds per inch of width, taken from the filament.

Example 4;

Bleached Tacoina kraft pulp was measured at a Schopper-Rlegler price of 750 ecm in a Noble and Wood circle

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wedded Dutchmen. This mass was adjusted to pH 9 1 above sodium hydroxide solution set and 1 $ the after resins obtained from Examples 18-20 of DAS 1,177,824 was added. It was then put on a Noble and Wood handbook chine using a closed System brought in Blattfona, in which the white water 300 parts per million sulfate ion and adjusted to pH 9 with 10% sodium hydroxide performance. The leaflets were dried on a conventional drum dryer. Part of it was additionally at 105 for an hour hardened. The leaves were soaked in distilled water for 2 hours and tested for wet fastness. the Results follow in Table IV.

Table IV Basic weight
Pounds / 3000
Quadra, tfufi Wet draft
sturdiness
Pound / s Wet draft
activity
hardened
Pound / ZSl Resin according to
example
the DAS
1 177 824 $ added
Harz basaogön
on the dry
kenstoff 4o, 6 5.7 8.7 18th 1.0 40.6 6.2 9.4 19th 1.0 4o, 3 6.3 8.6 20th 1.0 Leg & iel 5:

Bleached Weyerhäuser SaIfit softwood pulp was used in a pH 7 water with a Noble and Wood Krels runner to a Schopper-Riegler-Freiheii of 823 ecm. The pulp was diluted to $ 2.5 density with water at pH 7 diluted. The following chemicals were added to 2 liter portions of the slurry with stirring.

1a) A sufficient volume of the above aluminum sulfate

solution to lower the pH of the pulp to 4.5, 1b) 1 $ (based on the dry weight of the substance) of a dry-strength additive, consisting of a 90:10 acrylamide-acrylic acid copolymer, added as I ^ ige aqueous Solution. After a few minutes of stirring, enough alum solution was added to raise the pH of the pulp 4.5, as indicated under la). This

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OR! Q _INAL

" ^u " 1545369

Acrylamide / acrylic acid mixed polymer was produced by introducing the following substances in the specified order: e in oitie Druckfente Pol; merization fIacehe:

9s 0 g utnlrriptar.lisiorrtGs acrylamide 185.0 £ distilled water t _t 0 g distilled acrylic acid 0.5 g iscpropanoi
5.0 ecm 1% solution of ₃ in distilled water

Immediately after the addition of the catalyst, the contents of the bottle were placed under a nitrogen blanket brought for several minutes. The bottle was then capped and ni ± o a water aspirator during Evacuated for 1 minute. Nitrogen was sugesotzt up to a total geographic pressure of 3.16 kg / cm and the bottle was evacuated again. This rinse on and ejjcuieren was once again viederhev.t, after which nitrogen up

was added to a total pressure of 2.1 kg / cm. The polymerization bottle was then placed on a tilting device at 22 ° C. and rotated for several days. The viscous solution obtained was stopped with hydroquinone and a concentration of the total solids showed that complete curl was obtained in a polymerized product. The solution was then diluted to a concentration of 1 wt voué ^ (specific viscosity = "5G) diluted and adjusted its pH to 8.2 with NaOH it was daaa b at 1 C: '- o.:. ^R .- A orv: ending stored. Ic) 1? o (based on dry goods / icht dos substance) one

Polyanlci-epichlorohydrin condensate s product it as an aqueous solution. This condensation product was prepared according to the following procedure. To a mixture of 19 ¹ ^ g of triethylenetetramine and 600 g of water, 17 ^ 0 g of adipic acid were added in several portions, each portion being allowed to dissolve before the next was added. The resulting mixture was then frozen to 195-200 ° C for 1 1/2 hours and water became steady. abdsstilliert, the mixture -iurde then on

