US2694633A - Affixing organic and inorganic additaments to cellulosic materials - Google Patents

Description

United States Patent AFFIXWG ORGANIC AND INORGANIC ADDITA- MENTS T0 CELLULOSIC MATERIALS" Application February 23, 1950, Serial No. 145,923

Claims. (Cl. 92-21) No Drawing.

The present invention relates to the affixing of organic and inorganic additaments to fibrous organic and'inorganic materials, such asindividual fibers, filaments and aggregations of such filaments as felts and woven fabrics, both nitrogenous and non-nitrogenous, such as wool, hair, leather, cellulose and cellulose derivatives,etc.

The art of afiixing additaments to fibrous materials is well established, being exemplified by the dyeing of cellulosic filaments and fibers, textiles and the like; by the sizing of paper, both while the fiberszconstituting the paper are in liquid suspension or bythe impregnation of webs of paper; and by the deposition of various materials either upon suspended cellulosic fibers, upon filaments made thereof, or upon the webs and fabrics made therefrom.

A quite common form of affixing additaments to such fibers is by conjoint deposition from suspensions in a liquid, or by impregnation of webs and fabrics by solutions or suspensions of the added substances. However, when such substances are merely in the form of dispersions or solutions it has been the practice to soak or saturate webs of the materials with such solutions, which invariably required the elimination of the solvent employed, or involved the employment of molten materials.

In the art of sizing suspended paper fibers, such as is practiced in the making of paper and molded pulp articles, various substances have been added in the hope that they would attach themselves to the suspended fibers in adequate quantities; but in most cases the amount that could thus ,be added was quite small. Many attempts to efiect the addition of larger amounts, say up to or exceeding 100% by weight on the basis of the cellulose or other fibrous material, have been made, out have been unsuccessful.

It is therefore one of the primary objects of the present invention to provide methods for the affixing of additaments'to fibrous materials under conditions such that extremely large :amounts of the added substances can become firmly and substantially irremovably attachedand secured to the fibrous material.

A further object of the present invention is to condition fibrous material so that they will very strongly attract to themselves additaments comprising an extremely varied group of materials, which includes both organic as well as inorganic substances, such as sizing materials, waterproofing materials, fireproofing materials, coloring matter, dyes, pigments and fillers, plasticizers, toxics, and substances which are capable of altering the properties of the material to which they have become afiixed.

Still a further object of the present invention is to condition the additaments so that they will form cationically active emulsions or suspensions of a nature enabling the water-insoluble material contained in the emulsions or suspensions to attach itself to fibrous materials with great tenacity.

Another object is to treat the material with cationically active surface-active, water-insoluble but waterrdispersible substances having at least one hydrophobic group so that when subsequently a cationically active emulsion or dispersion of the additament is allowed to act upon the so treated material, the additament is firmly and substantially irremovably affixed thereto.

The term additament will be used in the present specification and claims as the broad and proper generic term for any substance that may, by the processes of the present invention, become affixed to the treated fibrous ice material, and the term includes such diverse materials asinorganic pigments, fillers and weighting materials, as well as organic resins, elastomers, polymers, plastics, etc. Among the materials which can be atfixed to the fibrous material by the processes and means of the present invention are the following:

(1) Loading and filling materials, e. g. diatomaceous earths, pigments, etc.;

E2) Coloring materials, e. g. pigment-colors and dyestu s;

(3) Sizing materials, e. g. glues, resins, gums, starches, casein and other proteinaceous substances;

(4) Plasticizing materials, 6. g. oils, waxes, plasticizers, etc.;

(5) Varnish materials, such as phenolic resin varnishes, alkyd resins, polyvinyl ester polymerization products, a great diversity of synthetic resins, elastomers such as natural or synthetic rubbers, and similar substances; cellulose esters and ethers, etc.;

(6) Unusual materials of high technical utility, e. g. chlorinated paraffins; chlorinated elastomers; anti-toxic, anti-fungus materials, preservatives, toxic substances and the like, even including subdivided metals.

It will be understood from a study of the more detailed description to follow, that there is substantially no limitation to the type of substances which may be combined with treated materials, provided that such substances be water-insoluble and capable of being formulated into a cationically reactive dispersion or emulsion, the particles whereof carry a high cationic i. e. an electro-positive charge. The amount of such addition is governed by the characteristics of the material and by the degree of the cationic reactivity of the dispersion or emulsion, and the addition is substantially quantitative, there almost always being no uncombinedor unretained material, provided the process is carried out within the teachings of the present invention.

By reason of the importance of the present contribution, particularly to the cellulosic material-fabricating arts, it will necessarily have to be exemplified by a large number of diverse examples, so that the true generic nature of the invention will be properly evaluated, and the generic claims hereunto appended be supportedby sufficient data to warrant them.

Although the present process was initially developed for use in the paper and paperboard industry, where the cellulosic fibers are carried in aqueous dispersions until the paper or paperboard is formed into a web on the conventional equipment used for such production, extended studies have established the fact that the present process is likewise equally adaptable to pulp-molding processes and to the treatment of textile threads,

yarns, and felted or woven fabrics, treatment of inorganic.

fibers, leather materials, woolen threads, yarns, and fabrics, etc.

While most of the examples hereinafter to be recited deal with the art of papermaking or the production of paperboard, insulation board, etc., it must be understood at the very outset that the invention is not to be limited thereby.

The present invention therefore primarily relates to the making of webs or forms of cellulosic fibers, notably paper, paperboard, and similar paper products by the usual paper-making procedures, as typified by the conventional single and multi-vat cylinder machines, Yankee, Harper, Fourdrinier, and wet machines; and fiber-molded forms as made in conventional pulp or fiber-molding devices.

One of the most useful applications of the present invention is to combine quantitatively with cellulosic fibers in aqueous suspension, and prior to their formation into cellulosic webs or forms, any type of water-insoluble material that is adaptable to formulation into a cationically reactive dispersion or emulsion, the water-insoluble particles of which are electro-positively reactive.

The fundamental basis of the present invention involves the pre-treatment or conditioning of the fibrous material with a water-insoluble but water-dispersible, highly polar, cationically active surface-active agent containing at least one hydrophobic group. This is carried out by means of either aqueous dispersions of such clays,

materials, or by the treatment of the fibrous material while in aqueous suspension with a dispersion or solution of the conditioning agent (as it will hereinafter be termed for sake of conciseness of expression), such solution or dispersion preferably being in an organic solvent that may or may not be miscible with water. It appears that, by reason of the polar nature of these conditioning materials, a sufficient amount of the conditioning material, even when contained in the dissolved state in an organic non-water-miscible solvent, will pass into the aqueous phase so as to enable it to act upon or to react with the fibrous materials, so as to place them into the proper condition for the subsequent treatment by means of which the desired additament is affixed thereto.

The affixation of the additament is brought about by mixing an aqueous suspension of, for example, a cellulosic material with an emulsion or suspension of the additament, which latter is contained as the disperse phase in a dispersion of a long-chain amide-amine salt, such as will hereinafter be more specifically enumerated. When suspended in a dispersion of such a salt, which itself is insoluble in water, the particles of the dispersion, irrespective of the nature of the dispersed material, will have a positive electrical charge, which ordinarily is expressed herein by stating that the emulsion or dispersion is cationically active or cationically reactive.

Broadly speaking, the determination of the amounts of the conditioning material required, and of the amounts of the additaments which may be afiixed to the fibrous material, may be readily ascertained by analytical methods involving electrometric titrations of, first, the suspended fibrous material with the conditioning agent, and then the electrometric titration of a fixed amount of a suspension of the conditioned material with an emulsion or suspension of the additament of known concentration. The amount of reagents then used in the practical application of the present invention may then readily be calculated.

Thus, for example, a given weight of cellulosic material, the exact bone-dry weight of which is known, may be suspended in a known amount of water, whereafter the suspension thus obtained is titrated with a volumetric suspension of the conditioning agent, that is to say, with a solution or suspension of the conditioning agent having a definitely known concentration. The changes in the hydrogen-ion concentration of the suspension is monitored by means of the usual glass electrode of a sensitive potentiometer assembly, so that the optimum amounts of addition of the conditioning agent may be ascertained. In the same way, the thus treated suspension is then further titrated with the suspension or emulsion of the additament.

The conditioning materials or agents can be rather broadly designated as being water-insoluble cationically active surface-active substances, which contain at least one hydrophobic group but which have some degree of dispersibility in water. They must, moreover, also be polar to a considerable degree, and generally speaking, the greater the polarity, the better is the conditioning effect. Conditioning agents which contain a heterocyclic group containing nitrogen, which group is directly connected with a hydrophobic group, have been found to be particularly effective. Another group of effective conditioning agents includes substances in which the hydrophobic group is joined to the cationic group through an intermediate linkage, e. g. an amide linkage, an ester linkage, an ether or related linkage, a sulfide or sulfone linkage, or an imino linkage. Surface-active phosphorus compounds have also been found to be highly useful. Another group contains basic nitrogen joined directly to the hydrophobic group, i. e. amines which are dispersible in, but not really soluble in water. Nitriles, dinitriles, dialkylcyanamides may also be used as conditioning agents. Examples of each of these generic groups will be given.

One example of a highly operable cationically reactive surface-active agent employed in the first or conditioning step of the present process, comprises a cationically reactive material resulting from the reaction products formed by the addition of water-soluble amines or readily water-dispersible amines, preferably lower aliphatic amines, to the oxidation products formed by the liquid phase oxidation of normally liquid fractions of petroleum, e. g., 3640 Baum fuel oils, or 45 distillate, or steam distillates of these oxidation products, said oxidation products or steam distillates therefrom being rich in aliphatic carboxylic acids containing from 10 to 16 carbon atoms (the average being 12 carbon atoms) per aliphatic chain. U. S. Patents Nos. 2,330,524 and 2,330,525 are illustrative of operable methods of producing such amineacid reaction products. These compounds may be considered as being substituted amides having the general formula in which R is an aliphatic group having from about 8 to about 20 carbon atoms, and R is an alkyl group having from about 4 to 10 carbon atoms. The products are substantially insoluble, non-ionizable, and non-dissociable in water but may be used in the form of disper- SlOIlS.

Such materials of which there are presently five types available, are known commercially as Alex L-IZOS-X'," .gsltlax 1561, Alox 1560, Alox 1650, and Alox 1 The electrometric titration of cellulosic fibers in aqueous suspension with the cationically reactive surfaceactive agents, gives typical titration curves, as will be further explained. A change in hydrogen-ion concentration is characteristic, and succeeding added increments of such materials will lead to a condition until a point is reached at which no further reaction is apparently effected.

A typical electrometric titration data table is shown below. The electrometric titration data is one of the criteria of the operability of the cationically reactive surface-active agent selected for use.

The cellulose fiber used in this particular evaluation was a fully bleached kraft pulp, the pulp freeness factor thereof being about 600 Canadian standard. The particular cationically reactive surface-active agent used, on an as is" basis was Alox L-1205-X' (a product of the reaction of an amine with a monobasic acid as hereinbefore stated). The fiber suspension was an exact 1% on the bone-dry basis, the suspension weight being an exact 1,000 grams.

TABLE I H value of Visual condition of Co. as is basis cationically reacp tive surface-active agent; added gi gg ggififi gggg gf (Alox bum-X) addition sion 7.30 clear. 7. 20 Do. 6. 60 Do. 6. 50 D0. 6. 40 Do. 6.30 Do. 6. 20 Do. 6.15 Do. 1.60 6.05 Do. 1.80 6. 00 D0. 2.00 5. oily rings form. 2.20 5. 90 oily rings. 2.40 5. 90 Do. 2.60 5. 90 oily surface. 2.80. 5. 90 black oily surface. 3.00. 5. 90 D0. 3.20. 5. 90 Do. 3.40 5. 90 Do. 3.60 5. 90 Do. 3.80 5. 90 Do. 4.00 5. 90 D0. 5.90 Do. 5.90 Do. 5. 90 Do. 5. 90 D0. 5. 90 Do.

The end point of reactivity was sharp (at about pH 6.0), not only as indicated by the pH value, but by visual observation of the liquid phase condition as well. It thus appears that a definite amount of the conditioning agent is fixed or adsorbed by the cellulosic fibers in this particular case.

Another example of an operable cationally reactive surface-active agent which may be employed in the first or conditioning step of the process is an alkyl amine salt of an alkyl amide of an alkyl phosphoric acid, having the structural formula as shown below. This material likewise has a long aliphatic chain.

This material is of a type fully described in United States Patent No. 2,406,423 as a-surface-active compositron consisting essentially of the formula ONHZRIRZ in which R R and R represent a radical of the class consisting of hydrogen and an alkyl group. R represents an alkyl group of at least 8 carbon atom chain length, and R represents an alkylgroup of ,1 to '4 carbon atoms chain length. These substances are long chain aliphatic amine salts of a long chain aliphatic amide of a short chain alkyl ester of-orthophosphoric acid obtained by reacting one mol proportion of a neutral alkyl ester of metaphosphoric acid in which the alkyl group contains from 1 to 4 carbon atoms with one mol proportion of each of two aliphatic amines in which at least oneof the amines has .an aliphatic radical containing-a straight chain of at least 8 carbon atoms. Thus the amine may be a lauryl amine or a stearyl amine.

The R and R may be ethyl groups. A particularly useful compound, and the one used in many of the subjoined examples, is the monolauryl amine salt of the monolauryl amide of ethyl phosphoric acid. It is commercially known as Victamine C. h

This material is but very slightly soluble in water, the water-solubilizing group being the alkyl group. It'does not have, when in water dispersion, the surface-active properties of the Alox materials, but nevertheless is most efficient in the combination of relatively large amounts of water-insoluble materials with cellulosic fibers treated with it in aqueous suspension.

This material is soluble in methanol, toluene, ether, kerosene, and similar hydrocarbons, and toluene solutions of it exhibit very appreciably increased reactivity with cellulosic fibers in aqueous suspension. Toluene itself has a surface-active action, and the composite of the water-insoluble cationally reactive lauryl amine salt of the lauryl amide of ethyl phosphoric acid with toluene makes for a most effective cationically reactive surfaceactive agent, as is evidenced by the pair of electrometric titration data tables relative to this material, the pulp that was electrometrically titrated being from thesame beater of fully bleached kraft pulp as was used in the evaluation ofthe already mentioned Alox material.

