DE3102038A1 - POLYURETHANE POLYMER AMINE SALT AS A PAPER ADDITIVE - Google Patents

Description

The invention relates to a method for improvement the properties of products made from watery sus pensions from cellulose fibers, wood pulp or synthetic Fibers or mixtures thereof are obtained. In particular, the invention relates to a method for Increases the wet strength of paper, cardboard and cardboard and other products obtained from aqueous suspensions of the aforesaid raw materials by molding processes getting produced. In order to simplify the description of the invention, the end products will be these Process hereinafter referred to generally as paper.

It is already known that paper has a characteristic Has property that makes it unsuitable for many applications, namely the limited durability of its fibrous structure against the action of water and other liquids. The bonds between the paper-forming fibers are loosened or destroyed by swelling, so that the mechanical strength of the The paper, when wet, is significantly reduced and the paper itself reverts to its original shapeless

25 fiber pulp is converted.

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The great consumption and variety of paper products has created a great need for continued efforts in the field of chemical additives, which impart various physical properties to paper products. Among the more important, strength Enhancing chemical additives include the synthetic or starch-derived cationic ones Polymeric, oxidatively crosslinked starch exanthates (US-PS 3,160,552) and starch polyethyleneiminothiourethane (US-PS 3 436 305), which is produced by reacting starch exanthate with polyethyleneimine. There are several activity factors which must be taken into account in the manufacture of paper products. These include the wet and dry tensile strength or tear strength, the dry burst strength, the crease resistance, the Tear strength factor, the folding strength and the Pick resistance. Most of the prior art belonging additives improve either the wet strength or certain of these drying properties, sometimes at the expense of the other properties. A problem that is common occurs is the low retention of the additive, which then ends up in the wastewater and causes environmental problems.

Many substances are added to aqueous suspensions of paper pulp fibers in an attempt to improve them Manufacture paper and improved paper products.

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Chemicals are often added to various types of paper pulps to improve finished paper with Properties such as wet and dry strength, increased Tear resistance, better surface properties and to produce similar ones. In addition, chemicals are added to paper pulps to improve processing properties the pulp in processing an aqueous slurry to improve a finished arch. For example, chemicals are added to facilitate retention to improve the fines and the fillers and around the absorption capacity of the paper for various additives to improve. The main goal of all of these processes is to produce better paper with a yield less waste or better utilization of the raw material

15 rials.

It would be a valuable advancement if a papermaking process and an additive or additives could be made available, thereby creating finished paper products With improved chemical and mechanical properties, either alone or in combination with other known additives for paper that could be used in low economical dosages and that itself into the Store paper and bond closely to it to produce a finished paper with improved properties deliver.

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Also of great importance would be a chemical additive for paper pulp, which comes in various types of papermaking processes such as the mechanical wood digestion, with the soda process, with Sulphite process, the sulphate process and the semi-chemical process Procedure could be used. Of additional usefulness would be an additive that comes in a wide variety of pH ranges would be effective, proportionately compatible with other known papermaking additives and would distribute itself evenly in the pulp so that the finished paper would contain the additive as an integral part.

The present invention is based on the concept that improved paper and improved paper products can be obtained by either (1) adding a novel thermosetting polyurethane polymer amine salt to an aqueous pulp slurry given, the paper web is formed and the paper web is cured or by (2) a paper web prior to the drying stage in the papermaking process a thermosetting polyurethane polymer amine salt in one aqueous system is sprayed or impregnated with this.

The new polyurethane polymer amine salts are the subject of DE-OS 30 15 143, to which with respect to the present Registration is explicitly referenced.

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The polyurethane polymer amine salt consists essentially of the reaction product of a prepolymer with oxime-blocked ones NCO end groups with an amine and then with an acid, with unlimited dilution with water Aqueous Po 1 yurethanpolyrnere are obtained.

In the context of this application, the term “waterborne” means the presence of the amine salts of the amine reaction product with the oxime blocked isocyanate prepolymers in an aqueous medium. Indeed, it is not always obvious whether the polyurethane polymers in water a microscopically heterogeneous mixture of two or more finely divided phases, that is Liquid in liquid and thus a dispersion or whether the polyurethane polymers are partially or entirely are dissolved in the aqueous medium and thus form a solution.

Polyurethane polymers are observed in water, in which the resulting product appears optically clear, which suggests a homogeneous solution. In this case it is assumed that the individual molecules the polyurethane polymers are not bonded to one another are. On the other hand, polyurethane polymers are also observed in water, in which the resulting product is cloudy, suggesting a dispersion. If so

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In the context of this application, the term "aqueous" ("waterborne") is used, this means that the new amine salts are present in an aqueous system and either a homogeneous solution, a dispersion or form a combination of the same.

It was'. ¹ found that, in order to obtain a satisfactory end product with good film-forming properties, branched reactants must also be used in the preparation of the aqueous polyurethanes in order to ensure the necessary crosslinking for obtaining a 3-dimensional polymeric structure on curing. Therefore, it should be noted that in the following description either the polyol, the polyfunctional amine, the prepoly animals, a portion thereof, or any combination thereof, has a reactive functionality greater than two.