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BAD ORiQINAL

Chilled under vacuum and 3 liters of 80 ° C warm vaseer were carefully added. The polyamide product had a total solids content of 5 **, 4 % and an acid number of 3.6. Water was added to dilute 2162 g of the product to a total weight of 10,751 (S. The aqueous solution was stirred and heated to 45 ° C. In this) state, the addition of 1025 g of b-pichlorohydrin was started. The addition was stopped by the time the temperature reached 60 ° C. The mixture was then held between 60 and 70 ° C until its Gardner-Holdt quality reached value E reached. Then 9 l of water and 250 ecm 3 of hydrochloric acid were added. The final product had a pH of 5 x 75 and a total solids content of 11.0 #.

1d) 1 $ 6 of the polyaraid-bpichlorohydrin condensation product of 1c) (based on the dry weight of the fabric). After a few minutes of stirring, an equal weight of the acrylic nide-acrylic acid copolymer from Ib) was added to the slurry. The pH of the final slurry for both Ic) and 14) was about 7.0.

All Breimuster were diluted to 0.25 $ density with water at pH 7, and then further diluted to a Decklekastendichte of 0.025 $> (χ 24 36-500 sheet ream) to handsheets of ko pound basis weight using a Noble and Vood sheet manufacturing apparatus to form. A closed white water system was used. The leaves formed were pressed wet to a Feetatoff content of 35 - K5 $ and then dried at 121 ° C. on a steam drum dryer. After conditioning for several days at 23 ° C and 50 ia relative humidity, the sheets were tested in the same environment for various paper strength properties using standard testing equipment. Strength values were corrected to Uo pounds / ream basis weight using the linear relationship S = kB, where S is strength property and B is sheet basis weight. The results follow in Table V.

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Table V Attempt dry strength inherent- $ increase in unhardened

shafts (corrected to the tear-Bess * »wet tensile strength

40 pounds / r base weight) Blade strength after 2

Elmendorf-Mullen- keit versus Stünden Ein

Tear, burst strength control (i) wtfchen in search for distillation

g.per leaf p.s.i. ten water

la 86 20th control Not checked Ib 60 35 16.4 1.6 pounds / ZdL lc 74 25th **. 5 3.4 ld 5h 39 20.0 6.3

(1) TAPPI 40, page 499, July 1947

The above values Beiges that when a cationic Polyavid-Spichlorhydrin resin is of the type disclosed herein is used with the acrylic * säuremischpolynier-TrockenfeetigkeitsKusats, an improvement was achieved in the entire tear Berstfestlgkeit 20 i "in comparison with the Alaunkontrolle while the resin alone gave an improvement of 4.5 ^ and the alum plus dry strength additive gave an improvement of 16.4 # * moreover, the polyamide-epilorohydrin resin product not only does wet strength while the alum treatment does not, but the combination of the acrylic blend polymer with it the resin exhibits a synergistic effect which is almost twice as great as the wet tensile strength caused by the resin alone. Thus, the dry strength additive and the resin mutually increase the ge ·? separated effects of each.

The following examples 6-9 explain the use of the cationic resins used according to the invention in connection with the incorporation of water-soluble coating, impregnating and sizing agents in paper and the like.

Example 6 A ketene dimer assembly was made in the following manner

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BATH ORIGINAL

produced: 10 parts of "Hl-SiI 303% a purified low-density silica, manufactured by Columbia-Southern Chemical Division of the Pittsburgh Plate Glass Company. The mixing vessel was heated in a steam bath to 50 ° C and 10 parts of the molten alk) lketendimer, made from a mixture of myristic and palmitic acid (melting point approx 33 ° C) were added dropwise to the vigorously stirred silica. The product was out of the mixer in shape of a free flowing powder, consisting of the ketene dimer supported on silica in a weight ratio of 1: 1.