In this instance a polybasic acid is the starting point of the amine reaction, and there is a polyvalent cation with a high degree of electropositivity, and a 12 carbon atom chain in the alkyl group. As distinguished from the Alox type of materials, this cationically reactive material is practically odorless and light tan in color, as contrasted 'to the deep black of the Alex materials, and not as oily in appearance.

The composite reagent, made by dissolving the cationi cally reactive material in a non-ionic organic type of surface-active agent, such as toluene, produces a most effective operable conditioning material for the first step in the operation of the present invention. The evaluation data of this type of reagent is detailed subsequently.

While a toluene solution of the VictarnineC is highly suitable, there is another way of using this substance, and that is in conjunction with a non-ionicliquid wetting agent, such, for example, one known as Victawet 12 which has the general formula of medium chain alkyl group R being a hydrophilic group, and which is furnished in the form of a liquid having a specific gravity of 1.121 at 28 C., and which is soluble in alcohols, acetone, toluene, etc., but merely forms a milky suspension in water. The liquid Victawet 12 is a solvent or diluent for the Victamine C. Thus the Victamine C may be dissolved in Victawet, and the resulting solution incorporated with an aqueous suspension of cellulosic fibers, as in a beater or similar instrumentality, and the process then being continued as outlined.

In carrying out the processes of the present invention, cellulosic fibers that have been treated with an amount of a cationically active surface-active agent of the desired type, as indicated by a preliminary electrometric titration as above mentioned, are subjected while in aque opsspspension, as in a beater, to the action of an emulsion or dispersion of the additament, which latter emulsion or dispersion has also been .rendered cationically reactive by the addition, for example, of a salt of a long chain fatty acid amine, preferably one having a '16 to 20 carbon atom chain. Substantially immediately after the addition of such an emulsion, the previously suspended material of the emulsion will attach itself-to the cellulosic fibers with a degree of tenacity that is *truly remarkable. The liquid in which the materials arefsuspended will become quite clear, and the adsorption or affixation of the suspended material upon the treated cellulosic fibers is substantially quantitative, and may equal, or even exceed, per cent by weight of the bone-dry weight of the cellulosic fibers.

For a better understanding of the present invention, the following examples are given. be given in greater detail, and the other examples then sketched in, with the understanding that similar manipulative details are employed. The later examples are therefore more in the nature of stated-results, using different materials and proportions; but generally speaking, procedurally they are equivalent to the earlier examples. While only about eighty or so actual examples are given to demonstrate the truly generic nature of the present invention, it can bestated that well over 350 examples have been carried out successfully, not only on a laboratory basis but on a Fourdrinier machine.

EXAMPLE 1 360 grams of bone-dry fully bleached southern kraft pulp were furnished to a'laboratory beater, and the stock well brushed out, after which 25.20 grams of Alox Ll205X were added to the beater furnish, and the beating continued for one and one half hours to afinished beater freeness of 680 (Canadian standard). The finished beater consistency was 1.50% (bone-dry basis) and thepH value of the beater stock was 8.40.

662 grams of beater stock as above prepared were weighed out and 338 grams of water added to give an exact 1% bone-dry suspension of Alox-treated cellulosic fibers. This suspension of treated cellulosic fibers was electrometrically titrated with a 20% non-volatilesolids emulsion of polymerized rosin, the emulsion being cationically reactive. The rosin used has the trade name designation of polypale rosin. The electrometric titration data is tabulated below.

1 pH Value 2 .Visual Appearcc. 20% N. V. Solids CationicallyReaetive after ance of Liquid Polymerized Rosin Emulsion Added Emulsion Phase of Addition Suspension 0 8. 40 clear liquid.

8. 40 Do. 8. 40 Do. 8:25 Do. 8.20 Do. 8.15 D0.

The rosin solids added to the treated cellulosic fibers equalled 10.00 grams. At the end of the titration cycle a hand sheet was made, which gave no evidence of sticking on the forming wire, press felts, or dryer surfaces, and no foam was in evidence. The white-water from the forming wire was crystal clear and completely free from fiber or rosin particles. The hand sheet was dried to a constant weight at 215 F., and the weight recorded.

A second sample of exactly 662 grams of beater stock was weighed out, and 338 grams of water added thereto, and a hand sheet made of this fiber suspension. The sheet was dried to a constant weight at 215 F. and the weight recorded. The results were as follows:

Bone-dry weight of cellulose-rosin hand sheet=20.l5

grams Bone-dry weight of blank cellulose sheet=10.l0..grams Bone-dry weight of rosin solids added=10.00 grams Bone-dry weight of rosin solids plus bone-dry blank:

20.10 grams Percentage rosin solids added=l00% on the cellulose weight Bercentagerosin solids combined -with"cellulose--l'00% The earlier examples will Example 2 360 grams, bone-dry basis, of unbleached southern kraft pulp were furnished to the laboratory beater, and the stock well brushed for one-half hour, whereafter 28.80 grams of Alox I /1205X," were added and the beating continued for one hour to complete the beating cycle. The finished beater freeness was 580; the bone-dry beater consistency was 1.55%. Thereafter a series of standard 10.00 gram (bone-dry basis) fiber suspensions were made up at exactly 1% treated fiber consistency, and various of the prepared samples were treated with different types of cationically reactive emulsions of water-insoluble materials, the said emulsions being used at a 2% solids concentration. A series of blank hand sheets were made from this treated beater stock, to use in the evaluation of the quantitative factors of combination of treated cellulosic fibers and cationically reactive emulsions or dispersions of the water-insoluble additament. The average bone-dry weight of the blank hand sheets of this treated stock was 10.50 grams, which figure is used in the series of evaluation studies made of this beater furnish.

To one of the standard 1% treated fiber suspensions containing 10.00 grams of treated cellulosic fiber was added 250 cc. of a 2% non-volatile solids emulsion of G. R. I.70 rubber, which is an isoprene-isobutylene type of synthetic rubber, the rubber emulsion being cationically reactive. A complete and instantaneous combination of the added rubber and the treated cellulosic fibers took place, the liquid phase of the suspension of the mixture clearing instantly after the addition of the cationically reactive emulsion. A hand sheet was made of the reacted mixture. No sticking tendencies were observed on the forming wire, press felts, or dryer faces, and the white-water from the forming wire was crystal clear and completely free from fibrous or rubber particles. The hand sheet was dried to a constant weight at 215 F. and the Weight recorded. The results were as follows:

To one of the standard 1% treated fiber suspensions of the above beater furnish containing 10.00 grams (bone dry) of treated cellulosic fibers, exactly 500 cc. of a 2% non-volatile solids emulsion of Piccoumaron-Sl15 (coumarone-indene) resin was added, the resin emulsion being cationically reactive. An instantaneous combination of the cationically reactive coumarone-indene resin emulsion and the treated cellulosic fibers took place, the liquid phase of the reacted mixture becoming crystal clear immediately after the addition of the cationically reactive coumarone-indene resin emulsion. A hand sheet was made of the reacted mixture. No sticking tendency was observed on either the forming wire, press felts, or dryer faces, and the white-water draining from the sheet forming wire was crystal clear and free from either fibrous or resinous matter. The hand sheet was dried to constant weight at 215 F. The results were as follows:

Bone-dry weight resin solids added grams 10.00 Bone-dry weight blank hand sheet do 10.50 Bone-dry weight processed sheet do 21.50 Percentage coumarone-indene resin solids added per cent 100 Percentage coumarone-indene resin solids combined with the fiber per cent..- 100 EXAMPLE 4 To one of the standard 1% treated fiber suspensions of the above beater furnish containing 10.00 grams of bonedry treated fiber, 500 cc. of a 2% non-volatile solids, cationically reactive emulsion of chlorinated parafiin was added. An instantaneous combination of the cationically reactive emulsion of chlorinated parafiin and the treated cellulosic fibers took place, the liquid phase of the mixture clearing immediately after the addition of the emulsion. A hand sheet was made of the reacted mixture. There was no evidence of sticking to the forming wire, press felts, or dryer faces, and the sheet was dried to a constant bone-dry weight and the weight recorded. The white-water draining from the forming wire was completely free of fibrous or water-insoluble particles, being crystal clear. The dried sheet was quite flame resistant, as would be expected. The results were as follows:

EXAMPLE 5 To one of the standard 1% treated fiber suspensions of the above beater furnish, 700 cc. of a 2% solids content cationically reactive emulsion of an hydrogenated esterified rosin were added. An instantaneous combination of the cationically reactive emulsion and the treated cellulosic fibers was efiected, and directly after the addition of the cationically reactive emulsion, the liquid phase of the reacted mixture became crystal clear. A hand sheet was made of the reacted mixture, and at no point in the processing of the hand sheet did any sticking occur. The white-water from the forming wire was free from fibrous and resinous material and was crystal clear. The hand sheet was dried to a constant bone-dry weight and the weight recorded. The results were as follows:

Bone-dry weight hydrogenated esterified rosin added grams" 14.00 Bone-dry weight blank hand sheet do 10.50 Bone-dry weight hydrogenated esterified rosin cellulose fiber complex hand sheet grams 25.00 Percentage hydrogenated esterified rosin added percent 140 Percentage combination hydrogenated esterified rosin with fiber "percent..-

EXAMPLE 6 To one of the standard 1% treated fiber suspensions of the above beater furnish, exactly 500 cc. of a 2% nonvolatile solids cationically reactive emulsion of methylmethacrylate resin were added. An instantaneous combination of the cationically reactive resin emulsion and the treated cellulosic fibers was effected, the liquid phase of the reacted mixture clearing immediately after the addition of the emulsion. A hand sheet was made of the reacted mixture. No evidence of sticking was noticed on the sheet forming wire, the press felts, or the dryer faces, and the sheet was dried to constant bone-dry weight and the weight recorded. The white-water draining from the forming wire was crystal clear and completely free from ieither fibrous or resin particles. The results were as folows:

Bone-dry weight methylmethacrylate resin solids added grams 10.00 Bone-dry weight blank hand sheet do 10.50

Percentage resin added with fiber percent 100 1 bination of treated cellulosic fibers and a poly-methylmethacrylate resin in the formulation of artificial leather is of importance, as the finished hand sheet exhibited many of the characteristics of such material.

EXAMPLE 7 This example is one of the most striking ones made of record in connection with the present invention. To one of the standard 1% treated fiber suspensions of the above beater furnish, exactly 500 cc. of a 2% non-volatile solids cationically reactive dispersion of chrome yellow pigment (a commercial pigment product marketed under the trade name of C. P. Chrome Yellow Medium No. 1085, of the lead chromate type) were added. An instantaneous combination with the treated cellulosic fibers was effected, the liquid phase of the reacted mixture becoming crystal clear and completely free from color. There was no settling of chrome pigment at the bottom of the reaction vessel notwithstanding the fact that the specific gravity of the chrome yellow pigment is 5.90. A hand sheet was made of the reacted mixture and dried to bone-dry weight. A new set of blank hand sheets was made and the average weights (bone dry) determined and recorded. There was no evidence of sticking on the forming wire, the press felts, or the dryer surfaces, and the white-water draining from the forming wire was completely colorless and free from any trace of either fiber or pigment. The results were as follows:

Bone-dry weight chrome yellow pigment added grams 10.00 Bone-dry weight blank hand sheet do 11.20 Bone-dry weight chrome yellow-cellulose fiber complex "grams" 21.50 Percentage chrome yellow pigment added percent 100 Percentage chrome yellow pigment combined with fibers percent 100 This is a most striking example of quantitative combinatlon of treated cellulosic fibers with water-insoluble inorganic mater1als by the methods of the present invention.

EXAMPLE 8 500 grams of bone-dry, full bleached, southern kraft pulp were furnished to the laboratory beater, and after the stock had been well brushed out, 90 cc. of Alox L-l205-X' were added to the beater furnish and the reaction continued for a period of five minutes. Thereafter an exact 1% bone-dry treated fiber suspension of the so treated beater stock was made up, and 1000 grams of such suspension, corresponding to exactly 10.00 grams of bone-dry treated fiber, made up for evaluation. To this fiber suspension of the beater stock 250 cc. of a 2% non-volatile solids content, cationically reactive emulsion of an acrylonitrile-butadiene elastomeric copolymer were added. This material was a product of the B. F. Goodrich Chemical Company and is identified in the trade as HyCar-OR-25-1502-X3 62. The reaction time for combination with the treated cellulosic fibers was of a much slower order than had been the case with other types of cationically reactive dispersions or emulsions, but

in a matter of from one to two minutes the liquid phase of the reacted mixture completely cleared, and a hand sheet was made. The elastomeric complex of cellulose and acrylonitrile-butadiene was'extremely free on the wire, gave no evidence of sticking on the forming wire, the press felts, or the dryer surface, and the white-water draining from the forming wire was crystal clear and completely free from fibrous or resin particles. The hand sheet was dried to constant bone-dry weight and the weight recorded. The dried sheet was extremely tough and rubberlike and had great tearing resistance. Itreadily lends itself to themachine production of rubberized material for the manufacture of bags and wrappings. The results were as follows:

Bone-dry weight acrylonitrile-butadiene' added I grams; bone-dry basis, of full bleached southern kra'ftpulp were furnished to-the laboratory beater, and

after the stock had been well brushed for one half hour, exactly 15.00 grams of Victamine C (solids basis), in the form of a 5% aqueous dispersion, and being a cat-' ionically reactive surface-active agent as already explained, were added to the beater and the beating continued for an added one and one-half hours to an approximate finished beater freeness of 600, Canadian standard. Thereafter the bone-dry beater consistency was determined and a series of standard 1% bone-dry treated fiber suspensions made up for evaluation work, each such suspension totalling 1000 grams in weight and containing 10.00 grams of treated bone-dry fiber.