The new polyurethane polymer amine sal comes in four basic Process steps produced. First will be a Polyol reacted with a polyisocyanate to form a prepolymer rrit to produce terminal NCO groups. That Prepol ^ mere is in the second step with a Oxime blocked. In the third process step this will be oxime-blocked, NCO-capped prepolymers with an or implemented several selected polyfunctional amines.

13ÖQ50 / Q478

The amine reaction product is then reacted with an acid. It has been found that in order to obtain a product with good properties, a reactant with a Functionality of more than 2 in the first and / or third procedural stage should be used. Accordingly is the functionality of the NCO prepolymer plus the functionality of the polyfunctional amine more a 1 s ν i e r.

It was also found that the reaction product of the polyfunctional amines with the oxime-blocked, NCO-capped Prepolymer tends to show an increase in viscosity over time to a complete one Gelation or solidification of the product takes place. Demented.

Speaking, it was surprisingly found that the gel time and the viscosity of the aqueous polyurethane polymer dispersion regulated and / or adjusted by the addition of a secondary amine to the reaction product can.

The isocyanate-masked ones which can be used in the process according to the invention Polyoxyalkylene polyols, prepolymers with terminal NCO groups or urethane prepolymers toluene diisocyanate, for example, by reacting polyoxyalkylene polyol with an excess of polyisocyanate manufactured. The polyol should have a molecular weight

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from about 200 to 200,000, and preferably from about 600 to 6,000. The hydroxyl functionality of the polyol and the corresponding isocyanate functionality after the reaction is 2 to 8. If the isocyanate functionality of the prepolymer is two, the functionality of the Amine used in the third process stage is larger than be two. If the isocyanate functionality of the Prepolymer is greater than two, functionality can of the amine in the third process stage down to to be two.

The preferred isocyanate-capped prepolymer or prepolymer with terminal NCO groups consists of a mixture of
(1) an isocyanate-capped, hydrophilic polyoxyethylene diol with an ethylene oxide content of at least 40 mol.%

(2) an isocyanate-capped polyol with a hydroxy functionality ranging from 3 to 8 prior to capping, with the isocyanate capped polyol in an amount from 2.9 to 50% by weight, based on the mixture of M)

and (2) is present.

The polyoxyethylene diol is the reaction product of alkylene oxides of which at least 40 mole percent is ethylene oxide with an initiator such as ethylene glycol, propylene

130050/047 «

glycol, tetramethylene glycol, hexamethylene glycol or Mixtures of the same. Preferably the molecular weight of the diol is from about 400 to 6,000.

Examples of suitable polyols (/ to be capped with polyisocyanates) include: (A) Essentially linear ³ olyols, which are obtained, for example, by reacting ethylene oxide with ethylene glycol as initiator. Mixing ethylene oxide with other alkylene oxides can also be used as long as the mol% proportion of ethylene oxide is at least 40 % . When the linear polyethers are mixtures of ethylene oxide with, for example, propylene oxide, the polymer can be either a random or a block copolymer. A second class of suitable polyols (B) includes, inter alia, those with a hydroxyl functionality of 3 or more. Such polyols are usually prepared by reacting alkylene oxides with a polyfunctional initiator such as trimethylolpropane, pentaerythritol, and the like. In the preparation of the polyols B, the alkylene oxide used can consist of ethylene oxide or mixtures of ethylene oxide with other alkylene oxides as described above. Further suitable polyols (C) are, for example, linearly branched polyfunctional polyols as indicated under A and B together with an initiator or a crosslinking agent. A specific example for (C) is

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a mixture of polyethylene glycol (molecular weight about 1,000) with trimethylol propane, trimethyl oil ethane or glycerin. This mixture can then be combined with an excess of polyisocyanate to form one according to the invention suitable prepolymers are implemented. Alternatively, the linear or branched polyols (for example Polyethylene glycol) are reacted separately with an excess of polyisocyanate. The initiator, for example Trimethylolpropane, can also be used separately with polyisocyanate implemented. Then the btiden masked substances combined to form the prepolymer will.

The polyoxyalkylene polyol is terminated or capped by reaction with a polyisocyanate. The reaction can be carried out in an inert, moisture-free atmosphere such as under nitrogen at atmospheric pressure and a temperature in the range from about 0 to 120 ^° C., depending on the temperature and intensity of the mixing, over a period of about 20 hours. This reaction can also be carried out under atmospheric conditions, provided that the product is not exposed to excessive moisture.

Capping of the polyoxyalkylene polyol can be accomplished using stoichiometric amounts of reactants.

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However, preference is given to using an excess of isocyanac, to ensure complete capping of the polyol. Accordingly, the molar ratio of isocyanate groups to hydroxyl groups is about 2 to 4 and preferably about 2 to 2.5.

