NO800754L - PROCEDURE FOR THE PREPARATION OF ADHESIVE COMPOSITIONS FOR CELLULOSE PRODUCTS - Google Patents

Description

The present invention relates to new and improved adhesive compositions. More particularly, the invention relates to new and improved adhesive compositions prepared from a specially modified rosin component and an ammonia and ammonium salt bearing material, such as ammonia, and ammonium salts, or their precursors, or reaction products of urea with a Léwis acid such as sulfuryl chloride .

Cellulose products. such as paper, stiff paper, paperboard, shaped products and the like, are produced mainly by applying a dilute suspension or solution of fibers in an aqueous medium to a fine mesh screen through which the aqueous medium is drained leaving a thin mat of fibers. The mat is removed from the screen, additional liquid is squeezed out, and the sheet is dried to form the desired product. The fibrous raw materials used in this process are generally one or more of the many commercially available pulp types. These masses include mechanical masses or grinding masses. bleached or unbleached, chemical masses e.g. bleached, unbleached and semi-bleached sulphate and sulphite pulps, as well as semi-chemical pulps. Other fibrous constituents used for the production of fibrous paper and paperboard raw materials include regenerated waste

paper, cotton fibres, inorganic and synthetic organic fibres, and mixtures of these materials.

The first step in paper production is the preparation of the paper raw material. Pulps are most conveniently handled in the form of a slurry to facilitate their mechanical processing, non-fiber additive mixing, and their feeding to the paper machine. Pulps are taken to paper production

tion in a slurry directly from mass production,

as both pulp and paper production are carried out in the same place; or they are received in the form of dry sheets and must be broken* up

to a pulp before use. This operation separates

the fibers and they are dispersed in the aqueous medium with minimal harmful mechanical impact to form a uniform starting material. The slurry is subjected to mechanical action, namely grinding or refining, before it is formed into a sheet of paper. During refining, the fibers are swollen, split, massaged

and unraveled under control to form smaller fibrillar elements and thus to influence the physical properties of the resulting end product. Unground pulp gives a light, flor-like weak paper, while well-ground pulp gives stronger, denser paper. During grinding or refining, many non-fibrous materials are added to the pulp solution. Among these are mineral pigments for filling such as kaolin, titanium dioxide, calcium carbonate and other well-known filling materials, color additives and dyes, adhesives and other known additives.

After the pulp slurry is ground and refined and the additives mixed in, this pulp slurry or "batch" is delivered to a continuous sheet forming apparatus,

such as a cylinder machine or a Fourdrinier, where it discharges onto a fine-mesh screen or strainer through which the liquid carrier or aqueous medium is drained

and on which a fibrous mat is formed. This fiber mat or sheet contains e.g. about. 80% water, when it leaves the screen and is therefore passed through one or more rotary presses to remove more water and finally passed through

a drying system, e.g. steam-heated rotating cylinders,

for obtaining the final product. Shaped pulp products are produced on other equipment by a similar process as

must shape, dry and press individual, shaped objects such as paper plates and the like.

As mentioned, adhesives are added to the mass slurry to make the finished product permanently

for liquid penetration. The adhesives can alternatively be excluded from the pulp additives and can be applied to the paper after it has been dried and has very effective penetration resistance. In this method, the dry sheet is passed through a glue solution or over a roller moistened with glue solution.

solution. Such sheets are respectively "post-glued" or "surface-glued".

Among the materials that are used as adhesives are rosin, various hydrocarbon and naturally occurring waxes, starches, adhesives, casein, asphalt emulsions, synthetic resins and cellulose derivatives. Rosin is the most widely used and most effective adhesive. Extracted rosin is often partly saponified with caustic soda and treated to form a thick paste with about 70-80% solids, of which up to approx. 30-40% is free, uf or soaped rosin. Dry (unsaponified) rosin and fully saponified rosin are also used as gluing agents. One. any of these rosin materials can be further modified, e.g. by adding maleic anhydride or another additive. In the paper mill, the rosin paste is dissolved or emulsified by dilution to around . 15% solids with hot water and then further dilution with cold water with vigorous stirring

to approx. 5% solids or less. This solution or dispersion is either used for surface bonding or it is added to the paper raw material, e.g. about. 0.1 or 0.5-4.0$ glue based on.dry fiber, usually before, but sometimes simultaneously with e.g. about. 1-3 times as much aluminum sulfate (papermaking alum). Aluminum sulfate is assumed

to form an ion-charged precipitant with the rosin glue

which is attracted to the oppositely charged fiber.