To one of these standard 1% Victamine treated cellulosic fiber suspensions exactly 250 cc. of a 2% non-volatile solids content cationically reactive emulsion of acrylonitrile-butadiene elastomeric polymer were added, and an instantaneous combination with the treated cellulosic fibers was effected, far more rapid in reaction than was the case in Example 8. The liquid phase of the treated cellulosic suspension became clear immediately after the addition of the cationically reactive emulsion of the elas tomeric copolymeric product. A hand sheet was made and there was no evidence of sticking at any point in processing. The treated cellulosic fibers were very free on the forming wire and dried readily. The sheet was tough and rubberlike when cured at 310 F. and exhibited great tearing resistance. The combination of acrylonitrilebutadiene elastomer with the treated cellulosic fibers was completely quantitative. The white-water from the wire was crystal clear and completely free from fibrous and rubber particles. The retention, when tested in the manner hereinabove frequently explained, was substantially per cent.

EXAMPLE 10 To one of the standard 1% treated fiber suspensions of the above Victamine C treated beater furnish exactly 500 cc. of a 2% non-volatile solids content cationically reactive mixed emulsion were added, being made up of 75% of hydrogenated ester gum solids and 25 of acrylonitrile-butadiene solids. An instantaneous combination was efie'cted between the emulsion and the treated cellulosic fibers, the liquid phase of the reacted mixture clearing immediately upon the addition of the emulsions. A hand sheet was made of the reacted mixture. No evidence of sticking was observed at any point in the manufactureof the hand sheet; the white-water draining from the forming wire was crystal clear and completely free from fibrous or resin particles. The combination of the combined cationically reactive emulsions and the treated cellulosic fibers was completely quantitative.

The finished hand sheet thus made was, after drying; placed in a small laminating press to compress the sheet and apply heat thereto such as would obtain in a diestamping operation. About 320 F. was maintained in the press, with a platen pressure of about 800 p. s. i. The finished sheet is useful as a base material for the diestamping of disposable plates. The hand sheet time in the laminating press was in excess of one minute. The cured sheet, as removed from the press, showed no evidence of sticking to the press platens and no evidence of extrusion or beading of resin on the sheet edges. The cured sheet withstood penetration by cottonseed oil for an excess of 30 minutes at F., and thus is shown't'o" 500 grams, bone-drybasis, of full bleached southern= kraft pulp were furnished to the laboratory beater, and

after the stock had been well brushed for one-half hour, 50 grams of Alox 1561, a cationically reactive surfaceactive agent, were added and the beating continued for one and one-half hours to give a heater freeness of about 600, Canadian standard. Thereafter standard 1% treated fiber suspensions of the so-treated-material were made up (bone-dry treated fiber basis), each standard'fiber suspension equalling 1000 grams or 10.00 grams of bone-dry treated fiber.

One of these standard 1% Alox 1561 treated fib'e'r' suspensions" of the beater stock was electrometrically titrated witha" 5% Valspar '(spar) varnishsolids in the" form of a cationically reactive emulsion, the data of which is tabulated below. Acommercial purchase of Val-; spar varnish was made and the non-volatile solids con-,

tent thereof determined to be approximately 40%. The varnish was cut with acetone, a suitable cationic emulsifier was added, and the solvated varnish and cationic emulsifier added to water by means of a colloid mill to make a varnish solids type of emulsion which was highly cationically reactive. This was used as the titrating medium in the electrometric titration of a standard 1% Alox 1561 treated (bone dry) cellulosic fiber suspension, containing 10.00 grams of bone-dry cellulosic fiber.

pH value after t 57 V 1 ti t 1i cc. 0 o aspar varca on ca y nish solids cationically reactive g gggtg ggg gfg y reactive emulsion added "Valspar" p s varnish emulsion 7. 50 clear. 7.00 instantaneous combination. 6. 60 Do. 6. 40 Do. 6.20 Do. 6.00 Do. 5.90 Do. 5. 80 Do. 5.80 Do.

1 Liquid phase completely clear 2 to 3 seconds after each addition.

A hand sheet was made at the end of the titration cycle. An excellent sheet was formed, there being no indication of sticking to either forming wire, press felts, or dryer surfaces. The hand sheet was dried to bone-dry weight and to a constant weight to eliminate drying oils, the cationically reactive Valspar varnish emulsion being based on Valspar varnish solids. The white water draining from the forming wire was crystal clear and free from fibrous and solid particles. The sheet was then dried at 310 F. to insure loss of volatiles. A blank hand sheet was made of a duplicate 1% treated cellulosic fiber suspension for comparison. The results were:

Bone-dry weight Valspar varnish solids added The practical application of this procedure is in the machine production of insulating papers, using a phenolic varnish of high dielectric properties, as against present methods of such production by methods of saturation and coating applications. The finished sheet was extremely flexible, quite tough, and highly resistant to penetration by water.

EXAMPLE 12 500 grams of bone-dry, unbleached kraft pulp were furnished to the laboratory beater, and the stock well brushed. Thereafter 25.00 grams (as is) of Alox Ll205-X were added and the beater circulated for an additional one and one-half hours with a hard roll action to effect a hard beating action and to complete the reaction cycle for the Alox L-]205X. Thereafter a series of standard 1% bone-dry Alox-treated fiber suspensions were prepared for evaluations, each suspension weighing exactly 1000 grams and containing approximately 10.00 grams of bone-dry treated cellulosic fiber. The finished beater consistency on a bone-dry basis was 1.55% and the freeness factor approximately 500 Canadian standard. The pH value of the finished beater was 6.40. A series of blank hand sheets were made to establish an average bone-dry weight of the fibrous content of the 1% standard cellulosic fiber suspensions. The average weight of the blank hand sheets was 10.60 grams; the variation was not over 0.20 grams in the weight of several blank hand sheets.

To one of these standard 1% treated fiber suspensions (bone-dry basis) were added 500 cc. of a 2% non-volatile solids content cationically reactive emulsion of a paratertiarybutylphenolformaldehyde resin. An instantaneous combination of the added resinous material was effected withthe treated cellulosic fiibers, the liquid phase clearing immediately after the addition of hte emulsion. A hand sheet was made of the reaction product. No sticking was evidenced at any point in the processing of the hand sheet, the white water draining from the forming wire being crystal clear and free from fibrous and resinous particles. The sheet was dried to constant weight and the weight recorded, the results being as follows:

Bone-dry weight of paratertiarybutylphenolform- To one of the standard 1% treated fiber suspensions from the treated beater stock of Example 12, 500 cc. of a 2% non-volatile solids cationically reactive emulsion of a high melting point parafiin wax were added. An instantaneous combination of the added wax materials with the treated cellulosic fibers was effected, the liquid phase clearing immediately after the addition of the emulsion. A hand sheet was made of the reaction product. No sticking tendencies were evidenced on either the forming wire, the press felts, or the dryer surfaces, and the white water draining from the forming wire was crystal clear and completely free from fibrous and wax particles. The sheet was dried to constant weight. The hand sheet was extremely soft and flexible, highly resistant to penetration by water, and very translucent and free from tack. The quantitative data are as follows:

Bone-dry weight of wax added grams 10.00 Bone-dry weight of blank hand sheet (average) do 10.60 Constant weight of cellulose-wax complex do 20.75 Percentage of wax solids added per cent l00 Percentage of wax solids combination withi fibers This sheet offers interesting possibilities in the use of waxes on the paper or molding machine, as contrasted to the impregnation of paper sheets subsequent to manufacture by means of a Waxing operation, such as saturation, dipping, or coating methods, and offers also the possibilities of wax-rosin combinations in paper production for the manufacture of highly sized materials that are not possible to produce today by the present conventional methods of coagulation and precipitation.

Further generalizations Instead of the particular forms of cellulose mentioned in the above fourteen examples, any of the following cellulosic fibers, or mixtures thereof, may be successfully employed: unbleached kraft pulp, semibleached kraft pulp, full bleached kraft pulp, unbleached sulfite pulp, semibleached sulfite pulp, full bleached sulfite pulp, unbleached semichemical pulp, semibleached semichemical pulp, caustic cooked chestnut fiber, unbleached soda pulp, semibleached soda pulp, full bleached soda pulp, unbleached and cooked cotton rag stock, semibleached and cooked cotton rag stock, bleached and cooked cotton rag stock, cooked bagasse fibers, cotton linter pulp of various types and grades, mechanical pulp both from coniferous and deciduous woods, cooked hemp, sisal, ramie, jute, caroa, and other bast fiber stock such as bamboo, palm, and many grasses, old paper stock made up of any or all or any mixture of used papermaking fibers, cooked straw fibers, cooked flax fibers, and in fact any cellulosic fibrous material that lends itself to the formation of cellulosic webs or forms from its aqueous suspension.

Among the types of condensation polymers that are adaptable to the practice of the present invention are'the following: phenol-formaldehyde resins, furfural-p'henol condensation product; resorcinol-formaldehyde condensation products; urea-formaldehyde resins, melamine-formaldehyde resins, the reaction-condensa'tion product ,of.cy.-

clohexanol, adiparnide, adipic acid and hexamethylenedi ace-twee amine, the trade name of which is nylon; the condensation-reaction product of phthalic anhydride, glycerol, and linoleic'acid, the trade name of which is Glyptal; the condensation-reaction product of cyclopentadiene, maleic anhydride, glycerol, and linoleic acid, e. g. Carbic resin; the condensation-reaction product of dibasic acid, maleic anhydride, glycerol and styrene, e. g. Laminac resin; the condensation-reaction product of sebacic acld, ricinoleic acid and glycerol, e. g. Paraplex resin; the condensation-reaction product of sebacic acid and ethylene glycol, e. g. paracon resin; condensation-polymerization products of ethylene oxide or Carbowax resins; the condensation-reaction product of ethylene dichloride and sodium tetrasulfide, e. g. Thiokol A resin; and condensation-polymerization products of dimethyldichlorosilane or silicone resins.

Also, several types of varnish resins such as: paratertiarybutylphenol formaldehyde resins; paratertiarybutylureaformaldehyde resins; and paratertiarybutylmelamineformaldehyde resins are within the scope of the present invention.

Among the rosin (abietic acid) derivatives that are applicable to the process operation are'the following: polypale rosin or polymerized rosin; esterified rosins inthe form of pure rosin esters; glycerol'esters of hydrogenated rosin; and the various grades of Wood and gum rosins as normally used in the manufacture of sizing materials for the paper industry.

The vinyl type of polymers adaptable to the process operation may include the following: polyethylene; polystyrene; polydichlorostyrene; Piccolyteresins; coumarone-indene resins; polyisobutylene (Vistanex") resins; methylmethacrylate; ethylmethacrylate; isobutylmethacrylate; butylmethacrylate; polyvinylacetate ((Vinylite"); polyvinylchloride (Geon); polyvinylbutylate; allyl alcohol copolymers (Allymer CR resins); and polyvinylformaldehyde (Formvar); etc.

Copolymeric types of plastics may include the following: vinylidene chloride plus acrylonitrile. (Saran), vinyl chloride plus acrylonitrile (Vinyon); vinylchloride plus vinylacetate plus maleic anhydride (maleic modified polyvinyl chloride acetate); vinylidene chloride plus vinyl chloride (Pliofiex); styrene plus drying oil (Styrenated oil), cyclo pentadiene plus drying oil (cyclo oil).

Special technical resins that are applicable to process operation are various types of synthetic rubbers.

Synthetic rubbers may include the following: Butadiene plus styrene (GRS latex), butadiene plus acrylonitrile (GRA latex), isoprene plus isobutylene (GR-I latex), chloroprene polymerized product (GR-M latex), dirnethyldichlorosilane polymerized product (silicone rubber), chlorohydrin plus formaldehyde plus sodium tetrasulfide (organic polysulfide latex). Other resins may include a class of resins known as hydrocarbon resins. Those are highly resinous materials of varying molecular weights and flow points and have a high utility value. Also included may be various types of asphalts, pitches, tars and the like.

The alkyd resins lend themselves to process operation and olfer interesting possibilities inthe production of new and unusual types of cellulose-alkyd resin-complexes. Among such resins finding application to quantitative'combination with cellulosic fibers in aqueous suspension, by the methods of this invention, are: Pure alkyds of the drying type; phenolated alkyds, styrenated alkyds, rosinmodified alkyd resins, phthalic free alkyd resins.

The drying oils generally used to modify the alkyd resins are linseed, perilla, oiticica, fish, and'tung oils; and in some alkyd resins use is'made'of soya bean oil, dehydrated castor oil, sunflower oil and walnut oil. The dry-- ing types of alkyd resins have a high degree of unsaturation due to their unsaturated fatty acid content, and due to the four double bonds in caseof the fish oil fatty acids. Such alkyd resins may be combined in emulsified form with urea-formaldehyde, phenol-formaldehyde, melamineformaldehyde and other types of plastic materials to give unusual products that impart a high utility value to the cellulose complexes that may be evolved by their use.

Natural latices are also adaptable to process operation,

and natural rubber latex, and its modifications such asprevulcanizednatural. rubber latex, chlorinatedv natural rubber. latex and other materials; that are derived by modificatitm ofl natural. rubbersg. arereadily? adaptable reformulation into= cationically reactive? emulsions or? dispersions, for use in the present process.

Natural gums andsynthetidgums' are readily formulated into' cationically'reactive emulsions or-dispersions, and therefore are adaptable to process operation.

Plasticizing materials maybe'combined with the many water-insoluble materials, where :a plasticizeris tolerated, and unusualfilming properties thusadded to the waterinsoluble materials which generally, in the instance of plasticization, is of the plastic, resin, orelastomeric type of water-insoluble:material.

There are many filling and loading-materials that are readily adaptable to the operation of the process, as without exception they can be formulated into cationically reactive dispersions, and may include the following waterinsoluble materials:' asbestine, clays, bentonite, diatomaceous earths, gypsum, talc, basic leadfcarbonat'e, whiting. titanium oxide; natural barytes, lith'ophone, silica and o ers.

The-waxes are alladaptable to the operatiomofitheprocess: the natural waxes, the petroleum waxes, andthe synthetic waxes in all their grades and: types, as alli are capable of being solvated and subsequently emulsified with an operable cationic emulsifier.