To achieve maximum strength, solvent 1 resistance, Heat resistance and similar properties are the isocyanate-capped polyoxyalkylene polyol reaction products formulated in such a way that a cross-linked polymer network is obtained.

All ketoximes, such as acetone oxime, butanone oxime, Cyclohexanone oxime and the like are suitable. One takes suggest that oximes based on relatively volatile ketones are preferred. The most preferred Oxime is butanone oxime, also commonly called methyl ethyl ketoxime referred to as. Mixtures of oximes can also be used. The amount of oxime used can be about 0.7 to 1.2 equivalents, based on the isocyanate groups present. A preferred one Range is 1.05 to 1.15 equivalents.

To prepare the blocked prepolymers, the oxime and prepolymer are simply at temperatures of 50 to 70 ° C over a period of about 1/2 to 1 1/2

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Hours mixed. Solvent is generally not required, although materials such as butyl cellosolve acetate are required can be used. Other suitable solvents are those that neither with the oxime nor the urethane groups react. The molar NOH / NCO ratio should be based on the number of moles of reactive oxime and NCO groups about 0.7 to 1.2, and preferably about 1.05 to 1.15. In general, it is most effective Use sufficient oxime to completely remove the NCO groups to implement.

For the preparation of the blocked prepolymer, the oxime is selected so that a product is obtained which cures in a reasonable time and at a reasonable temperature. A variety of oximes and catalysts that can be used are in Petersen. Liebigs Ann. Chem., 562, p. 215 (1949); Wicks, Progress in Organic Coatings, 3_ (1975), pp. 73-99 and Hill et al, Journal of Paint Tech., 43 (1971), p. 55. Oximes with the above Entblockungstemperaturen are liquid substances at temperatures of about 80 ⁰ G and the condensation products with urethane prepolymers are miscible with water or can be dispersed by means of surfactants in water. In general, the oxides are aliphatic, cyclic, straight-chain or branched compounds having 2 to 8 and preferably 3 to 6 carbon atoms.

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The oxime-blocked, NCO-capped prepolymers are reacted with an amine capable of curing the polymer at a low temperature. Many of the suitable amines are well known and are referred to as polyfunctional amines. Specific Examples of suitable amines include ethylenediamine, 1,3-propanediamine, diethylenetriamine, triethylenetetramine, IminobispropyIamin, Tetraethylenpentarrin, MethyliminobispropyIamin, 2 (2-AminoethyIamin) -eihanol and the polyoxypropylene amines manufactured by Jefferson Chemical Company, Inc. and sold under the tradenames JEFFAMINE D-400, D-2000 and T-403. the Polyoxypropylene amines are aliphatic polyether (primary di- and trifunctional11e) amines derived from propylene oxide

15 adducts of diols and triplets.

As can be seen from the list of amines, some of these amines can be represented by the general formulas NH _? R'-NH_ and HO-R'-NH_ are shown, where R ¹ is a C -C_ group.

It has been found that polyfunctional amines with a Functionality of at least 2 primary amine end groups the preferred amines for achieving suitable curing of the subsequently produced polyurethane polymers are.

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Some of the suitable polyfunctional amines can by the formula

H ₀ N- (CH _0n -N) -C _n 2 η 2n. ζ η

in which ζ is an integer from 1 up to 4, η is an integer greater than 1 and R is hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms mean.

The polyoxypropyleneamines can be by the formula

15 NH ₂ CH (CH ₃ ) CH ₂ - [OCH ₂ CH

in which χ is greater than 2 and by the formula

^{20 ru ru} , —C-CHp-

CH ₂ OCH ₂ -CH- (CH ₃ ) -

in which χ + y + ζ is about 5.3. The molecular weights of these polyoxypropyleneamines are about 200 to 2,000 or more, preferred polyoxy-

130050 / OA78

propylenamine molecular weights from about 400 to 2,000 own.

The amount of polyfunctional amine that the oxime-blocked, NCO-capped prepolymers are added, should be in the range of 0.6 to 1.5 equivalents and preferably 0, P to 1.1 equivalents based on the stringed equivalents te of all actual cyanate groups present in the NCO-capped prepolymer.

Who η the isocyanate functionality of the NCO-Verkar. pten Prepolymer is two is a polyfunctional one Amine with a functionality of more than two is required to obtain satisfactorily crosslinked products.

When the isocyanate functionality of the NCO capped Prepolymer is more than two, the functionality the polyfunctional amine has such a small value like own two. It follows from this that the functionality of NCO-capped prepolymer in the reactive system and amine or polyoxypropylene amines is greater than four in total.