An aqueous slurry of the Ketendlaer composition so prepared was prepared in a Varing mixer with gentle whipping. Different proportions of this pulp were processed for 3 minutes each in a Varing mixer with 500 ecm Veyerhauser bleached sulfite pulp with a density of 2.5 $, which had previously been prepared on 750 Schopper-Riegler-Freiheit in pH 8 tap water with dea Valley-Holländer. The pulp mixture in each case was diluted to 5 liters (0.25 $ density) with pH 8 tap water and then various amounts of a 1% solids solution of the various retention aids were added and mixed. For each sheet, 450 ecm of each pulp mixture was diluted to 1.1 l (0.1 # density) for sheet formation on a 100-mesh stainless steel screen in a circular sheet shape 15 »5 cm in diameter. The sheets were pressed between felts and dried on a steam-heated drum dryer at 115 ° C. for 60 seconds. For the first sheet, tap water was used to dilute it to 0.1 % density. White water was used for the dilution of the remaining leaves. Sheets made in this manner had a basis weight of about 40 pounds per 3,000 square feet. The sizing in the leaves was measured with the Hercules photometer using 20% lactic acid ink after the leaves had aged for k8 hours at room temperature. The results

009821/1564 " ¹⁵ "

Table 6 is average times (5 sheets tested in each row) versus 85 ¹ P of the original reflectance.

Table VI

Retention Ketendimer · Photometer «Gluing results / help in $ together« seconds

position Type of restraint assistance

Cato 3 Epichloro-Adrin-Polyatnid-

resin

$ 0.5> 0.6? O 445 + 100O ¹ 0.25 1 » 0.6 # 960 91.8 % 0.125 1 ° 0.6 ^ 535 + 1000 0.5 I » 0.3 ^ ' 180 90 f> £ 0.25 0.3 pounds ₉₃ . 1185 $ 0.125> 0.3 pounds 75 775 725 490

At 100 seconds the reflectance was still over 85 9 ° of the original and equal to the specified percentages.

The epichlorohydrin-polyamide resin used ~ in Example 6 was prepared as follows: To 3 ¹ 9 g and 100 g TriäthylentStramin heated to 123 ⁰ C water 29Ο g of adipic acid were added in small portions. After the acid addition, the mixture Beandigung vurde to about 190 ° C and heated to I90 - held 205 ° C for about 105 minutes. After this time, the "heat source" was removed and the pressure over the resin reduced as much as possible without excess foaming over a period of 10 minutes. 500 cc of water was then added to give a flowable solution of 49.8 ρ solids. 6.3 S of this solution was diluted with 225 cc water and heated to 50 ° C. the heat source was removed and begun the addition of 22 g of epichlorohydrin and a speed was maintaining ", which was the temperature of the solution to about 55 C. the addition required 3 minutes The mixture was heated to about 60 ° C. and held at about 60-66 ° C. for 70 minutes while

009821/1564 -16- *

BATH ORIQINAL

ity of the day of solving rose to E. - In

3 225 ccai ¥ ater sweetsetäBt u »d da» pE eai? 5 adjusted with SGisf ^ tas? © _β Di © band viscosity was about G and the © gas solids content about 8-9 _s 5 $ *

The iss Example & - / e3n> j © Mdeta C © t3 8 starch is a cationi «εοίΐ. '^ Starch (GssrSifisiert corn starch with eiaein nitrogen« · about O ₈ S ¹ S $), manufactured »sold by the kid

Starcla Products Company "

Example 7

The procedure of Example 6 was repeated with the following changes.

1. Unbleached St.Marj's Kraft pulp, ground up 730 Schopper-Riegler-Freiheit was used.

2. 5 cc of a 0.15 ^ aqueous Älkylketendimeremulsion (0.5 based ia alkyl ketene dimer on dry matter) of the substance was added after dilution to 0.25 $ density to each part. The aqueous ketene dimer solution was prepared from a mixture of 5 parts of alkyl ketene dimer made from a mixture of palmitic and stearic acid and 1 part of Atlox 2 ^ 95 (this Hendel product from the Atlas Powder Company is the hexaoleate of a sorbitol ethylene oxide complex).