Oils are also amenable to the process, such as natural oils, e; g., vegetable oils, the'mineral oils, and the synthetic oils, all being capable of solvation and subsequent emulsification into a suitable and. operable cationically reactive emulsion. Such materials may serveto plasticize cellulose, and to impart-unusual characteristics of high utility value to cellulosic' webs and forms, and many new types of cellulose-oil complexes may be evolved.

There are a number of cellulose derivatives and modified celluloses that are likewise adaptable to the present process, such as: ethyl cellulose, carboxymethylcellulose, ethylenecellulose, butyral cellulose,- cellulose acetate, and others. Nitrocellulose, because of its highly combustible nature, is not indicated, although it is operable in the operation of the present process.

It is to be noted that other Water-insoluble materials may prove to be of utility value in the production of a cellulosewater-insolublematerial' complex 'web or form, and if such materials are adaptable to formulation into cationically reactivedispersions or emulsions they may be included in the practically unlimited list of waterinsoluble materials adaptable-to'the present invention.

Other types of similar materials that may be included are: chlorinated parafiins; chlorinated rubbers; rubber hydrochloride; and many others.

There are many inorganic, organic and-resinated pigment colors that are completely adaptable to this process of'operation, and so oflfer many interesting possibilities in new methods of coloring cellulosic products. The following are suggested as representative of this: class of materials: lead-sulfo-chromate; lead chromate; zinc chromate; Hausa Yellow (a primary aromatic amine coupled with aceto-acetanilid); basic lead chromate; lead chrome molybdate; lead-chrome green; iron blue pigments; Prussi n'blue pigments: Lithol reds (the pigment produced by diazotizing Z-naphthylamine-l-sulfonic acid, coupling with beta-naphthol and salting out with either barium or calcium salts); resinated barrium Lithol red: resinated calcium Lithol red; toluidine red (Z-nitro- 4-toluene-azo-beta-naphthol pigment dyestuff);.para reds' (similar to the toluidine reds); red lakes (barium salts of l-naphthol-azo-2-oxynaphthalene-3 6 disulfonio acid); phth l cva ne blue. Tar ner red (an a c upling of ortho-chloro-paranitraniline tobeta naphthol); etc., all of which can readily be formulated to a cationically reactive dis ersion. as was done in the instance of lead chromate (Example 7 hereinabove).

There are of course many other types. of, coloring materials that can readilybe made into suitable cationically reactive dispersions for use in the process,. such as: Bone black; carbon black; lamp black; ochre, umber, cobalt blue, mineral brown, red'lead, iron yellow; cadmium red, Tuscan red, cadmium yellow, graphite, whiting, blanc fixe, and others. Metals such as comminuted aluminum, zinc, lead, etc., may also be used.

Preparation of cationically active emulsions forstagetwo' of the present process As the materialthat is tobe deposited upon the' cellulosic fibers must be in an emulsion. ordispersion that 3 exhibits. cationic.activity,. andasthetprcparatiorr; o'fisuch emulsions is of considerable importance in the present connection, there will now be given a number of examples of the preparation of such cationically active emulsions and dispersions. In order not to confuse the example numbers, these examples have been given designations of letters of the alphabet. Any of the subjoined formulas may be employed for the afiixation of the particular additaments to the cellulosic fibers that have been conditioned by treatment with the various types of conditioning materials. It will be noticed that in most cases an organic liquid that itself exhibits surface-active propensities is employed in the formulation of the emulsions or dispersions, usually as a solvent. The outstanding ingredient in these emulsions or dispersions is an 18- carbon atom amine salt, such as the acetate or hydrochloride. It appears that this type of amine salt is an essential and more or less critical part of the emulsions or dispersions, as in their absence the remarkably high degree of deposition of the additament is not obtained. Where hereinafter the amine salt is mentioned, it is intended as a shortened expression for the 18-carbon atom chain amine salt.

Emulsion A: Parts by weight Methyl methacrylate resin 40 Toluene 60 IS-carbon atom ch in amine salt 2 Dissolve the above in the toluene and add to Water 100 Homogenize thoroughly.

Emulsion B:

Polypale rosin 60 Toluene 60 18-carbon atom chain amine salt 3 Dissolve the above in the toluene and add to- Water 180 Homogenize thoroughly.

Emulsion C:

Hydrocarbon resin S-50 500 Toluene 750 Amine sal 25 Dissolve resin and the amine salt in the toluene and add to Water 1259 Homogenize thoroughly.

Emulsion D:

Piccoumaron S-l15 resin 700 Xylene 300 Amine sal 35 Dissolve in the xylene and add to- Water 1000 Homogenize thoroughly.

Emulsion E:

70% chlorinated paraffin 700 Xylene 300 l8-carbon atom chain amine salt 35 Dissolve in the xylene and add to Water 1000 Homogenize thoroughly:

Emulsion F:

P-190 Hydrogenated Ester Gum 400 Xylene 100 Amine salt Dissolve in the xylene and add to- Water 500 Homogenize thoroughly Emulsion G:

GR-I-70 rubber 330 Rubber solvent 710 Xylene 400 Amine salt 15 Dissolve above in the xylene and add to Water 1000 Homogenize thoroughly.

Emulsion H:

Polyethyl butyl methacrylate non-ionic dispersion 200 Amine salt 20 Homogenize in- Water 580 Emulsion I:

Parafiin wax 128 (melt wax) 200 Amine salt 40 Homogenize hot, at least heated to the melting point of the wax. Water 800 Emulsion J:

Toluene-soluble vinyl resin 300 Toluene 700 Amine salt 40 Dissolve in the toluene and homogenize l1't Water 1000 Emulsion K:

Polymerized rosin ester 45 Toluene 20 Amine salt 7 Homogenize in- Water 35 Emulsion L:

Polystyrene 150 Toluene 250 Amine salt 15 Homogenize in- Water 1000 Emulsion M:

Coumarone-indene resin 350 Toluene 150 Amine salt 35 Homogenize in- Water 965 Emulsion N:

Low molecular weight Vistanex (polyisobutylene) 500 Toluene 500 Amine salt Homogenize in- Water 900 Emulsion O:

Pentaerythritol ester of rosin 250 Toluene 250 Amine salt 50 Homogenize in Water 950 Emulsion P:

Hydrocarbon resin S-5 325 Toluene 325 Amine salt 100 Homogenize in Water 900 Emulsion Q:

#2000 super Beckacite l8-gallon varnish with china-wood oil 1 2000 Reduce to 50% N. V. solids with V. M. P.

naphtha. Amine salt 55 Homogenize in Water 1000 Emulsion R:

Phenol-formaldehyde resin 1000 Xylene 1000 Amine salt 55 Homogenize in Water 1000 Emulsion S:

Neoprene GR-M latex 300 Xylene 700 Amine salt l5 Homogenize in Water 1000 1 A dielectric phenolic varnish.

The above examples of cationically active emulsions o r dispersions are in addition to those previously mentioned in connection with the fourteen examples. In all cases the acetate of the 18-carbon chain amine has been used. Among the l8-carbon atom chain acids from which the amines are derived may be mentioned the following:

Qctadecanoic acid (oleic acid); octadienoic acid (Vaccenlc acid); octadecadienoic acid (linoleic acid). There are, of course, many other saturated and unsaturated 18- carbon atom chain fatty acids that may be used to advantage. It has been found that the octadecyl, octadeeenyl and octadecadienyl amines that are most desirable for use should have a mean molecular weight, of the primary amine content of the high molecular weight aliphatic amines, of within the range of from about 240 to 270, and the mean molecular combining weight of the primary amine should be in the range of from 270 to 320. To prepare the acetate of the amine of such a fatty acid, about 100 parts of the amine of octadecanoic acid may be treated with about 19.2 to 22.5 parts by weight of glacial acetic acid. In case of the octadienoic acid, about 19.4 to 22.2 parts of glacial acetic acid will be required. The glacial acetic acid should be added slowly to the amine at a temperature just above the melting point of the amine, say at about 55 to 75 C. Such an amine will have the formula of II RNHaO OCH:

These amine acetates are convertible into a substituted acetamide by the action of heat. This is an important fact, for it appears that the amine acetates are also deposited upon the cellulose fibers. When the sheet or molded pulp object has been prepared, and heat is applied, as during drying or during the hot-pressing operation, the amine acetate is converted into a substituted acetamide. This serves to render the material deposited upon the cellulosic fiber irrernovable by water, and greatly enhances the effect.

Further examples of the bonding of additaments to cellulosic fibers To show the bonding of a heavy inorganic pigment to suspended cellulosic fibers in substantially quantitative proportions, the following example is given.

EXAMPLE 14 500 grams of unbleached southern kraft pulp were furnished to the laboratory beater and the stock well brushed for 30 minutes, after which, 40.00 grams of Alox L-1205-X, were added, and the beating operation continued for 1 /2 hours to develop a stock freeness of approximately 600 Canadian Green standard. At the end of the beating cycle a series of approximately 1% (bone-dry basis) treated fiber suspensions were made for a number of evaluations. I

All of the cationically reactive dispersions and emulsions used were 2% nonvolatile solids dispersions or emulsions.

To one of the treated fiber suspensions were added 50 cc. increments of a 2% nonvolatile solids dispersion of titanium oxide (TiOz); the pH value being taken on each addition, as below:

A hand sheet was made. There were no sticking tendencies evidenced at any point in processing. The whitewater draining from the forming Wire was crystal clear and free of visible particles. The sheet was dried to constant weight at 215 F.

A duplicate 1% fiber suspension was used to form a blank hand sheet, which was also dried to constant weight at 215 F. The results obtained were as follows:

Bone-dry weight titanium oxide solids --added grams 3.00 Bone-dry weight blank hand sheet do 13.64 Input total Weight do 16.64

Bone-dry weight processed sheet as above ..do 16.86 Percentage of combination TiOz with treated cellulose per-cent 100 EXAMPLE 15 To another of the approximately 1% treated fiber suspensions from the beater stock of Example 14 were added, in 50 cc. increments, a cationically reactive 2% N. V. solids dispersion of Hansa Yellow (a primary lAbbreviatiou tor.nonvolatile.

aromatic amine coupled with aceto-acetanilid-e. g., an organic pigment color) and the pH values taken after each addition as in the preceding examples.

DATA.

. i H Value Condition cc. 2? N. V. Solids Cationicaily reactive p d ispcrsion Hansa Yellow added fggg g g 0 7. clear. 50 7. 70 D0. 7. 60 DO.

grams 15.60 Percentage of solid pigment color added per cent 20 Percentage of combination Hansa Yellow-treated cellulose per cent 98 EXAMPLE 16 500 grams of untreated, uncooked, raw cotton linters of the lowest grade were furnished to the laboratory heater, to the water of which had been added 5 grams of a nonionic surface active agent-Victawet M12 in order that the raw cotton linters would be sufliciently wetted to permit beater circulation. Thereafter exactly 40 grams of Alex L1205-X" were added, and the cotton linters brushed for one hour to defiber the linter bundles. Thereafter the beater stock was dumped into a 20-gallon stoneware crock to permit an exact mixing and samplingthe stock agitated to a uniform suspension and the bone-dry consistency determined to be 2.16%. Thereafter exact 1% bone-dry treated cotton linter suspensions were made up for evaluation purposes. The liquid phase of the beater stock was noticeably dirty-the liquid being a blackish-gray in color.

To one of the 1% treated cotton linter suspensions were added successive 50 cc. increments of combined emulsions of cationically reactive emulsions as follows:

(a) 50% polymerized esterified rosin (b) 50% acrylonitrile-butadiene latex DATA cc. 2% V. solitds combilfieii cat- H l ionica y reae ive cm s onsp va ue 50% 50% after Oonditiggg liquid (a) Polymerized esterified rosin addition P (b) Acrylonitrile-butadiene latex 7. 10 dirty gray black liquid phase. 7. 00 liquid phase noticeably lighter in color. 6. 70 clear liquid. 6. 70 D0. 6. 50 D0.

Titration stopped at 200 cc., as this was end point desired.

hand sheet was made. There was noevidence of sticking at any point in the processing, and the stock was extremely free on the wire. An excellent sheet was produced, which was dried to constant weight at 215 Bone-dryfweight processed sheet 13.95 Total input weight (based on blank hand sheet on sheet forming wire and consequent shrinkage loss) 12.75 Gain in weight over 100% combination of added resin solids 1.20 ,Loss in weight blank hand sheet from normal 1.25

-sible and immersed in a 2% nation.

linters.

Per cent Percentage of combination added resin solids with cellulose Percentage of combination on retention, including the dirt solids The processed bone-dry sheet was cured at 800 p. s. i.

and 320 F. for one minute. A tough, flexible, highly liquid-resistant sheet resulted, which had the feel and texture of leather.

EXAMPLE 17 A sample of pure cotton cellulose gauze, e. g., Johnson and Johnson sterilized surgical gauze, was obtained and used in these evaluations. Samples of the gauze were cut to 16" x 16" and bone dried to constant weight at 215 F. The average weight of the untreated gauze samples was 6.10 grams. A number of samples of gauze were immersed for approximately 5 minutes in a 5% solids dispersion of Victamine C. Thereafter thesamples to be used were removed, squeezed as dry as possolids dispersion of a'series of cationically reactive resin emulsions for a'period of approximately 5 minutes, and thereafter were thoroughly rinsed and washed several times with .water, and thereafter stretched flat on an inclined board and thoroughly washed with a hose to completely remove all unbonded material. Thereafter the samples were dried to a constant weight at 215 F. The material used was a' 2% N. V. solids cationically reactive emulsion of chlorinated paraflin. The results were as follows:

A. sample of pure cotton cellulose gauze, e. g., Johnson and. Johnson sterile surgical gauze was weighed, and then immersed in a 2% active solidsdispersion of Victamine C" for several minutes. The sample was then squeezed as dry as possible to remove excess liquid and thereafter immersed in a 2% N. V. solids cationicallyreactive emul- 'sion of polymethylmethacrylate for several minutes,

washed with five wash waters and thereafter stretched flat on an inclined board and washedwith a-hose to remove all unbonded material. The gauze was then dried toconstant weight at 215 F.