The reaction between the oxime blocked prepolymer and the polyfunctional amine is regulated by Adding an acid or a mixture of acid and water before completing the reaction. Failure

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regulating the reaction between amine and oxime blocked Timing prepolymer can result in an amine reaction product that is too viscous. Accordingly, appropriate amounts of blocked prepolymer and polyfunctional amine are added to a reaction vessel and under controlled heating and control Stirring conditions implemented. The course of the reaction can be determined by observing the increase in viscosity. With the use of suitable devices, the reaction can be carried out more quickly at elevated temperatures. The reaction times can be, for example, at about 95.degree about 3 minutes, at 80 ° C about 4 minutes and so on. Preferred reaction times are between about 1/2 to Hour at temperatures between about 40 and 60 C. To reduce the pH to about 5 or less, will sufficient acid or water-acid mixture in the amine reaction product stirred in.

The cationically stabilized aqueous polyurethane polymers.will prepared by the amine reaction product in the presence of sufficient amounts of acid for adjustment a pH of about 5 or less is dispersed in water. In the preparation of the aqueous polymers can add a concentrated acid solution directly to the amine reaction product are given and mixed with this, followed by dilution with water

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he follows. This is the preferred practice. It is however, it is also possible to add the acid to the water first and then to disperse the amine reaction product. Other additives such as surfactants, UV absorbers, stabilizers, ators, Pigments, etc. can be added to the aqueous polyurethane polymers if necessary.

It has been found that settling problems arise and / or parts of the amine reaction product are formed a crust react with the water if the pH value is not regulated in the wide range given above will. In this regard, it has been found that about 1 to 10 parts or more of acid per 100 parts of amine reaction product can be used. The use of 4 to 8 parts of acid per 100 parts is preferred Amine reaction product. These aqueous polymers have proved to be stable for several months at room temperature (e.g. 20 ° C) and show excellent Resistance to freeze-thaw cycles.

Although every organic or inorganic acid leads to the formation of the amine salt and to the regulation of the ■ Suitable pH values were, in particular, glacial acetic acid, acrylic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), formic acid, glycine (aminoacetic acid), hydrochloric acid, Lactic acid (Q ^ -hydroxypropionic acid), orthophosphoric acid

130050/04 ^ 8

(H ₀ PO.), Phosphorous acid (H ₀ PO ₀ ), amidosulfuric acid, sulfuric acid, tartaric acid (dihydroxysuccinic acid), p-toluenesulfonic acid and mixtures thereof are used.

Some of these acids, for example sulfuric acid, hydrochloric acid and acetic acid are prone to discoloration. But when further additives such as pigments and UV absorbers can be added to the aqueous polyurethanes These acids tend to discolour Additives are masked. It has been found that a mixture of acetic acid and phosphoric acid increases too results in less discoloration than other acids or combinations of other acids. Phosphoric acid alone provides good color stability.

It has been found that amounts as low as 0.1% by weight, based on the weight of the fibers, of the polyurethane prepolymer amine salt improve the physical properties of the paper product. The preferred one The range is based on the fiber content of the paper at about 0.1 to 2% by weight of amine salt, but it can also as much as 10% can be used. In other words, the amount of the polyurethane prepolymer amine salt is about 0.02 to 0.2% by weight, based on the amount of water in the aqueous to be used in papermaking Slurry.

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Although all known papermaking materials are within the scope of the invention Preferred papermaking fibers include fabric used newsprint, corrugated cardboard material (corrugated carton slock), bleached and unbleached pulps such as Southern Western Kraft, High Alpha Southern Sulphite, and Hardwood Kraft. Fs can also be beneficial to the paper approach Add glass fibers to give the finished product the desired properties / u.

In the following, the invention is to be explained in more detail by means of examples, it being pointed out that that correspondingly improved results also with other combinations of different compositions, as above

15 specified, are available.

Herste Settin g of Polyurethanprepolymeraminsalzes

A preferred isocyanate-terminated polyol prepolymer is produced by a hydrophilic polyoxyethylene diol with an ethylene oxide content of at least 40 mole percent with a polyol with a hydroxyl functionality in the range of 3 to 8, with the polyol in the mixture in an amount in the range from 1.0 to 20 weight percent is present. The mixture becomes sufficient at a temperature in the range of 0 to 120 ° C long with an amount of diisocyanate accordingly

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1.8 to 1.9 NCO to OH equivalents] ducks reacted, to cap substantially all of the hydroxyl groups in the mixture. Additional diisocyanate is added, by 0.1 to 0.3 equivalents of NCO per initial Equivalent OH in excess to that for the reaction with the hydroxyl groups theoretically required amount to deliver.

To 100 g of the NCO-capped Polyolprepolymers 22 g of butanone oxime was added at 24 ⁰ C in a stainless steel vessel with stirring. The reaction of the oxime with the isocyanate is exothermic and the temperature rises to 60 ^° C. A hot water bath is used to regulate the temperature between 80 and 90 ° C. for 20 minutes.

After 20 minutes and at a temperature of 90 ° C., 12 g of diethylenetriamine are added with stirring. The reaction with the amine is also exothermic, which is the chain lengthening accelerated.