3. After 2-3 minutes of gentle stirring, various Metigen (10 ecm, 5 ecm, 2.5 ecm and 1.25 ecm, which correspond to 1 $, 1/2 $, i / k ia and 1/8 % resin, based on the dry pulp) added to a 1.25 # strength pesticide solution of the epichlorohydrin-polyamide resin from Example 6,

The results of the photometer conductivity test with Zotiger lactic acid ink and the Mullen burst strengths after soaking in water for 2 hours are shown in Table VII.

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Table VII

Epichlorohydrin * photometer gauze "bursting strength Polyamide resin # time / seconds p.s.l.

ι # τ4ο 16.0

0.5 £ 196 τι, 2

0.25 # 3 7.0

0.125 i » 0 k, o

The average mullenberet strengths of the same Paper, but made without the epochlorohydri », polyamide resin were 3.2 p.s.l *

Example 8

The procedure of Example 7 was used with the modification that 5 cc of a 1.25 $ Wachseaulsion> solid content in place of the 5 cc of 0.15 $ Ig "ii Alkylketeneotulsion were used. These are Q, h <$> Wach @emulsion «solid, based on the dry matter. The wax "tu" Is ion was containing a commercially available product of HercuJoa Powder C ^ iapany what 45 # Oesamtfeststoffe and H'3 _t k ^ completely Vaffialertes paraffin wax and as Paracol Hohr is known.

The results of photometric glues ^ ngsprüfung with 20 iL lactic acid ink and the Mullenberetfeetigkeiteprüfung by Zk hours soaking arising VIII table.

Tabel 009 82 VIII 1 / 15S4 egg. - 18 - Epichlorohydrin Photometer ^ , 3 BATH Polyamide resin Time / sec. Mullen Burst Strength , 2 . * ■ 25th p. , 4 $ 0.5 29 12th ,1 0.25 % 11 TI 0.125 i> 3 6th k

The average Mullen bursting strengths of the same " Paper made without the epichlorohydrin polyamide resin was 3.2 p.s.i.

1.25 B McNemee "clay" were added to 5 liters of a "bleached ta coma fuel of 0.25 Ί" density. This substance was ground to 750 Schopper-Riegle women at a density of about 5% in pH 8 tap water C _t 25 i> with pH S Leiuuzagawceeer verdücat. After thorough mixing of the material, 25 oca of an O _f 125fSigen £ pichlorhy "3rlQ" PGlyai £ id "HAr8" a _{} was} prepared as in Example 6 b & ückri & .b "©, added $, tesm & gmw: mu £ that Troc! f «u £ t @ fl ^> . Ftiisf butter

manufactured in bite game 6 . Eit'j the same sata of five sheets utarä® ahß @ d & s Hera gsifartist, The white water for everyone * Reiläovutu »üuT- <sa o« »© od # r # Fil'i« z ^il paper filtered, w * leb $ Ssach KoBcSitisiisisr € & for 2 ^ hours it in a room of constant $ s> Te-Tiparat-ar iind k on β button moisture won. were warssj "The filter paper® with the Weißwaaeerfeinen was dried, conditioned and weighed again. I * aε dish of the fine divided by the weight of the F © i; .ne? Ä plus d # ri weight of the leaf egg in each row, multiplied by 1Ci? ₉ gives the percentages of fabric and clay used for 5 sheets, welch® by de * P «. pi er her et el lungesieb hißdurchgegee ^. The aeche content of the first, third and fifth leaves in each row was determined. The results follow in Table IJC.