It was recently discovered that new adhesive compositions can be produced which are more effective than the well-known types dg which. are compatible with the currently used pulp and raw material as well as additives... Some of these adhesive compositions are described in U.S. Pat. Patent No. 4,022,634. These sizing compositions contain a specially modified rosin, ammonia and an ammonium salt. Other sizing compositions exhibiting these improved properties are described in U.S. Pat. Patent No. 4,141,750. These sizing compositions also contain a specially modified rosin, ammonia, an ammonium salt and additionally contain the reaction product of urea with a Lewis acid such as sulphuryl chloride, para-toluenesulfuryl chloride and the like, which urea reaction product can provide part of the ammonia and the ammonium salt which is essential in the compositions.

It has now been discovered that adhesive compositions such as those described in U.S. Pat. patents no. 4,022,63-4 and no. 4,141,750 can be provided with gluing properties that are significantly improved also compared to the compositions produced using the techniques described in said patents. These improved sizing compositions are provided by

to combine first and second components in such compositions,., while the second component is finely divided into liquid or solid particles, and the reaction time for these components is regulated to achieve the desired result. In one embodiment of the invention, the first component can also be finely divided into either fine liquid or solid particles for combination with the finely divided second component. The combination of the composition components in this way clearly accelerates the chemical reaction between the materials in the two components,

and this gives compositions which are surprisingly effective in substances.

The first component comprises one or more materials which yield both ammonia and ammonium salt when combined with other adhesive composition components. This ammonia/ammonium salt providing material is selected from the group consisting of ammonia, or its precursor; ammonium salts or their precursors; and reaction products

of urea and at least one Lewis acid selected from sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzenesulfonyl chloride, benzenesulfonic acid, ortho-toluenesulfonic acid, para-toluenesulfonic acid, ortho-toluenesulfonyl chloride and para-toluenesulfonyl chloride. Mixtures of these ammonia/ammonium salt-providing materials can also be used. Ammonia, e.g. ammonium hydroxide which is an aqueous solution of ammonia, and ammonium salt can be used as such in the first component, or precursors which produce ammonia and/or ammonium-. salt, e.g. in situ in the bonding composition, can be used

in the first component. Like for example. more fully described in U.S. patent no. 4,022,634, the ammonia and ammonium salt can be formed as the reaction product of urea and an acid, and optionally further ammonia or ammonium salt can be added to the urea-acid reaction product, ammonia can be reacted with salt-producing components, e.g. . acids, i. rosin to provide an ammonium salt, or ammonium salt can be reacted with ammonia-producing constituents in rosin to form ammonia. Acids which can be used for reaction with urea to form the ammonium salt and which can be present in the first or the second component are sulfamic acid and phosphoric acid as well as oxalic acid, methanesulfonic acid, trichloroacetic acid, nitric acid, sulfuric acid, hydrochloric acid, stearic acid and acetic acid.

The first component may also contain the reaction product of urea with at least one selected Lewis acid which

more fully described in U.S. Patent No. 4,141,750. Por formation of the reaction product, urea and at least one Lewis acid selected from the group consisting of sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzenesulfonyl chloride, benzenesulfonic acid, ortho- or para-toluenesulfonyl chloride, and ortho- or para-toluenesulfonic acid, are mixed and reacted. The preferred Lewis acids.' are sulfuryl chloride, chlorosulfonic acid, benzenesulfonyl chloride and benzenesulfonic acid, and the most preferred acids are ortho- or para-toluenesulfonyl chloride and ortho- or para-toluenesulfonic acid. If water is present, it is preferably included in amounts, parts by weight, which roughly correspond to urea plus Lewis acid, although urea can be reacted with the Lewis acid using water in excess of

shot of equal parts, or with a little water or without water.