The results: Bone-dry weight of processed gauze grams 10.42 Bone-dry weight of untreated sample do 5.63 Polymethylmethacrylate combined with gauze grams.. 4.79 Percent polymethylmethacrylate combined per cent by weight 85 EXAMPLE. 19

Afpiece'of'soft English chamois was obtained for eval- A piece of this leather material was weighed and thereafter immersed in a 2% active'solids dispersion of Victamine' C' "at-60* C; for a-period of two minutes."Thereafter the chamois was thoroughly squeezed I and washed in six wash waters. on an inclined board, and well washed with a hose to to remove. all excess liquid and then immersed in a 2% N. V. solids cationically reactive emulsion of polymethylmethacrylate for approximately two minutes, then rinsed Thereafter stretched fiat The processed The adsorpremove all excess unbonded material. leather was then dried to constant'weight.

tion of the resin was remarkably high as shown by the results:

Bone-dry weight. processed chamois leather 7 grams 43.30

Bone-dry weight untreated chamoisleather grams 18.60 Polymethylmethacrylate combined with leather grams 25.70 Percentage polymethylmethacrylate combined per cent 138 Theprocessed leather was extremely tough and very .fiexibli, and. no resin was visible on the leather surface :as suc In order: further to illustrate. the wide range of materials that canbepermanently afiixed to cellulosic fibers by the. processes of the present invention, and to demonstrate the conjoint use of Victamine C with a nonionic EXAMPLE 20 300 grams (bone-dry basis)"of low grade, untreated, uncooked, raw cotton linters and 200 grams (bone-dry basis) of unbleached southern kraft pulp were furnished to the laboratory heater, to the water of which had been added /2 of 1% of Victawet. 12 (a nonionic surface active agent) to permit an effective wetting of the cotton linters. After brushing out the fibers for one-half hour, 1%-of :V1ctamine C was added (based on bone-dry fiber weight), the addition being made in the form of a 15% aqueous. dispersion. The beating was continued for 1 /2 hours, after which the bone-dry beater consistency was determined and a series of 1% (bone-dry basis) treated fiber suspensions made up for evaluation.

A 2%. N. V.'solids cationically reactive emulsion of Pentalyn K (a hlgh melting point pentaerythritol ester of rosin) was made up for evaluation in electrometric tltrations of' the standard 1% (bone-dry basis) treated fibersuspenstons (1,000 grams total suspension weight). cc. increments thereof were added at a time and the pH values determined on each addition.

DATA

cc. 2% N. V. solidscatlonicall reactive emulsion of higii pH values melting point pentaerytmr after Comments on liquid phase tol ester of rosin added additmn 7. 60 clear. 6. 70 in ant pickup-clear. 6. 40 D0. 6. 10 Do. 5.90 Do. 5. 70 Do. 5.65 Do. 5. D0. 5. 50 Do. 5. liquid phase white hazy. 5. 65. liquid phase white opaque.

To a duplicate 1% treated fiber suspension 400 cc. of the above 2% N. V. solids cationically reactive emulsion were added, and, after reaction, a hand sheet made therefrom. The liquid phase was crystal clear, as was also the white-water. A blank hand sheet wasv made for 3 During the.titration,rat the points marked XX onlthe above table, there were great fluctuations and oscillations in the lndlcator needle durmgtheelectrometric titration,

EXAMPLE 21 To one of the standard 1% (bone-dry basis) treated fiber suspensions from the beater stock of Example 20, 50 cc. increments of a 2% N. V. solids cationically reactive emulsion of polyisobutylene were added, the pH value being determined at each addition.

DATA

cc. 2% N. V. solids cationically pH value reactive emulsion of polyisoafter Comments on liquid phase butylene added addition clear. instant pickup-clear. I

white cloudy liquid phase.

whige opaque liquid phase.

500 (XX) II The pH value of the 2% N. V. solids cationically reactive emulsion of polyisobutylene was 5.20.

To a duplicate 1% treated fiber suspension of the treated beater stock of Example 20, 350 cc. of the above 2% N. V. solids cationically reactive emulsion were added, and after the reaction, a hand sheet was made therefrom and the sheet dried to constant weight at 215 F. During the formation of the sheet the liquid phase and white water were crystal clear, and there was no sticking at any point in the processing. An excellent sheet was produced, which was cured at 310 F. and 800 p. s. i. for 2 minutes. The results were as follows:

Bone-dry weight polyisobutylene solids grams 7.00 Bone-dry weight blank hand sheet do 9.37 Bone-dry weight processed hand sheet do 18.01 Per cent combination of polyisobutylene treated fiber per cent 100 EXAMPLE 22 To one of the standard 1% treated fiber suspensions prepared from the treated beater stock of Example 20, 50 cc. increments of a 2% N. V. solids cationically reactive emulsion of polystyrene resin were added, the pH value being determined at each addition.

The pH value of the 2% N. V. solids cationically reactive emulsion of polystyrene resin was 5 50.

To a duplicate 1% treated fiber suspension, there were added 350 cc; of a 2% N. V. solids cationically reactive emulsion of polystyrene resin and, after the reaction; a

hand sheet made therefrom,' The liquid phase and' white, water were crystal clear, and there was no sticking at any point. The sheet was dried to constant weight at 215 F. The results were as follows:

Per cent combination of polystyrene resin solids with treated cellulose fibers was A series of further examples, e. g., 23, 24, 25, 26, and 27, are the result of evaluation studies in the production of resin-cellulose complexes, designed to serve as replacement material for asphalt saturated felts, such as now used in the manufacture of floor coverings. The primary objectives were to produce base materials of approximately 0.055" caliper; 350# bias weight 24" x 36"480# (finished); which, upon curing at 310-320 F. and at a pressure of 800 p. s. i. for 5 minutes, would result in a tough, rubber-like, flexible, liquid-resistant material, suitable for use as a replacement of the present materials. The total resin-solids content was desired to be approximately 40% of the fiber weight. All of the examples employ two types of resins in the resin component of the complex material, the resins being selected for reasons of their indicated properties. All of the base materials produced in this series of examples exceeded all the desired specificationsall were acceptable for use. All were flowed or cured under the conditions as detailed hereinabove, and in no instance was there any evidence of flash, bleeding, or extrusion of the resin content, even though all samples were pulled hot, i. e., at 3l0320 E, which normally cannot be done with either thermally plastic or elastomeric types of resins. This is most unique to the present process. Although no platen lubricant was used (such as stearic acid), there was no evidence of sticking to the hot platens (310- 320 F.) when pulled hot, which is abnormal for the materials used. All evidence on conversion definitely points to a primary bonding of resin to cellulose. With the exception of the resin complexes used, the procedure was identical throughout this series (Examples 24-28, inclusive). 14" x 14" hand sheets made for sample purposes, and 6 /2" x 6 /2 sheets made for curing cycle evaluations. The details as to these examples are as follows:

EXAMPLE 23 To a standard 1% treated fiber suspension (stock of Example 20) 50 cc. increments of a 2% N. V. solids cationically reactive combination emulsion were added and the pH values determined. The combination cationically reactive emulsion used consisted, in this case, of equal parts (solids basis) of:

(a) A pentaerythritol ester of rosin, and (b) An acrylonitrilebutadiene copolymer elastomer DATA cc. 27 N. V. solids cationically pH value reaciive combination emulsion after Cowman? on hqmd as above added addition p 356 o clear. t k cl O instan pic up ear. 6. 85 D0. 6. 70 D0. 200 (40% IBSl-Il) 6. 70 D0.

The pH value of 2%N. V. solids cationically reactive combination emulsion as above used was 5.80. A hand sheet was made at the end of the titration cycle. The white water was crystal clear, and no sticking was evidenced at any point. The sheet was bone dried at 215 F. The results were:

Bone-dry resin combination solids added grams 4.00 Bone-dry weight hand sheet (blank) do 9.37 Bone-dry'weight processed hand sheet do 13.74 Peg cent combinationresin solidstreated fi- This produced an excellent cured product, which was extremely tough, flexible, and resistant to penetration -by liquids.

added, pH values being'taken at each addition.

*egeeeess T23 JEXAMP LEM To a standard 1% treated fiber suspension (stock of 'Example 20) 50 cc. increments of a 2% N. V.'solids cationically reactive combination resin emulsion were The combination resin emulsion consisted of equal parts (solids basis) of:

(a) Pentaerythritol rosin ester, and

(b) Polyisobutylene (Vistanex rubber) DATA cc. 27 N. V. solids combination pH value cati nlcaily reactive emulsion as after f z gg liquid above added addition 8.10 clear. 7 instsisig pickup-clear. 150 1110 Do: 200 (40% resin) 7. Do.

The pH value of 2% N. V. solids'resin combination emulsion as above was 6120. A hand sheet was made at the end of the titration cycle. The white water was crys-* tal clear, and there were no sticking tendencies. The sheet was bone dried at 215 F. The results were:

Bone-dry weight resin solids added.. grams 4.00 Bone-dry weight blank hand sheet do 9.37 Bone-dry weight processed hand sheet do 13.38 Per cent combination, resin solids treated -fiber uper cent 100 Sheet composition:

60 parts raw cotton linters 40 parts unbleached kraft pulp 20 parts pentaerythritol ester of rosin 20 parts olyisobutylene (Vistanex) It produced an excellent cured product, which was tough, flexible, and waterproof, and which did not show the slightest evidence of sticking to hot platens (310-320 F.) when pulled hot.

EXAMPLE 25 To a standard 1% treated fiber suspension (stock of Example 21) 50 cc. increments of a 2% N. V. solids cationically reactive combination resin emulsion were added, pH values being taken at each addition. The combination resin emulsion consisted of equal parts (solids basis) of:

(a) Pentaerythritol ester of rosin, and (b) Hydrocarbon 'resin (modified rubber S-S) DATA cc. 2% N. V. solids combination pH value cationically reactive emulsion after m if g liquid added as above addition p 0 7. 60 clear.

50. 6. 90 instant pickupclear.

100 6. 70 D0. 150 6.50 D0. 200 (40% resin) 6. 25 Do.

The pH value of-2% N. V. solids cationically reactive resin combination emulsion as above was 5.30. Hand sheets were made at the end of the titration cycle. The white water was crystal clear, and there was-no sticking.

' The sheet was bone dried at'215 F. The 'resultswere:

Bone-dry weight resin solids added "grams" 4.00 Bone-dry weight blank hand sheet do 9.37 Bone-dry weight processed hand sheet ..do 13.90 Percent combination resin solids treated fiber per cent 100 An excellent cured product, which w'as't'ough, flexible, and waterproof, resulted. It had the following composition:

60 partsraw 'cotton linters 40 parts unbleachedkraft pulp ,20 parts pentaerythritol ester of rosin i H 20 parts hydrocarbon resin (modified rubber S-'-5").

24 EXAMPLE 26 To a 'standard.1% treated fiber suspension (stock of Example 20) cc. increments of a 2% N. V. solids cationically reactive combination resin emulsion were added, pH values being taken at each addition. The combination resin emulsion consisted of equal parts (solids basis) of:

(a) Pentaerythritol ester of rosin, and (b) Polyethylbutyl-methacrylate resin The pH value of the 2% N. V. solids resin combination emulsion as above was 5.20. A hand sheet was made at the end of titration cycle, and the White water was crystal clear, and there was no sticking. The sheet was bone dried at 215 F. The results were:

Bone-dry weight resin solids added grams 4.00 Bone-dry weight blank hand sheet do 9.37 Bone-dry weight processed hand sheet do 14.03 Percent combination resin solids treated fiber per cent 100 This formed an excellent cured product which was "extremely tough and rawhide-like in feel, very flexible,

and waterproof. It had the following composition:

parts raw cotton linters 40 parts unbleached kraft pulp 20 parts pentaerythritol ester of rosin 20 partspolyethylbutyl-methacrylate resin EXAMPLE 27 To a standard 1% treated fiber suspension (treated stock of Example 20) 50 cc. increments of a 2% N. V.

solids cationically reactive resin combination emulsion were added, pH values being taken at each addition. The combination resin emulsion consisted of equal parts (solids basis) of:

(a) Polyisobutylene (Vistanex), and

. (b) Polyethylbutyl-methacrylate resin DATA cc. 2% N. V. solids combination cationically reactive emulsion added above pH value after Comments on liquid addition Phase 0 clear. 5 instant pickup-clear.

Do. Do.

ppayqq was 000 150 1 200 (40% resin) The pH value of the 2% N. V. solids resin combination emulsion as above was 5.40. A hand sheet was made at the end of the titration cycle, and the white water was crystal clear, and there was no sticking. The sheet was bone dried at 215 F. The results were:

Bone-dry weight resin solids added grams 4.00 Bone-dry weight blank hand sheet do 9.37 Bone-dry weight processed hand sheet do 13.38 Percent combination resin solids treated fiber per cent 100 "Thislformed anex'cellent' cured product with peculiar properties; 'very,'very"tough and yet very flexible, and a 0.055" cured sheet was impossible to tear by hand. It

wasiresistant to hotand cold water forv hours and ap- 26 peered translucent, with apparently no grain visible. The sheet composition was as follows:

60 parts raw cotton linters 40 parts unbleached kraft pulp 20 parts Polyisobutylene (Vistanex) 20 parts polyethylbutyl-methacrylate resin EXAMP'ILE 28 (a) Polyisobutylene (Vistanex rubber) (b) Pentaerythritol ester of rosin (Pentalyn K) (c) Hydrocarbon resin S-S (modified rubber) (d) Polyvinylchloride resin (e) Coumarone-indene resin (1) Polyethylbutyl-methacrylate resin DATA cc. 2'7 N.V. solids cationically pH value reac ive complex resin emulsion after zg liquid as detailed above addition p clear.

Do. Do.

150 200 (40% resin) instant pickup-clear.