Table IX Restraint aid ^ through the # ashes

di «hÜ £ n- '■ ^Sheet 3 ·"«" 5 sheets of fine art

0.25 # epichloride polyamide

7.70 9.72

O O 3 8 2 1 /

3. * 1.2

1.5 1.6

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BATH ORIGINAL

546369

The following Examples 10-12 explain the BrauofebwrSec.it ication. Li & a Har-asc la des ⁰ lies »* position" ¥ € ES fibrous leaves _t Maν & en and d'gjl _e aee a «« · noise

Example IC

Fe-g asbestos fibers were sifted to a Weriieg- ^ liseköi ' ⁵ pounds meow with 600 ecm tfaeter. © fees as in the H * iaple2 "· ά®τ DAS 1 177 S £% manufactured resin» ugeeetzt (2 5 · »Hare« related to .des Troekenfaserg ^ icht). Iles ³ Bs ^j ei itUE ^ iSe 2 Miau » ten stirred sad -then formed into a tar mat tsit tiatr Hsiaöblattfera. The mat from pressed mndi fislf <2er Treea®! geo dries. Other asbeetfaseff ^ lst tar were made as @b "n the bottom The leaves are withered for 30 minutes in distilled water, sexaek they aia "d @ ss ¥ & es * © rn ^ noemisti ^ s ^ ia excess water -Bsretffeetigkelteprüfer are checked. The results £ @ figs: 1h Tftbelle 1 »

Table X

$ added Kars bszogeE Maßfeetijfkcit ( based on dry weight pounds / square

2 5 ₉ ϊ

0 none

(The leaves couldn't even get out of the water in which they were soaked to be removed)

Example 11

Hand sheets are produced from Asb «@ ti'asersi by stirring k g of fibers in 600 ecm of water for 2 mirauts in a Waring mixer. A 0.1 liter aqueous solution of the resin, prepared as in Example 1 of DAS 1 177 824, was then added and the pulp was stirred for a further 5 minutes. The handsheets were molded onto a 15 cm circular sheet mold, "pressed" and drum dried. the

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BATH ORIGINAL

dry leaves were additionally cured in an oven at 105 ° C for one hour. They were then in de » soaked in still water for 30 minutes and tested for wet strength using a Mullen Beratfeatigkeitaprtifera. The results follow in Table XI.

Table XI

i> Resin added based on wet strength (Mullen) based on dry weight pounds / square inches

2 k * k

Z 4.5

k 5.6

k 5.0

O O *

0 0 *

* The leaves could not be removed from de »Vaeser without aie disintegrated, to be taken out.

Example 12

Hand sheets were made from a mixture of 75 H glass fibers and 25 % booked Ta coma fuel. They were fortified in a circular leaf shape 15 ca in diameter. A slurry was made from 2.25 g glass fiber plus 0.75 β bleached Tacoma fuel in 300 cc »water. This was then stirred for 2 minutes in a Waring mixer. The pH was adjusted to 9.5% with 10% NaOH and 36O g of a 0.1% solution of the resin, prepared as in Example 1 of DAS 1,177 & 2k (12 £ Solids based on dry fibers) added. After stirring for 2 minutes, the slurry was sheeted, pressed and drum dried. A bleached sheet was produced except that no resin was added. Both sheets were soaked in distilled water for 30 minutes and then tested for wet strength with a Mullen Burst Tester. The results follow in Table XII.

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Table XII

f> Resin added based on wet strength (Mullen) versus dry fiber weight (pounds / square inches

12 5.0

0 too awake for the exam

The following Examples 13-16 illustrate the application of the Cationic resins according to the invention for preventing shrinkage and matting of solid.

Example 13

A sample of cleaned, carbonized and bleached woolen flannel cloth was treated in the following manner with a S ^ igmo aqueous solution of the cationic thermosetting resin, prepared as in Example 1 of DAS 1,177,824. The dry piece was double-padded with a solution of the resin at room temperature on a 25 cat laboratory peg. The moisture uptake was 113 # ( $ 5.6 resin solids based on the dry weight of the cloth). The treated piece was air dried and left to stand at 150 ° C for 5 minutes, followed by 45 minutes in an oily neutral soap solution at 55 ° C was washed. After air drying, the total shrinkage of the piece was x 9.1 #. Compare this to £ 50 shrinkage for an untreated specimen. It should be noted that these values represent the total shrinkage, i.e. relaxation shrinkage plus matting shrinkage, feel and color of the piece after washing were not impaired by the previous treatment.