The viscosity continues to increase and after 10 minutes it increases At 90 to 95 C, 7.1 g of glacial acetic acid and 7.1 g of orthophosphoric acid are slowly dissolved in to regulate the viscosity 100 g deionized water added. After complete Adding all of the acid / water mixture will

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rial chilled and packaged. To achieve the desired Percentage of non-hazardous components'% N.V) and water can be added to the desired viscosity.

Typical physical properties of the manufactured Emulsifiers are:

% N.V. 10 pH viscosity (Brookfield LVF) Appearance

52.0

4.5-6.9 600-1000 cps clear, straw-colored solution

15 Example 1

A mixture of newsprint and corrugated cardboard (corrugated carton stock) was in a Waring mixer Slurried to a grind of 550 Canadian Standard. The polyurethane prepolymer amine salt became the Pulp was added and the slurry became 5 minutes stirred, [in a 30.5 30.5 cm Williams arch former Sheets (25 g, dry) were made, one minute

pressed at a pressure of 106 kg / cm and in one

Wi] liam sheet dryer dried at 93.3 ° C. After one hour of curing at 101.6 C and 16 hours of conditioning at 22.8 ⁰ C and 50% relative humidity, were the

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Arches tested. To determine the wet tensile strength or The samples became tear-resistant for 6 hours in one Soaked 1% solution of AEROSOL OT wetting agent. The test results are in the table below for a series of sheets, the amounts of polyurethane prepolymer amine salt added to the pulp increase.

sample

T r ο c k e η -

% Polyurethane tensile- wet tensile- Gurley prepolymer- strength- strength- Elmen- stiff igamine salt in ability village ability of pulp # / 2.54cm # / 2.54cm g mg

NH473-1 / 2 0 15.7 0.6 140 3800 3/4 0.1 19.1 4.3 173 3850 5/6 0.2 21, 9 5.9 192 4100 7/8 0.5 22.1 5.9 203 4450 9/10 1.0 33, b 10.9 233 4700 11/12 2.0 27.9 10.2 228 5950 13/14 5.0 33.7 14.4 221 5550

20 Example 2

Sheets were made as in Example 1 with the difference that 50 g sheets were made and different ones Pulps were used. The results are given in the table below.

0050/0478

% Poly dry

urethane train wet train Gurley

prepolymer- firm- firm- stiff-

Bcgen used amine salt in the ability

No. _ ^Pul P? ___ I * er_Pu lpe_ | / 2 _, _ 54 £ m # _ / _ 2 ^ b4c_m _ mg

NH432-1 unbleached O

-2 Western Force 2.0 5

-7 bleached O

-8 Western Force 2.0

-10 High Alpha 0 -11 Southern

Sulfites 2.0

-13 Bleached Southern 0 -14 Hardwood Kraft 2.0

BeJ sp Λ e .1 3

50 g sheets were used as in Example 1 a mixture of newsprint and corrugated cardboard

15 produced with the difference that after the addition of the polyurethane prepolymer amine salt and before the molding of the bow in the Williams bow shape a 90/10 styrene / butadiene 1.alex was added to the slurry. The added ones Amounts of polyurethane prepolytneraminsal ζ and

Latex were varied.

38.5 1.5 29,400 93.9 30.4 42,800 40.2 2.4 19,800 60.3 24.6 25,000 19.8 1.0 17,200 25.2 10.4 21,200 38.3 1.1 26,700 41, 9 13.2 27,600

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- 38 -

% Poly dry

urethane train wet train Gurley

prepolymer-% latex solid- solid- stiff-

arc
No. arnine salt in
the pulp 1 4 0 in the
Pulp speed
# / ?, 54cm speed
# / 2.54cm speed
mg NH417-1 0.4 0 36.8 1.2 21 NH415-1 1.0 0.8 51.2 6.5 27 -2 1.5 >, 6 43.4 11.9 29 -3 4.0 5.0 58.0 16.3 35, ~ 6 6.0 18.0 65.3 30.7 52. -7 0.0 31, 0 90.3 37.8 56. -8th 1 60.0 199.3 82.0 82. Example .500 .300 .200 .200 .200 .900 .900

50 g sheets as in Example 3 were used made of unbleached Western Kraft pulp and with the addition of polyvinyl acetate latices.

% Poly dry

urethane-wet / ug-

prepolymer-% latex solid- solid-

Arc amine salt in the PVActivity No. of pulp pulp latex # / 2.54cm

NH432-1 0 0 - 38.5 1.5 NH439-1 0.5 5.0 B. 67.6 21.1 -6 2.0 15.0 B. 82.2 35.5 -2 0.5 5.0 61 67.7 20.7 -7 2.0 15.0 61 156.5 56.0

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B = DARATAK B, a polyvinyl acetate copolymer emulsion

61 = DARATAK 61L, a high molecular weight polyvinyl acetate homopolymer i on

DARATAK is a registered trademark of W. R. Grace & Co.