The pH value of the above 2% N. V. solids complex resin emulsion as above was 6.20. A hand sheet was made at the end of the titration cycle. The liquid phase and white water were clear, and there was no sticking at any point. A peculiar but excellent sheet resulted, showing great uniformity of formation and having a leathery feel and appearance. The hand sheet was dried to constant weight at 215 F. The results were as follows:

Bone-dry weight resin solids added grams-.. 4.00 Bone-dry weight blank hand sheet do 9.85 Bone-dry weight processed hand sheet do 13.80 Percent combination resin solids treated fibers per cent" 100 The composition of the sheet thus made is:

60 parts raw cotton linters 40 parts unbleached kraft pulp 6.66 parts olyisobutylene 6.66 parts pentaerythritol ester of rosin 6.66 parts hydrocarbon resin 8-5 6.66 parts olyvinylchloride 6.66 parts coumarone-indene resin 6.66 parts polyethylbutyl-methacrylate resin This sheet was cured at 310 320 F. at 800# p. s. i. for minutes. A tough, highly glazed, leatherlike product resulted, impervious to penetration with water over a long period, diflicult to tear, and very pliablea peculiar combination of physical characteristics.

Special aspects of the invention In the development of suitable cationically active dispersions or emulsions of the additaments by the aid of the salt of the 18 carbon atom chain fatty acid amines, it was found that the type of organic solvent employed to form the disperse phase was important, and that the hydrocarbons that gave satisfactory results were aromatics rather than aliphatics. Thus, toluene and xylene were found to be eminently satisfactory, while petroleum types of solvents were inoperative, even when used conjointly with an aromatic such as toluene or xylene. Benzene is counterindicated, mainly because of its low boiling point and the resulting fire hazard because of its volatility, and possibilityof the formation of explosive mixtures. Also, benzene is quite toxic, while toluene and xylene are com- 26 paratively innocuous. In place of the pure aromatic by drocarbons, coal tar oils may be used, as these contain toluene, xylene and their higher homologues.

There will now be described an example (29) which has some very outstanding characteristics, in that there were noticed, in connection with the operations, rather striking phenomena, namely, the formation of clusters or' rope-like agglomerations of the cellulose fibers and the additament, so that it would appear asthough at least a sort of physical co-polymerization or condensation had taken place. Thus, while the suspension of the cellulose fiber after treatment with the conditioning reagent and the emulsion of the additament were both murky and almost opaque, yet as soon as the two suspensions were added to each other there would be an almost instantaneous physical reaction by which large, and in some cases star-like, and in other cases, rope-like, agglomerations would form, leaving the liquid otherwise clear. These agglomerations would persist in spite of the most vigorous agitation, showing a very strong attachment of the ad- To one of the standard 1% treated fiber suspensions as prepared with Victawet l2 and Victamine C, as already described, 50 cc. increments of a 2% N. V. solids cationically reactive combined resin emulsion, consisting of'2 parts of polyethylbutyl-methacrylate and 1 part of pentaerythritol ester of rosin, were added, and the pH value determined at each addition. This combined resin emulsion is a combination of large molecules, and complicated molecules, as will be understood. In this titration the above-mentioned phenomenon of complex fiber clusters appeared. The clusters formed at a fixed pH value, and during their formation there was observed a great lack of electronic stability, as will be noted. At the end of the titration, the liquid phase, although initially white and cloudy, and with a wildly fluctuating indicator needle, cleared in from 1 to 2 minutes, and the indicator needle dampened down to a fixed reading as the liquid phase cleared.

The formation of this example could be termed a cluster rather than a rope but nevertheless a definite agglomeration or complex configuration of the complex fibers took place.

This phenomenon could well be related to what might, for lack of established nomenclature, be termed an (a) Emulsion polymerization, if the cellulose fiber suspension could be considered an emulsion of cellulose; or x ([2) Suspension polymerization," if the cellulose fiber iuspension could be regarded as a suspended monomer;

(c) It most probably is Polar polymerization of which little is known and nothing as yet published. If such can be considered the case, then cellulose in an activated condition as treated with a cationically reactive surface-active conditioning agent, could be considered as. a catalytic cationic monomer in a chain addition type of polymerization where electron availability for promoting such chain addition polymerization will come from the numerous double bonds in the reacting cationically active solids phase of the long chain, large molecular sized, resin additaments as it has been noted that the formation of complex fiber clusters or ropes (which definitely appear to be products of chain addition polymerization) takes place mostly with long chain, highly complex, large molecular sized resins.

There is all reasonable basis to establish this phenomenon as a cationic polymerization of:

(a) Cationically activated cellulosic structure containing double bonds; and a (b) Cationically activated complex long chained, large molecular size non-cellulosic materials containing double bonds.

The southern unbleached kraft pulp used in these tests had a very high lignin content and, therefore, was high in double bonds. It is Well known that a simple double bond has a pair of electrons readily available for the promotion of addition reactions. Thereis thus a basis for this theory of cationic polymerization. The process could, therefore, quite aptly be described as one of polar polymerization of cationically reactive complex ,monomers, each or all of which containa multiplicity of double bonds and a high degree of electron availability.

EVALUATION DATA OF EXAMPLE- 29 cc.C2% sfilidstcomlllaineii ation on y eac ive mu sionbof 2 pitrts Poliyethylbutyli gg ifig gg Liquid met .aery ate an par pentaerythritol ester of rosin Adamo 7. 60 clear. 6. 80 instant pick up-clear. 6. 50 Do. 6.25 Do. 6.10 Do. 5. 90 Do. 300 5. 85 Do. 350 clusters 5. 75 D0. 400 (XX) clusters form. 5. 60 Do. 450'(XX) clusters" form 5. 60 Do. 500 (XX) clusters" form..- 5.60 Do. 550 .(XX) clusters" form. 5. 60 slow adsorptioncloudy. 600(XX) "clusters form. 5. 60 cloudy-clear 1 minute. 650 (XX) elustcrs" form. 5. 60 cloudy-clear2m1nutes. 700 (XX) clusters" form....... 5. 60 Do.

1 Note lack of change in hydrogen ion concentration.

The pH value 2% N. V. solids combined emulsion as used above was 4.75 pH.

To an exact duplicate 1% treated fiber suspension, as immediately above, 200 cc. of the above cationically reactive combined resin emulsion was added, with agitation, and after reaction, hand sheet made and dried to constant weight at 215 F.

The liquid phase and white-water were clear, and there was no sticking evidenced at any point. A very tough, leatherlike sheet, when cured at 310 F. at 800 p. s. i. for three minutes resulted. The results, as to the product,

were:

Bone-dry weight resin solids added grams 4.00 Bone-dry weight blank hand sheet do 9.90 Bone-dry weight processed hand sheet do 13.95 Percent combination resin solids--treated fiber percent 100 EXAMPLE 30 To a 1% (bone dry basis) Alox treated fibcrsuspension, weighing 1,000 grams, 50 cc. increments of a cationically reactive emulsion consisting of equal parts of polyethylbutylmethacrylate and paratertiarybutylphenolformaldehyde resin were added and the pH value determined at each addition.

A series of 14" x 14" hand sheets were made corresponding to the end of the above titration cycle, although the end point of the resin-cellulose combination had not been reached. These sheets are among the most striking examples of the process operation of the present invention. The liquid phase was crystal clear, as was also the white water. There was no sticking at any point. Fiber-resin ropes were apparent in the sheet which dried normally, and was calendered, and cured at 310 F., and 900 lbs. p. s. i. for two minutes. There was extremely uniform resin flow. The sheet was highly grease and water resistant.

The actual composition of this sheet was:

50% unbleachedkraft pulp 25% paratertiary-butylphenolformaldehyde resin 25% polyethylbutylmethacrylate 28 EXAMPLE 31.

A cationically reactive emulsion of butyl rubber'was:

usedmade up to a 2% N. V. solids emulsion. A standard 10 grams of 1% Alex treated fiber suspension was,

electrometrically titrated with the above emulsion.

EVALUATION DATA cc. 2% N. V. Solids Cationically pH Value Reactive Emulsion of, Butyl after gg gg Liquid Rubber Added Addition 7. 40 clear, 6.60 instant pickup-clear. 6.30 Do. 150.-.. 6.10 Do. 200 (XX) ropes for1n 6.00 Do. 250 (XX; ropes" Iorm. 5. D0. 300 (XX ropesform 5.90 Do.

A series of 60 grams (bone dry fiber base) 14 x 14" hand sheets were made by adding to a 1% treated fiber suspension containing 60 grams of bone dry treated fiber,

1,800 cc. of a 2% N. V.- solids cationically reactive,

emulsion of butyl rubber. The liquid phase and white water were clear, and the retention was completely quantitative. Excellent sheets resulted which were dried'normally, and then calendered and embossed. Actual sheet composition:

62.5% unbleached southern kraft pulp 37.5% butyl rubber The rope-like fibers were very apparent in the sheets,

stock there was added, in 25 cc. increments, a 2%v N..V. solids cationically reactive emulsion of Lithol Red .(a-

pigment produced by diazotizing Z-naphthylamine-l-sulfonic acid; coupling with beta-naphthol and salting out with a barium salt, and classified as a resinated organic pigment), a total of cc. being added, the. liquid phase remaining crystal clear and free from color throughout the addition. A hand sheet was made. No sticking was evidenced. The white water was crystal clear and free from color. The sheet was dried to constant weight at 215 F. The sheet was brilliant scarlet in color, and no trace of two sidedness was evident. The ultimate results were: Bone-dry weight Lithol Red solids addedugrams 2.50 Bone-dry weight hand sheet blank d 10.42 Bone-dry weight processed sheet H g 13.05 Percentage Lithol Red solids added- ..pe r cent 25 Percentage Lithol Red solids combined with fiber per cent..- 100.

EXAMPLE 33 A supply of soft English chamois was secured and.

samples cut therefrom and weighed. Samples were immersed in a 2% NY. solids dispersion of Victamine C for several minutes and thereafter squeezed dry to remove excess liquid, and immersed in a 0.50% cationically reactive dispersion of an organic type pigment for several minutes at room temperature (approximately 75 F.), the pigment used being known as Hansa Yellow.

Thereafter, the colored leather samples were taken from the cationically reactive dispersion, washed until no trace of color appeared in the wash water, stretched fiat on an inclined board and washed with a hose to remove all .unbonded materials, and thereafter dried to Percentage Hausa Yellow solids combined-36%. This is a remarkably high retention for leather.

EXAMPLE 34 To demonstrate the ease with which uniformly colored products could be made by the use of water-insoluble coloring matter, standard lO-gram treated fiber suspension, treated with 6% Alox L-1205-X' and beaten as usual, was electrometrically titrated with a 0.50% N. V. solids of a cationically reactive dispersion of Phthalocyanine Blue. The primary objective of this evaluation was to determine the rapidity of reaction, as showing possibilities of coloring paper products by the addition of cationically reactive dispersions of pigment dyestuifs to a machine head box, to eliminate by so doing the washing up of beaters and stock chests that normally takes place with color changes. Such a method of coloring paper would, therefore, be of great benefit as related to the production of colored papers. Overall operating costs would be considerably reduced by such a procedure.

The Phthalocyanine Blue is a coordinated copper complex of tetra-azo-tetra-benzo-porphin and has a complicateddstructural formula, being essentially a chelate compoun Phthalocyanine pigments are insoluble in water and substantially insoluble in the vehicles and solvents used commercially in the pigment-consuming industries. They may be dissolved in strong acids, e. g., sulfuric, from which they are precipitated in the original chemical form upon dilution. Their resistance to chemical agencies, e. g., oxidation and reduction, is unusual. They are essentially unreactive.

EVALUATION DATA OF EXAMPLE 34 cc. 0.50% N. V. Solids cationically pH Value Reactive Dispersion of Phthaloafter Addigif gg Liquid cyanine Blue Added tion 7. 50 clear. 5.... 7. 65 instant pick-up-elear.

7. 65 Do. 7. 65 Do. (XX) violent oscillation..- 7.65 D0. (XX) violent oscillation... 7.65 D0. (XX) violent oscillation..- 7.65 D0. 7.50 Do. 7. Do. 7. 50 D0. 7. 45 D0. 7.45 Do. 7. 45 Do. 7. 45 Do. 7. 45 D0. 7. 45 Do. 80 7. 45 Do. 85 (XX) slight oscillatiom. 7. 40 D0. 90 EXX) slight oscillation" 7. 35 Do. 95 XX) slight oscillation 7. 35 Do. 100 (XX) visual end 7. 3O slight bluish tint in liquid phase that disappeared in 1 minute.

A hand sheet was made at the end of the titration cycle. The liquid phase was colorless, as was the white water. There were no sticking tendencies, nor bleeding on white blotters used to couch the sheet, which was dried to constant weight at 215 F.

HAND SHEET DATA Bone-dry weight of Phthalocyanine Blue solids added grams 0.500 Bone-dry weight of blank hand sheet --do 9.168 Bone dry weight processed sheet as above do 9.672 Per cent actual Phthalocyanine Blue in sheet per cent 5.04 Per cent actual retention Phthalocyanine blue per cent 100 Demonstration of variations in conditioning agents ventiort which relates primarily to the conditioning of the material upon which the additaments are deposited.

' EXAMPLE 35 A 5% N. V. solids aqueous dispersion of this material was made up at C., and used in this evaluation work.

It was necessary to maintain the temperature at 80 C.,

to insure the stability of the dispersion, as with a drop in temperature of 15 to 20 C., the waxy solid separated from the aqueous phase and floated on the surface.

A standard 1,000 gram, exact 1% untreated fiber solid suspension was electrometrically titrated with a 5% N. V.

solids aqueous dispersion of this Victamine analog (un- The electrometric titration is .saturated acid B-6518). most interesting and extremely unusual. It is noted that no foaming and no oscillation took place at any point on the titration cycle.

EVALUATION DATA pH Value after Additiou Comments on Liquid Phase cc. 5% N. V. Solids Aqueous Dispersions of Victamine Analog Added to Untreated Pulp 4 cc. of 5% N. V. solids aqueous dispersion of Victamine analog (unsaturated acid B6518) were added to a standard 1,000 gram exact 1% untreated fiber solid dispersion and the mixture agitated for 15 minutes. Thereafter, the mixture was electrometrically titrated with a'2% N. V. solids cationically reactive emulsion of the acrylonitrilebutadiene copolymer.