Example 1.4

The treated sample of Example 13 was used a second time as in example. 13 washed followed by a one-half hour dry cleaning at room temperature from a third Wasden. No additional shrinkage was found after these treatments.

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Example 15

A sample of woolen fabric was made as in Example 13 with a 5 »1 $ aqueous solution of the cationic resin as in Example I of DAS 1 177 824, treated and Cured at 100 ° C for 5 minutes. The moisture pickup was $ 100 ($ 5.1 resin solids on a dry weight basis of the fabric). Bs was washed and dried like describe beforehand. The total shrinkage was found to be $ 6.1.

Example 16

A sample of woolen fabric was treated with a 3 »above aqueous solution of the cationic resin prepared as described above and treated further as in Example 13. The moisture pickup was $ 100 ($ 3.13 > resin solids based on fabric dry weight). After washing, the total shrinkage was 3t 19 °. This sample was washed four times in a row. The increase of the shrinkage due to the extended Waschbahandlung was 4.8 f "or a total of 7.9 f ^Q after washing five times.

The following Examples 17-22 explain the ending of cationic resins according to the invention during manufacture of non-woven pieces.

Example 17

A web of 15 denier 4 ca light, crimped staple rayon fibers was made with a 10 ^ igen solution as in Example 1 of the resin produced by DAS 1 177 824 and in a laboratory Butterworth ^ Klotziaaschine on a dry resin recording padded from 7 »4 $. The piece was dried and 5 minutes cured at 100 ° C. The wet and dry tensile strength the hardened piece was tested on an Inatron testing machine with a crosshead speed of 30 cm per minute measured. The values were given as the maximum load in pounds to fi tearing a $ 2.4mm wide strip in place of the ordinary pounds per square i. because of the uneven surface fj.lic-ie des ^ tück "indicated. The resin treated as above

009821/1564 ~

The third piece had a dry _{tensile strength of 0 9} 17 + 0.4 pounds and a wet tensile strength of 0 _f 09 + 0.1 pounds.

Examples 18-20

Two samples of the same type of nonwoven web were made with a pely vinyl acetate latex (du Pont Elvacet 81-900) treated as in Example 17 and a third with a combination of a Polyainid-EpichlorhydriEi-Hars (manufactured as in Example 1 of DAS 1 177 824) and the latex. The properties of the resulting pieces follow in the Table XIII.

Table XIII

With binder fi dry weight maximum load up to asum

play on the piece of tearing, in pounds _ _i

dry wet

18 $ 7.86> polyvinyl acetate 0.13 + 0.04 0.05 + 0 * 01

19 16.91 # polyvinyl acetate 0.30 + 0 _s 01 0.04 + 0

20 $ 10.28 polyvinyl acetate 0.4 + 0.02 0.09 + 0.02

+ $ 5.14> resin

Examples 21 and 22

3 denier webs of 5.1 cm light common staple paleon fiber were made with a polyacrylic latex. (Rohm & Haas' AC-33, presumably consisting of 70s30 mixed polymer of ethyl acrylate and Methyl methacrylate) as in Example 17 with a combination this latex and polyamide-epichlorohydrin resin (manufactured as in Example 1 of DAS 1 177 824). The properties of the resulting pieces are shown in Table XIV specified.

Table XIY

For- binder $ dry- Maximum load up to play weight on the piece tearing, in pounds

dry wet

21 £ 17.2 polyacrylate 7 + 2 0.7 + 0.2

22 (19.7 ¹ P Pol3 ^r acrylate)

( $ 3.9> resin) 13 ν! 5 + 1

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SAD OPJGiNAL

The following examples 23 and 24 illustrate the application of the cationic resins of the present invention in the treatment of non-fibrous regenerated cellulose film for improvement the bonding of this film to a subsequently applied coating.