Be j played 1 5

50 g sheets were produced as in Example 3 using pure bleached Kraft pulp and acrylic polymer (see p.
10

% Poly dry

urethane pull

prepolymer- % latex solid- solid-

arc
No. amine salt in
the pulp in the
Pulp acrylic
latex speed
# / 2.54cm I-eit
# / 2.54cm NH432-1 0 0 - 38.5 1.5 NH440-1
-4 0.5
2.0 5.0
15.0 410
410 36.9
64.0 15.5
28.1 NH440-2
-5 0.5
2.0 5.0
15.0 400
400 52.8
99.7 18.9
53.8 NH440-3
-6 0.5
2.0 5.0
15.0 442
442 48.3
114.7 16.7
54.5

410 = DAREX X410, a vinyl modified acrylic polymer latex 400 = DAREX X400, a self-curing polyacrylic latex 442 = DAREX X442, a styrene / acrylate copolymer latex

DAREX is a registered trademark of the company W. R. Grace & Co.

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Example 6

50 g sheets were prepared as a mixture of newsprint and corrugated board material, the glass fibers were added manufactured in Beispi ^o 1 3 using. Alternating amounts of polyurethane prepolymer amine and a 90/10 SBR latex were added.

3005 Sheet no. % Glass
fibers
in the
Pulp Glass
fiber type Ό polyurethane
prepolymer
aminsaiz in
the pulp % Latex
in the
Pulp Latex- Dry train
solid
speed
M / 2.54cm Wet draft
consolidate
speed
# / 2.54cm Gur j.ey
Stiff
speed
mg I. CO 0/0 ΝΗ476-12 0 - O 0 - 48.9 1.3 29,700 O
I. I02038 .ρ »
-J;
α> - 2
- 1 15th
15th DE636-1 / 4
It O
4th O
O 21.0
38.7 0.5
16.0 34,100
41,400 - 4th ■ * ZZ
ι D ti 1 10 SBR 35.2 5.9 46,400 -11 15th M670-1 / 2 4th 4th SBR 75.5 20.0 54,300 - 7th 15th DE610-1 / 2 4th 4th SBR 44.3 13.4 48,800

Claims (34)