EVALUATION DATA Results: Hand sheet made at end of titration cycle; liquid phase clear; white water clear; a very noticeable rope-like formation in the sheet; no sticking or foaming tendencies; sheet dried at constant weight of 215 F.

Bone-dry weight of blank hand sheetgrams- 9.60 Bone-dry weight of processed hand sheet (avg.)

grams 19.94 Per cent acrylonitrilebutadiene solids in sheet per cent-.. Per cent retention added solids do 100 The :processed-sheet in: the .wet state was extremely- Evaluation of Sapamine KWC."'Sapamine KWC is a cationically 'reactive surface-active agent, and is properly described as being a compound in which a hydrophobic group is joined-to the cationic group through anamide intermediate linkage. Sapamine KWC is made under United States Patents 1,737,458, 2,186,464, 2,329,406, and 2,357,598, and is a quaternary ammonium salt of an analog of diethylaminoethylolethylamidehydroacetate. It is a cocoa brown powder, insoluble in water at normal temperatures, and forms a brownish colored viscous dispersion in water at 212 F. A 2% aqueous dispersion of Sapamine KWC, at 212 F., was prepared for evaluation, and the temperature of the dispersion maintained at this point as it was found that a decrease in temperature resulted in breaking the dispersion. details of which are here omitted to shorten the specification.

8 cc. of 216% N. V. solids aqueous dispersion of Sapamine KWC were added to a standard 1000 gram 1% untreated fiber solids suspension and the mixture agitated for fifteen minutes. Thereafter, the mixture was electrometrically titrated with a 2% N. V. solids cationic reactive emulsion of acrylonitrilebutadiene. There was a very pronounced formation of rope-like aggregations.

A hand sheet was made at the end of titration cycle, which showed a very noticeable rope formation,.but no sticking or foaming tendencies. The white water was cloudy; The sheet was dried to constant weight at 215F. Results:

Bone-dry weight of blank hand sheet grams 9.60 Bone-dry weight of processed'sheet do 18.90- Per cent acrylonitrilebutadiene solids in sheet per cent 93 Per cent retention resin solids. do... 93

EXAMPLE- 37 Evaluation of "Armac I8-D.-Arrnac 18-D is a high molecular weight aliphatic amine acetate, having the structural formula:

II RNHsOCCHa where R is an 18 carbon atom aliphaticchain, and constitutes the hydrophobic group. It is water-insoluble and disperses with difficulty to a thick viscous dispersion of 2 /2% N. V. solids concentration. It was considered advisable to evaluate this material for the reason that it is extremely cationically reactive, and further has ,a multiplicity of unsaturated linkages in the fatty acid hydrophobic group. Accordingly, a 2%% N. V. solids aqueous dispersion of Ar'mac l8-D was prepared for evalu- The reaction between the treated fibers and the cationic reactive resin emulsion was extremely slow,and from the first addition of cationically reactive acrylonitrilebutadiene emulsion, very pronounced rope-like fibers formed, which formation continued throughout the titration. For reason of the uniqueness of this reaction it was decided to carry the reaction through to clear liquid phases regardless of the time element. At the end of the titration cycle foam developed in the mixture and the stock floated on the top -of the liquid phase. A hand sheet was made after the liquid phase was clear to minutes). like fibers were evident in the sheet, particularly in the wet stage before pressing There was no sticking on Fluctuations were evident duringthe titration,

Very pronounced ropeation, and also because it is a material useful'in step -II 32 the wire, but a slight sticking tendency on the felts. The sheet was driedto a constant weight at215" F. Results:

Bone-dry weight of blank hand sheet grams 9.90 Bone-dry weight processed hand sheet do 20.00 Per cent acrylonitrilebutadiene solids in sheet per cent Per cent retention added resin solids do... 100

EXAMPLES 38A and 38B This is an evaluation of a new type of cationic reactive surface active agent, e. g., a crude reaction product resulting from condensing one mol of triethylenetetramine with four mols of naphthenic acid having an acid number of 210. The resultant product has an acid number of approximately 30, indicating the presence of a small amount of unreacted naphthenic acid and some incompletely reacted amine. The product may be technically termed tetranaphthenoyltriethylenetetramine, i. e.,

and can be classified as that type of cationic reactive surface active agent in which the basic hydrophilic group is linked in a heterocyclic ring.

The material-can further be classified as an imidazoline, e. g., the reaction product of the condensationreaction of polyethylene polyamines with long chain acids, i. e.

ample 38B. Both solutions were brown-black in color,

and free from. any visible suspended. particles. The labroatory beater was furnished with unbleached southern kraft pulp and the stock beaten to a condition closely duplicating the beater stock as used in foregoing evaluations. Thereafter the bone-dry consistency was determined and a series of 1,000 gram exact 1% (bone-dry basis) untreated fiber solids suspensions prepared for evaluations and hand sheet production.

Four cc. of a 5% N. V. solids toluene solution of the tetranaphthenoyltriethylenetetramine were added to a 1,000 gram, 1% untreated fiber solids suspension and the mixture agitated for 15 minutes. Thereafter, the reacted mixture was electrometrically titrated with a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene. A hand sheet was made at the end of titration cycle. The liquid phase had cleared and the white water was clear. There were no sticking tendencies at any point in the processing. The hand sheet was 0. K. and was dried to constant weight at A series of untreated fiber suspensions of 1,000 grams each were made into blank hand sheets; the sheets dried to a constant weight at 215 F. and the average bonedry weight of the blank hand sheets determined.

Bone-dry weight blank hand sheet grams 9.60 Bone-dry weight processed hand sheet above grams 13.93 Bone-dry weight blank hand sheet above.. do 9.60 Per cent resin solids in sheet per cent 40 Per cent retention added resin s0lids do 100 EXAMPLE 39 A 1,000 gram, 1% untreated fiber solids suspension (bone-dry basis) was electrometrically titrated with a 5% N. V. solids aqueous dispersion of a naphthenoyl amide salt, the dispersion being a cloudy, grayish brownblack suspension of finely divided particles. It is the diacylated (acetate) salt of naphthenoyltetramide.

Four cc. of a 5% N. V. solids aqueous dispersion of the naphthenoyl amide-salt M153.1 were added to 1000 grams of a 1% untreated fiber solids suspension (bone-dry basis) and the mixture agitated 15 minutes. Thereafter, the reacted mixture was electrometrically titrated with -a 2% N. V. solids cationically reactive "emulsionof acrylonitrilebutadiene.-

EVALUATION DATA Co. 2% N. V. Solids Oationie Reactive Emulsion pH Value of Aerylonitrilebutadiene after Comments on Liquid Phase added to above treated Addition fibers 7. 75 clear. 7. 60 instant pickup-clear. 7. 50 slower pickup-clear. 7. 50 slower pickuplear 1 min. 7. 45 O. 7. 45 slower pickupclear 2 mins.

Hand sheet made at end of titration cycle. Liquid phase clear. White water clear. No sticking tendencies. lillasud 1 sheet O. K. Sheet dried to constant weight at Bone-dry weight processed hand sheet grarns 14.67

Bone-dry weight blank hand sheet do 9.63 Per cent resin solids in sheet per cent 50 Per cent retention added resin solids do 100 The naphthenoylamide salt M153.1 is a water-insoluble, very high viscosity, dark brown-black oil.

EXAMPLES 40A AND 40B It is dispersible in water with difficulty, and aqueous dispersions prepared are not stable and readily break, necessitating constant agitation to keep the oil particles in a good suspension. It is, however, soluble in a variety of organic solvents, including toluene. The aqueous dispersions prepared are brown-black in color and unstable. A N. V. solids aqueous dispersion of the naphthenoylpolyamide M152 was prepared for evaluation. It was quite unstable, requiring constant agitation during titration additions, being brown-black in color. A 5% N. V. solids toluene solution of it was also prepared for evaluation. This was clear and deep brown-black in color.

The untreated beater stock as used in Example 38A was used in the evaluations of Example 40A and the untreated beater stock as used in Example 383 was used in the evaluations of Example 40B. The naphthenoylpolyamide M152 is at present manufactured as a pilot plant product by the Dearborn Chemical Company of Chicago, Illinois, and is considered to be an ampholytic surface active agent, having both basic and acidic groups in the same molecule.

EXAMPLE 40A EVALUATION DATA Co. 2% N. V. Solids cationically Reactive pH Value Emulsion of Aeryloafter Comments on Liquid Phase nitrilcbutadieneaddcd Addition to above treated fibers 9.15 clear. 9.00 instant pickup-clear. 8.90 Do. 8. 85 Do. 8. 75 Do. 200 8. 50 slower pickup-clear. 300 (visual end) 8. 50 very slow pickupelear 3 min. 350 8. 4O cloudy white.

Bone-dry weight processed hand sheet grams 15.86

Bone-dry weight blank hand sheet do 9.60

Per cent resin solids in sheet per cent 63 Per cent retention added resin solids do EXAMPLE 40B A 1000 gram, exact 1% untreated fiber solids suspension (bone-dry basis) as used in Example 38B was electrometrically titrated with a 5% N. V. solids aqueous dispersion of naphthenoylpolyamide M152. The titration proceeded smoothly, the pH gradually increasing to 10.15. There was no foaming at any point and the solution remained clear.

Thereafter 4 cc. of a 5% N. V. solids aqueous dispersion of naphthenoylpolyamide M152 were added to 1000 grams of a 1% untreated fiber solids suspension (bone-dry basis) and the mixture agitated for 15 minutes. Thereafter, the reacted mixture was electrometrically titrated with a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene.

EVALUATION DATA Ce. 2% N. V. Solids Cationically Reactive Emulsion of pH Value Aerylonitrilebutaafter Comments on Liquid Phase diene Added to Addition Above Treated Fibers 8.80 clear. 8. 75 instant pickupclear. 8.65 Do. 8. 55 slower pickup-clear. 8.40 Do. 8.30 Do. 3. 20 Do. 8.10 slower p1ekups11ght haze 1 mm.

Hand sheet made at end of titration cycle. No sticking tendencies at any point. Very, very slight haze in liquid phase and white water. Hand sheet 0. K. Sheet dried to constant weight at 215 F.

Bone-dry weight processed hand sheet grams 16.50

From this example it will be seen that the aqueous dispersion of naphthenoylpolyamide M152 is more effective in process reactions than is the toluene solution of this material.

EXAMPLE 41 In this example, the conditioning agent was of a type in which a basic hydrophilic group is linked in a heterocyclic ring. Accordingly a sulfonated alkyl benzimidazole was used in the form of a 5% N. V. S. aqueous dispersion, as the material is substantially insoluble in water but forms a dirty gray, highly turbid suspension. Thus to a 1% untreated fiber suspension 4 cc. of such an emulsion were added and, after agitating the suspension for 15 minutes, it was titrated with a 2% N. V. S. cationically reactive emulsion of an acrylonitrile-butadiene copolymer. Rope formation was noted early in the process and the pH of the suspension dropped from 7.65 to 7.15. The pick-up was perfect and amounted to EXAMPLE 42 is 175. The boiling point is 235 C. Viscosity at 100 F. equals centipoises. It is soluble in mlneral and vegetable oils, in common organic solvents and is very slightly soluble in water, but for all practical purposes it is insoluble in water. The commercial product as ob tained contains 80% of the cyclic glyoxalidine, the balance being the linear amide of oleic acid and aminoethylethanolamine. Aqueous dispersions of Amine 220 are alkaline, though the material is highly cationically reactive.

A 5% N. V. solids aqueous dispersion of Amine 220 was prepared with difiiculty-it being found necessary to heat the Amine 220 water mixture to about 195 F.and to pass the heated mixture through a colloid mill three to four times to effect a smooth suspension that remained stable only at elevated temperatures, and rapidly became unstable as the temperature of the dispersion decreased to approximately room temperature, necessitating the maintenance of an elevated temperature of approximately 190 F. of the Amine 220 aqueous dispersion during the titration cycles. The dispersion so made was light, creamy and translucent.

A 1000 gram, 1% untreated fiber solids suspension (bone-dry basis) was electrometrically titrated with a 5% N. V. solids aqueous dispersion of Amine 220, it being noted that the pH increased from 8.10 to 9.15.

An exact duplicate 1000 gram, 1% untreated fiber solids (bone-dry basis) suspension was treated by adding thereto 4 cc. of the 5% N. V. solids aqueous dispersion of Amine 220, and the mixture agitated for 15 minutes. Thereafter, the reacted mixture was electrometrically titrated with a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene.

EVALUATION DATA Cos. 2% N. V. Solids Cationic Emulsion 1 Note the peculiar titration, and the very slow reaction at end. An extremely tough hand sheet resulted. Liquid phase clear. White Water clear. N sticking tendencies at any point in processing. Excellent tough sheets resulted. Sheet dried to constant Weight at 215 F.

Bone-dry weight processed hand sheet grams 19.80 Bone-dry weight blank hand sheet do 9.78

Pickup do 10.02

Percent resin solids in sheet percent" 100 Percent retention added resin solids do 100 Amine 220 is made by condensing oleic acid with Z-aminoethylethanolamine at above 150 C., and xylene is used to remove the Water of reaction as fast as it forms. A second terminology for Amine 220 is hydroxyethylimidazoline and it belongs to the class of cationically reactive agents in which the basic hydrophilic group is linked in a heterocyclic ring. United States patents covering the manufacture of this material are: 2,267,965, 2,268,273, 2,355,837, 2,200,815 and 549,328 (British).