If the Lewis acid is a solid, the reaction with urea can be carried out at a temperature somewhat. above the melting point of the acid.

The urea material is usually reacted with the Lewis acid in such amounts and at a temperature sufficient to cause a change in the pH of the mixture from an acidic pH before the reaction begins to a basic pH when the reaction is complete, as determined by of a pH meter. This temperature will usually vary from approx. 100-215°C and is to a certain extent dependent on the mixture's water content, and can generally be higher for mixtures with a lower water content.

Although the pH change is an important indication that the urea-acid reaction is complete, a more important ratio is the total acidity of the first component reaction product. This total acidity is measured as the amount of sodium hydroxide,

expressed as equivalent parts by weight of calcium carbonate, which should give a pink color to one million parts of a phenolphthalein-containing, 50% by weight, aqueous solution of the reaction product, and can be determined using the "Hach Chemical.Company Total Acidity Test (Model AC-5 Acidity Test Kit)". When the acid is reacted with urea, ammonia is formed, and an ammonium salt and this reaction not only raises the pH value, but also affects the total acidity of the mixture. This higher degree of acidity of the first component (higher than pure urea) is believed to partly explain the good bonding properties of the final composition obtained. The ratio between acid and urea is thus an important feature and is best defined as the resulting total acidity (ppm). which it creates. The desired mini-mill total acidity is at least approx. 1,000 ppm and is preferably at least approx. 4,000 ppm. The total amount of acid that reacts with urea is usually at least approx. 0.1%, and preferably from approx. 0.2 - approx. 8.0%, based on the weight of urea,

although more can be used, e.g. 15 or 20% acid, based on the weight of urea, to achieve the desired results.

The reaction of urea with acid is preferably, but not necessarily, carried out in the presence of rosin. and the organic acid material used to modify the rosin. If desired, however, urea can be reacted with the Lewis acid, while it is in mixture with the modi- . fissured rosin, as discussed in more detail below.

Additional amounts of ammonia, e.g. up to

about. 6% by weight of the total mixture of ammonia, water and urea-acid reaction product can optionally be added to the mixture of the urea-acid reaction product and water after

it is cooled to room temperature to promote the bonding results achieved by combining with the specially modified cplofonium material. E.g. 20 parts of 29% aqueous ammonia can be mixed, at room temperature, with 80 parts of the mixture of the urea-acid reaction product and water. This mixture can then be combined with the modified rosin, other components discussed in more detail below.

In another embodiment, an additional amount of ammonium salt combined with urea and a Lewis acid selected from the group consisting of sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzenesulfonyl chloride, benzenesulfonic acid, p- or o-toluenesulfonyl chloride, and p- or o-toluenesulfonic acid to provide the present sizing composition. The additional ammonium salt. is in addition to the ammonium salt formed by the reaction between urea and the selected Lewis acids according to the invention, and at least substantially the entire amount, e.g. at least 90% by weight, of the ammonium salt that is formed by reacting

The reaction between urea and an acid is preferably provided by reaction with the selected Lewis acids according to the invention. The weight ratio between urea and further ammonium salt, . if such is used, can often vary from approx. 2:1 to approx.

1:4, and is preferably from approx. 1:1 to 1:4. This first component reaction product can then be combined with modified rosin instead of .urea-acid reaction product-.

tet alone, to form an adhesive substance.

The ammonium salt used in the first component according to the invention can be the salt of an ammonium salt-forming acid which reacts with ammonia to form an ammonium salt such as e.g. sulfamic acid, chlorosulfonic acid, phosphoric acid, oxalic acid, p-toluenesulfonic acid, trichloroacetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric acid, stearic acid, acetic acid and sulfuryl chloride.