UEXKULL A STOLBERG PATE NTANWA UTE Rl Sf I EHSTRASSE 4 D 3ΟΟΟ hamburo oa AVIORNEYS DR J O PRHB by UEXKULL DR ULRICH GRAF STOLBERG DIPL ING JÜRGEN SUCHANTKE DIPL ING ARNULF HL) BER DR ALLARD by KAMEKE OR KARLHEINZ SCHULMEYER W. R. Grace & Co. 6; Whittemore Avenue
Cambridge, Mass./V.St.A. (Prio: Jan. 28, 1980 US 116 287 - 17352) January 1981 Polyurethane polymer amine salt as a paper additive Claims 1 / Process for improving physical properties of paper products, characterized in that A. a paper stock system is presented, B. e: n polyurethane polymer amine salt is produced, by doing (1) made an isocyanate-capped prepolymer is, the isocyanate-capped prepolymer from a mixture of (a) about 2.9 to 50% by weight, based on the mixture, an isocyanate-capped polyol with a hydroxyl functionality in the range of 3 to 8 before capping and 1300 5 0 / OA 1 9 (b) about 97.1 to 50% by weight, based on the mixture, of an isocyanate-capped hydrophilic polyoxyethylene diol with an ethylene oxide content of consists of at least 40 mol%, (2) the prepolymer to form an oxime-blocked Prepolymers with about 0.8 to 1.2 equivalents of a ketoxime selected from the group consisting of from acetone oxime, butanone oxime, cyclohexanone oxime and mixtures thereof for blocking the NCO groups of the prepolymer is implemented, (3) forming the oxime blocked prepolymer an amine reaction product is reacted with a polyfunctional amine which has at least two contains functional groups and is capable of curing polyurethane polymers at low To effect temperatures and (4) the amine product with an organic or inorganic one Acid forming an infinitely dilutable with water at low temperature curable polyurethane polymer amine salt is reacted, C. Formed a paper web from the paper stock system will and D. the salt either before or after the formation of the paper web but before the passage of the paper web through the drying stages of the papermaking 130050/0478 Process is intimately dispersed in the paper stock in a sufficient amount so that the salt is present in a concentration of about 0.1 to 10 % based on the dry fiber weight.
5 2. The method according to claim 1, characterized in that the salt in the distribution in the paper stock in
Is in the form of an aqueous system. 3. The method according to claim 1, characterized in that that the salt is in the form of an aqueous system and is sprayed onto the paper web prior to the drying step will . 4. The method according to claim 1, characterized in that that the paper stock system selected a paper additive from the group consisting of styrene / butadiene latices, Polyvinyl acetate latices, acrylic polymer latices and mixtures thereof. 5. The method according to claim 4, characterized in that the paper stock system contains glass fibers. 6. The method according to claim 1, characterized in that that the paper stock system is a mixture of newsprint and corrugated cardboard stock. 130050/0479 7. Paper stock, characterized in that it is treated according to the method according to claim 1. 8. Aqueous additive composition for use in papermaking, characterized in that it contains aqueous polyurethane polymers, which are prepared by adding a first component, which is a contains isocyanate-capped hydrophilic polyol with a reaction functionality of 2 or more, with a second component that contains a ketoxime, to form an oxime-blocked prepolymer is implemented, the oxime-blocked prepolymer under Formation of an amine reaction product with a third Component is implemented, which is a polyfunctional Contains amine with a functionality of 2 or more, the amine reaction product is reacted with a fourth, an acid-containing component, wherein a polyurethane polymer amine salt which can be diluted with water indefinitely is formed, and that polyurethane polymer amine 20 salt is diluted with water. 9. Composition according to claim 8, characterized in that it is an additional additive selected from the group consisting of styrene / butadiene latexes, polyvinyl acetate latexes, acrylic polymer latexes and mixtures the same contains. 130Ö50 / OA7Ö 10. A process for the manufacture of paper products, characterized in that
A. / υ of a paper pulp about 0.1 to 10% by weight, based on the weight of oven-dried pulp fibers, of a polyurethane polymer amine salt, which is an aqueous composition consisting essentially of the successively obtained reaction products of the following reactions, wherein (a) a first component, the isocyanate-capped, hydrophilic polyether polyol prepolymer having a reactive functionality of at least two contains, with (b) a second component containing a ketoxime is reacted to form an oxime-blocked prepolymer, the oxime-blocked prepolymer with (c) a third containing a polyfunctional amine Component is reacted to form an amine reaction product, and the amine reaction product with (d) a fourth, an aqueous acid-containing component to form a thermosetting, aqueous polyurethane polymer composition 25 is set, and B. from the pulp resulting from stage A paper will be produced. 130050/0478 11. The method according to claim 10, characterized in that that the paper pulp is a paper additive selected from the group consisting of styrene / butadiene latices, Polyvinyl acetate latices, acrylic polymer latices, and Contains mixtures thereof. 12. The method according to claim 11, characterized in that the paper pulp contains glass fibers. 13. The method according to claim 10, characterized in that that the paper pulp is a mixture of newsprint and corrugated cardboard material. 14. A process for the production of paper products from cellulose fibers suitable for paper production, characterized in that about 0.1 to 10% by weight, based on the weight of the fibers, of a composition which consists essentially of an aqueous polyurethane polymer are added to the fibers wherein the polymer is formed by reacting about 0.7 to 1.2 equivalents, based on the NCO groups of the prepolymer, of a ketoxime with a polyurethane prepolymer having free NCO groups to form an oxime-blocked prepolymer which blocked Prepolymer with about 0.6 to 1, b equivalents, based on the NCO groups of the prepolymer, 130050/0478 a polyfunctional amine to form a Amine reaction product is reacted, the amine reaction product with about 1 to 10 parts of an acid per 100 parts of the amine reaction product to form an amine salt is implemented and the amine salt is diluted with water to a total non-volatile content of less than 60 % , and then the composition thus obtained is cured into a water-insoluble form. 10 15. The method according to claim 14, characterized in that the composition is cured ^{by heating to a temperature between about 104 and 149 ° C.} 16. The method according to claim 15, characterized in that that the fibers also have a paper additive selected from the group consisting of styrene / butadiene latices, Polyvinyl acetate latices, acrylic polymer latices, and 20 mixtures thereof is added. 17. The method according to claim 15, characterized in that that glass fibers are also added to the fibers. 