Example 23

A cationic resin was prepared by following the procedure of Example 1 of DAS 1,177,824 using 0.97 moles of diethylenetriamine, 1.0 moles of adipic acid and sufficient epichlorohydrin to provide a ratio of 1.15 moles of epichlorohydrin to 1 mole of secondary amine in the to give polyamide formed from diethylenetriamine and the adipic acid. An aqueous solution of this resin with a content of 6 _t $ # solids was applied to plasticized cellophane by means of conventional spraying and dried in an oven at 90 C with artificial train. After 15 minutes of drying time, the film was non-wrinkled, non-tacky, non-retardant, transparent and glossy. It was sprayed on both sides in such a way that a film thickness of 0.00254 mm of dried coating was obtained.

The film was then sprayed with a nitrocellulose-based coating similar to that described in US Pat. No. 2,236,546 and dried at 66 ° C. for 30 minutes. A film thus prepared was immersed in water. In the same way, a film with no anchoring coating, but only with the nitrocellulose coating, was immersed in water. The film with both the anchoring coating made of cationic resin and the nitrocellulose coating remained unchanged after 4 weeks of immersion, while the film without an anchoring coating and only with a nitrocellulose lacquer layer was started already after 1 hour. The tensile strengths of the resin-coated film were the same as those of a non-coated plasticized cellophane.

"- 25 -

0 0 9 8 2 1/1 5 6 4 ^AD

Example 24

A plasticized, untreated cellophane film was immersed in a 9.6 solids solution of the cationic resin, allowed to drain, and the film was then heated to 65 ° C. for 2 hours under a pressure of 10 mm of mercury. Films which were so treated and then provided with a protective, moisture-repellent nitrocellulose lacquer coating and dried as in Example 23 had a water vapor transmission rate of 4.2-4.9 g / 24 hours / square meter, while films which did not have an anchor coating but only a spray coating Nitrocellulose varnish had a water vapor transmission rate of 6 »8 g / 24 hours / square meter.

_BATH 009821/1564

Claims (5)

Claims 1. Process for the production of paper, cardboard and the like. With improved wet strength from cellulose fiber !! by impregnation of the cellulose fibers kept in aqueous suspension with a thermosetting epichlorohydrin resin, forming a paper sheet or the like, causing curing of the resin on the fiber, characterized in that a polyamide-epichlorohydrin condensate is added to the aqueous fiber suspension according to DBP 1 177 82 ^ in such a Amount is added and mixed so that 0.1-5 wt. $, Based on the dry weight of the fibers, des Condensate is adsorbed on the fiber, the fiber « then mass into a sheet of paper or the like Veise is processed, which is then heated to harden the resin. 2. The process according Axtspruch 1, characterized in that to the aqueous fiber suspension after addition of the condensate even from 0.25 to 10 wt ^, based on the dry weight of the fibers, a water-soluble, carboxylic groups-containing polymer is added.. 3 · Process according to claim I _1, characterized in that a water-insoluble coating, impregnation and / or glue agent in an amount of 0.1-5% by weight, based on the dry weight of the Fiber, is added. k ·. Process according to one of the preceding claims, characterized in that the hardening of the resin is carried out by heating to a temperature of 90-100 ° C for 1 / 2-30 minutes. 5. Modification of the method according to claim 1, characterized in that that the polyamide-epichlorohydrin condensate only after the sheet formation by spraying or immersion is applied to the fiber mass, whereupon the Paper sheets or the like. Is heated to harden the resin. 009821/1564 Documents (Art. 7, Paragraph I, Paragraph 2, No. 1, Sentence 3 of the dta amendment,! »Sf ··. V. 4th year