EXAMPLE 43 A special type of cationically reactive material, Norane R, was used in this example. It is Norane R, manufactured under United States Patents 2,261,097, 2,282,948, 2,315,135 and 2,386,631. It is not described technically by the manufacturer, but is said to be made (according to the patent disclosures) by the combination of stearic acid chloride, formaldehyde and pyridine. It is a soft, tan-colored paste, insoluble in water, and extremely difficult to disperse. A N. V. solids aqueous dispersion of Norane R was prepared by beating the Norane R water mixture to about 200 F., and passing the heated mixture through a colloid mill several times. A light cream-colored dispersion resulted of poor stability-necessitating the continual agitation of the dispersion during titration cycles. The stability remains satisfactory at 200 F., but decreases as temperature of dispersion decreases to room temperature. The general structural formula of Norane R is:

Bone-dry weight processed hand sheet grams 19.95

Bone-dry weight blank hand sheet do 9.78

Pickup do 10.17

Percent resin solids in sheet percent Percent retention resin solids do 100 EXAMPLE 44 Dithiobiuret is an off white colored crystalline solid, having a melting point of 193-195 C. It is a strong reducing agent, nearly completely insoluble in cold water. Very slightly soluble in hot Water and is classified as water dispersible. Soluble in dioxane, pyridine, aqueous caustic solution, acetone, Cellosolve and ethanol. Its structural formula is as follows:

II II HzNCNHCNHz Laboratory beater was furnished with unbleached southern kraft pulp, and stock beaten to a condition closely approximating the stock condition of previous evaluation runs. Thereafter, bone-dry beater consistency determined, and a series of exact 1000 gram, exact 1% fiber solids suspensions (bone-dry basis) prepared for evaluations and hand sheet data. Bone-dry beater consistency1.61%.

To a 1000 gram, 1% untreated fiber solids suspension (bone-dry basis) 4 cc. of a 5% N. V. solids aqueous dispersion of dithiobiuret were added, the mixture agitated for 15 minutes, and thereafter electrometrically titrated with a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene.

The usual tests were made. During the addition of the acrylonitrilebutadiene emulsion the pH of the fiber suspension dropped from 8.00 to 7.60, and the pick-up was good. Sixty per cent of resin solids were incorporated in the sheet and the retention was 100%.

EXAMPLE 45 Diallylcyanamid is a water-insoluble product-a clear mobile liquid having a boiling point of 153 C., and a melting point of -70 C. It is very soluble in most organic solvents. It dissolves many synthetic and natural resins. It has possible uses as an intermediate inorganic syntheses and as a solvent, and has the structural formula detailed below:

A 5% N. V. solids methyl ethyl ketone solution of diallylcyanamid Was prepared for use in evaluations and hansd sheet production. The pH value of this solution was 7.5

To a 1000 gram, 1% untreated solids suspension 4 cc. of a 5% N. V. solids methyl ethyl ketone solution of diallylcyanamid were added, the mixture agitated for 15 minutes and thereafter electrometrically titrated with a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene. Ropes formed right at the start of the titration and the pick-up was clear.

Hand sheet made at end of titration cycle. Liquid phase clear. White water clear. No sticking tendencies at any point in processing. Sheet dried to constant weight at 215 F. Excellent sheet, clear and uniform.

Bone-dry weight processed hand sheet grams 19.90 Bone-dry weight blank hand sheet do 9.91 Per cent resin solids in sheet per cent..- 100 Per cent retention added resin solids do 100 37 EXAMPLE 46 In this example, the cond tioning agent was phenylblguamde MBT salt, the letters MBT standing for mercaptobenzothiazole, the formula for which is given as EXAMPLE 47 Phenylguanidinestearate is a water-insoluble, creamcolored crystalline solid that softens at 60 C. The pH of a saturated aqueous dispersion equals 8.5 pH. It is dispersible in Warm water and very soluble in alcohol and benzene. The structural formula for phenylguanidinestearate is:

H H IfiIH HC NEoNH2-o11rn5o OH A N. V. solids aqueous dispersion of phenylguanidinestearate was prepared for use in this evaluation, the pH value of which was 10.05.

To a 1000 gram, 1% untreated fiber solids suspension 4 cc. of a 5% N. V. solids aqueous dispersion of phenylguanidinestearate were added, the mixture agitated minutes, and thereafter electrometrically titrated with a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene, as standard practice. Rope formation was very marked.

Hand sheet made at end of titration cycle. Liquid phase clear. White water clear. No sticking tendencies at any point. Execellent sheet clear and well formed. Sheet dried to constant weight at 215 F.

Bone-dry weight processed hand sheet grams 20.07

Bone-dry weight blank hand sheet do 9.91

Per cent resin solids in sheet per cent 100 Per cent resin solids added do 100 Per cent retention resin solids do 100 EXAMPLE 48 This example represents the addition of neoprene to kraft fibers. Using the techniques already described, the conditioning agent employed was phenylbiguanidehydrochloride and the additament was neoprene in the form of a 2% N. V. S. cationically active emulsion. Enough of the latter was added to amount to 40% addition. The pick-up was perfect and amounted to 100%.

EXAMPLE 49 Rosin Amine D is a water-insoluble primary amine of highv molecular weight derived from rosin acids. It is a pale yellow, viscous liquid having a density of 0.997 at C. It is soluble in most organic solvents, but practically insoluble in water. It readily forms salts With mineral acids and with organic acids of low molecular weight. The bromine number of Rosin Amine D is 49. The flash point is 192 C. The nitrogen content is from 4.3% to 4.5%.

To a 1000 gram, 1% untreated fiber solids suspension 4 cc. of a 5% N. V. solids methyl ethyl ketone solution of Rosin Amine D were added, the mixture agitated 15 minutes, and thereafter electrometrically titrated with a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene, as hereinabove outlined as a standard evaluating procedure. As in other examples, the pick-up Was 100% and no difficulties were encountered.

Addition of metal powders One of the remarkable features of the present invention is the possibility of introducing relatively large amounts of metal powders into a paper sheet or pulp product. It would hardly be expectable that such electrically conducting substances as zinc powder, aluminum powder and the like. would be operative froma cationobtained.

EXAMPLE The laboratory beater was furnished with unbleached southern kraft pulp and after brushing out the fibers for one-half hour, exactly 6% as is basis of Alex L-1205-X was added and the beating continued for one hour. Thereafter the bone dry consistency was determined and a series of exact 1% bone dry basis treated fiber suspensions prepared for electrometric evaluations and hand sheet production.

1000 grams of a standard, 1% bone dry basis treated fiber suspension (equivalent to 10 grams fiber solids) was electrometrically titrated with a 5% N. V. solids cat ionically reactive dispersion of metallic aluminum.

EVALUATION DATA Ce. 5% N. V. Solids Oationically pH Value Reactive Dispersion of Alnmi- After on Llquld num Added Addition ass 7. clear.

6.90 instant pickupc1ear. 6. 30 DO.

Bone dry weight metallic aluminum added grams 10.00 Bone dry weight blank hand sheet do 10.03 Bone dry weight processed hand sheet do 20.38 Actual metallic aluminum in sheet per cent 100.0 Retention metallic aluminum added do 100.0

This is without doubt the most spectacular example to date-for reason of the silvery metallic appearance of the sheet, which would be more spectacular with a clean, fully bleached fiber base. It is a striking example of nietallized cellulose, and the example indicates industrial possibilities in making metallized paper for a variety of uses, such as gaskets etc.

EXAMPLE 51 The usual beater stock was used in this evaluation, having been treated with Alox. A cationically reactive dispersion of Zinc dust was prepared for use in this example.

A standard l0-gram Alox-treated fiber suspension (exact 1% bone dry fiber solids) was electrometrically titrated with a 2% N. V. solids cationically reactive dispersion of metallic zinc.

EVALUATION DATA Co. 2% N. V. Solids Cat- I pHValue ggggg i gggifig After Comments Liquid Phase dded Addition 8.25 clear. 8. 00 instant pickup-clear. 7. Do. 7. 50 Do. 7.40 Do. 7.40 Do. 7.40 Do. 7.40 Do. 7. 50 slower adsorptiongray hazy. 7. 60 slow adsorption-gray cloudy. 7.65 gray cloudy liquid.

A hand sheet made from an exact duplicate 1% treated fiber suspension-after reacting it with 350 cc. (70% metallic zinc) of a 2% N. V. solids cationically reactive dispersion of metallic Zinc. Instant pick up. Liquid 39 phase clear. White water clear. 'Excellent gray-brown sheet made. Dried sheet to constant weight at 215 F.

. HAND SHEET DATA Bone dry weight metallic zinc added grams 7.00 Bone dry weight blank hand sheet do 10.86 Bone dry weight processed hand sheet do 18.10 Actual metallic zinc in sheet per cent 70 Retention of added metallic zinc solids.... do 100 glazed surface.

EXAMPLE 52 The treated beater stock of Example 50 was used in this evaluation. Previous electrometric titrations were used as a basis of additions.

A series of 14" x 14 hand sheets were made of 30- gram bone dry treated fiber base, using a 2% N. V. solids cationically reactive emulsion of acrylonitrilebutadiene and a 5% N. V. solids cationically reactive dispersion of metallic aluminum.

Liquid phase clear. Instantaneous reaction. White waters clear. No sticking tendencies at any point in processing. Spectacular appearing hand sheet resulted. No metallic bleeding on white blotters used to couch and press sheet. Sheets dried normally and calendered. On drying sheets assumed a silvery sheen, which was accentuated on calendering.

Actual sheet composition:

50% unbleached kraft pulp 25% metallic aluminum 25% acrylonitrilebutadiene A strip of the sheet was cured at 320 F. at 800 p. s. i. and 20 minutes. Cured strip had silvery metallic lustre and was tough and flexible.

Powdered minerals Another important feature of the present invention is the fact that it enables the introduction into paper and pulp products of quite unusually high filler contents, such as calcium carbonate (an alkaline filler), diatomaceous earth and other forms of silica, and similar substances that lend specific properties to the paper or pulp products. While ordinarily it is not possible to introduce more than about 20% by weight of such fillers into paper or pulp, the present invention makes it quite feasible to introduce 100% or even more, which is totally unexpectable and entirely novel. The following examples are illustrative of such processes.

EXAMPLE 53 The primary objectives of this example were:

To formulate a cationically reactive dispersion of calcium carbonate of fine particle size, to evaluate the control factors governing the incorporation or combination of such a cationically reactive dispersion of calcium carbonate with treated cellulose; and to evaluate the resultant product of such combination as a flame resistant material, and also as a calcium carbonate filled sheet, which would have a high utility value in itself, regardless of its flameresistant properties. It was considered that the selection of Atomite a highly developed calcium carbonate pigment was a logical selection based on the physical and chemical properties of this material as detailed below.

Average mean particle size microns 2.

This Atomite contains practically no water-soluble salts, shows no adsorbed or occluded ions, and is not bygroscopic.

(A) 300 grams of Atomite dispersed in 1000 grams of water containing 10 grams of Victawet 12, a non-ionic surface active agent which was added to the water to insure a complete wetting of the calcium carbonate particles.

(B) 60 grams 18 carbon atom chain amine acetate dissolved in 1630 grams of water at 60 C. (A) added to (B) through colloid mill, making several passes through mill to secure complete homogenization and smooth dispersion of N. V. solids. Water added to make suspension equal to 10% solids content.

A laboratory beater was furnished with unbleached kraft pulp, and after brushing the stock for one-half hour, exactly 6% as is Alox L-1205-X' was added and the beating continued for one hour. Thereafter the bone-dry consistency was determined and a series of exact 1% treated fiber suspensions prepared (bone-dry basis) for electrometric evaluations and hand sheet manufacture.

A series of exact 1% bone-dry treated fiber suspensions, each weighing 1,000 grams, were used to make blank hand sheets. These hand sheets were dried to constant weight at 215 F. and the bone-dry weight established.

Average bone-dry weight blank hand sheetl0.20 grams.

A standard 10-gram, 1% treated fiber suspension (bonedry basis) was electrometrically titrated with a 2% N. V. solids cationically reactive dispersion of Atomite" (calcium carbonate).

EVALUATION DATA Cc. 2% N. V. Solids Cationically pH Value Reactive Dispersion of Atomite After g f gg Liquid (Calcium Carbonate) added Addition 7.55 clear. 7. instant pickup-clear. 7. Do. 8.10 Do. 8.10 D0. 8.10 Do. 8.15 cloudy liquid phase. 8. 20 Do.

This is a peculiar electrometric titration, showing a sharp break point. Hand sheet made of exact duplicate fiber suspension plus 250 cc. above dispersion. Liquid phase clear. White water clear. Sheet 0. K. Dried hand sheet to constant weight at 215 F.

HAND SHEET DATA Bone-dry weight calcium carbonate added Actual sheet composition:

66.66% unbleached kraft pulp 33.33% calcium carbonate EXAMPLE 54 The treated beater stock of Example 53 was used in this evaluation. A cationically reactive dispersion of diatomaceous silica, e. g., Dicalite BP-45" was prepared for evaluation. A IO-gram standard treated fiber suspension, 1% bone-dry treated fiber solids suspension was electrometrically titrated with a 2% N. V. cationically reactive dispersion of diatomaceous silica, which latter is the fossil remains of tiny marine plants called diatoms. Other terminology for this material includes the following: Infusorial earth, diatomaceous earth, kieselguhr diatomite, amorphous silica, Celite and Dicalite. The material is both chemically and physically inert and contains no adsorbed or occluded ions. The principal use thereof heretofore in paper making has been that of a bulking agentdispersing agent for asphalt, pitch, etc. Large percentages of diatomaceous silica incorporated or combined with cellulose may produce a unique material. The greatest amount of such material that has been used commercially in paper is about 20% (on the fiber weight) and in this instance, in excess of 50% (on the fiber weight) was added in order to retain 20% diatomaceous silica solids in the sheet, the normal retention by precipitation being very low.

Using the already familiar technique, a hand sheetsolids

Claims (1)

1. PROCES OF AFFIXING WATER-INSOLUBLE ADDITAMENTS TO FIBROUS MATERIALS WHICH COMPRISES CONDITIONING SAID MATERIALS BY SUBJECTING THEM IN AN AQUEOUS ENVIRONMENT TO THE ACTION OF FROM ABOUT 1% TO ABOUT 20% OF THEIR DRY WEIGHT OF A CATIONICALLY ACTIVE SUBSTANTIALLY WATER-INSOLUBLE BUT WATER-DISPERSIBLE HIGHLY POLAR SURFACE-ACTIVE AGENT FROM THE GROUP CONSISTING OF: (1) SUBSTITUTED AMIDES HAVING THE GENERAL FORMULA