18. The method according to claim 15, characterized in that the fibers consist essentially of a mixture consist of newsprint and corrugated cardboard. 130050 / 047Ö 19. Containing paper product having improved wet strength Cellulosic paper fibers which, based on the weight of the fibers, comprise about 0.1 to 10% by weight of a composition included that is obtained by (1) a hydrophilic polyoxyethylene diol having an ethylene oxide content of at least 40 mol.% a polyol with a hydroxyl functionality in the range of 3 to 8 is mixed, the polyol in the mixture in an amount im Range from 1.0 to 20 wt.% Is present, the mixture at a temperature in the range from 0 to 120 ° C long enough with an amount of diisocyanate corresponding to 1.8 to 1.9 NCO equivalents is reacted to cap substantially all of the hydroxyl groups in the mixture, and then additional diisocyanate added to form a prepolymer with terminal NCO groups is compared to the amount theoretically required for the implementation of the hydroxyl groups to provide an excess of 0.1 to 0.3 equivalents of NCO per initial equivalent of OH, (2) the prepolymer with terminal NCO groups to form a butanone-oxime-blocked one Prepolymers is reacted with about 1.05 to 1.15 equivalents of butanone oxime, (3) the butanone oxime blocked prepolymer below 130050 / OA7Ö Formation of an amine reaction product with about 0.9 to 1.1 equivalents of diethylenetriamine implemented will and (4) the amine reaction product reacted with water is, the per 100 parts of amine reaction product about 4 to 8 parts of a mixture of vinegar and Contains phosphoric acid, so that the resulting film-forming aqueous composition about 20 to Contains 50% by weight of non-volatile components, and "then the composition thus obtained is cured into a water-insoluble form. 20. Paper product according to claim 19, characterized in that it is a paper additive selected from Group consisting of styrene / butadiene latices, polyvinyl acetate latices, Acrylic polymer latices and mixtures of the syllables. 21. Paper product according to claim 19, characterized in that it contains glass fibers. 22. Paper product according to claim 19, characterized in that the cellulose paper fibers are a mixture made of newsprint and corrugated cardboard. 25th 23. Paper that is impregnated with a polyurethane polymer amine salt in such amounts that the impregnated 130Ό50 / 0Λ70 Nated paper, based on 100 parts by weight of the paper, consists essentially of about 0.1 to 10 parts of a polyurethane polymer amine salt prepared by
(1) made an isocyanate-capped prepolymer is, the isocyanate-capped prepolymer from a mixture of (a) about 2.9 to 50% by weight, based on the mixture, an isocyanate-capped polyol with '^ a hydroxyl functionality in the range of 3 to 8 before capping and (b) about 97.1 to 50% by weight, based on the mixture, of an isocyanate-capped hydrophilic Polyoxyethylene diols with an ethylene oxide content ¹⁵ consists of at least 40 mol%, (2) the prepolymer to form an oxime-block i prepolymer with about 0.7 to 1.2 equivalents of a ketoxime selected from the group consisting of acetone oxime, butanone oxime, cyclohexanone oxime and mixtures thereof are reacted to block the isocyanate groups of the prepolymer, (3) forming the oxime blocked prepolymer an amine reaction product is reacted with a polyfunctional amine which is at least Contains two functional groups and is capable of curing polyurethane polymers 130050/0478 at low temperatures, and (4) the amine reaction product with an organic or inorganic acid with formation of an infinitely dilutable with water, at lower Temperature curable polyurethane polymer amine salt is implemented. 24. Paper according to claim 23, characterized in that it is a paper additive selected from the group consisting of styrene / butadiene latices, polyvinyl acetate latices, Acrylic polymer latices and mixtures thereof contains. 25. Paper according to claim 24, characterized in that it contains glass fibers. 26. Paper according to claim 23, characterized in that that it is made from a pulp consisting essentially of a mixture of newsprint and Corrugated cardboard material. 27. Process for increasing the wet strength of paper, characterized in that (1) Paper pulp with a wet strength enhancer Amount of an aqueous solution or suspension a crosslinkable polyurethane polymer amine salt product, the crosslinkable $ 130050/047 Polyurethane polymer amine salt product essentially from the successive reaction products ■ the following reactions exist, where (A) a first component, which is an isocyanate capped hydrophilic polyether polyol prepolymer with a reactive functionality ve η at least contains two, with (b) a second component containing a ketoxime to form an oxime-blocked one Prepolymers is implemented, the oxime-blocked Prepolymer with (c) a third, a polyfunctional amine contained component is converted to form an amine reaction product and the amine reaction 15 tion product with (d) a fourth, an aqueous acid-containing component to form a thermosetting, aqueous polyurethane polymer amine salt product is implemented, (2) from that with the polyurethane polymer amine salt product mixed pulp is formed into paper; and (3) the paper is dried at an elevated temperature the cross-linking of the polyurethane polymeramine salt product is effected. 25th 28. The method according to claim 27, characterized in, that in step (1) a paper additive is selected from 130050/0478 the group consisting of styrene / butadiene latices, polyvinyl acetate latices, acrylic polymer latices and mixtures thereof is mixed with the paper pulp.
5 29. The method according to claim 27, characterized in that the paper pulp is mixed with glass fibers. 30. The method according to claim 27, characterized in that the paper pulp consists essentially of newsprint and corrugated cardboard material. 31. Paper having a wet strength increasing amount a crosslinked polyurethane polymer amine salt product, the latter substantially prior to crosslinking from an aqueous polyurethane polymer amine salt product which is formed by about 0.7 to 1.2 equivalents, based on the NCO groups of the prepolymer, a ketoxime with a polyurethane prepolymer are reacted with free NCO groups to form an oxime-blocked prepolymer, the blocked prepolymer with about 0.6 to 1.5 equivalents, based on the NCO groups of the prepolymer, a polyfunctional amine is reacted to form an amine reaction product, the amine reaction product with about 1 to 10 parts of an acid 130050 / CH78 per 100 parts of amine reaction product reacted to form an amine salt and the amine salt is diluted with water to a total content of non-volatile components of less than 60 % . . 32. Paper according to claim 31, characterized in that it selected a papermaking additive from the group consisting of styrene / butadiene latices, Polyvinyl acetate latices, acrylic polymer latices, and Contains mixtures thereof. 33. Paper according to claim 31, characterized in that that it contains glass fibers. 34. Paper according to claim 32, characterized in that that the paper is made from a mixture of newsprint and corrugated cardboard fabric is made. 130050/047 «