Solid, previously formed ammonium salts can be used or the salt can alternatively be formed by reacting the desired acid with ammonia. Dry powders of ammonium

sulphate, urea and chlorosulphonic acid are thus heated, e.g.

together to approx. l60°C at which temperature the mixture

goes from an acidic pH value to an alkaline pH^ value of approx. 8 for the formation of the ammonia/ammonium salt-containing^first component.

The second component in the present adhesive compositions comprises a rosin material which has been modified with an organic carboxylic acid material which may be an a, 3-unsaturated organic acid, an anhydride of such an acid or mixtures of such acids and anhydrides.. The a, 3-unsaturated acid or a derivative thereof can e.g. be an a, 3-unsaturated aliphatic acid usually containing approx. 3-10,. preferably approx. 3_6 carbon atoms, such as e.g. acrylic acid, and the preferred ones are maleic acid, maleic anhydride and fumaric acid.

Rosin is a mixture of resin acids. (including abietic acid, pimaric acid and levopimaric acid), hydrocarbons'

and high molecular weight alcohols which are obtained from a variety of sources. Gum rosin is the residue left after the distillation of turpentine oil from crude turpentine bleosin obtained from living pine trees, wood rosin is the residue left after the distillation of volatile fractions in the solvent extraction product (usually using naphtha as a solvent) from pine stumps,

and tall oil rosin is a by-product of the fractionation,

of tallow oil (an oily mixture of colophoic acids, fatty acids and neutral materials obtained from the acid treatment of spent black liquor from paper and pulp processes). All three types are chemically very similar, with the exception that tall oil rosin often contains 1-5% fatty acids that remain after fractionation, while this is not the case with rubber rosin and wood rosin. As mentioned above, rosin can be used in the adhesives in "dry" form or can be partially or fully saponified. In the present adhesive compositions, rubber, wood and tall oil rosin or mixtures thereof can be used. tall oil rosin

ium is preferred, however, because it usually gives the best results, possibly due to the presence of the fatty acids, although this is not fully understood.

The organic acidic materials that can be used to modify the rosin material are, as mentioned, a, 3-unsaturated organic acids and anhydrides and their mixtures. Amounts of the organic acidic material used to achieve the desired results usually vary from about 5~50% or, more, based on the weight of rosin, but preferably from about 5-30$, especially about 15% is used. The modified rosin can be converted into a soap by known methods, e.g. . by the addition of sodium hydroxide, potassium hydroxide, or ammonium hydroxide to form an alkali metal or ammonium soap of the rosin acids. The rosin material can usually be saponified after it has been modified. In all cases, the saponification need not be complete, but is preferably sufficient to make the final sizing composition water soluble In the case of the embodiment of the present invention which comprises the reaction product of ammonia and modified Vrosin, amm oniakk. preferably used as one of the saponifying bases.

According to the present invention, the first and second components of the composition as described above are combined while the second component and preferably also the first component are in a finely divided liquid or solid state or are finely divided mixtures of liquid and solid substances. The second component and optionally the first component may be finely divided into particles which may be solid or liquid, i.e. small droplets, by means of various methods which will be known to the person skilled in the art. The average diameter for such liquid or solid particles varies from approx. 10-1000 ym, preferably from approx. 20-250<y>m..

According to the invention, the reaction between the first and the second component can be regulated to provide products with improved properties. Such regulation can be carried out using relatively short reaction times. The reaction time can be of the order of magnitude up to approx. 1 minute, preferably up to approx. 30 seconds, e.g. 15-30 seconds. The reaction time can often be approx. 10 seconds. ' A particularly effective way of regulating reaction-

the time of and provide" adequate mixing of it

first and the second component, is to form a coincident spray of these materials in the desired particle size range.

It has been found that conversion of the second component to fine particles can be achieved by adding the liquid or solid second component to the first component. while the first component in liquid form is subjected to high shear agitation in a mixer. Addition of the second component to the agitated first liquid component results in comminution of the second component when it comes into contact with the agitated liquid. The agitation element in the mixer can be operated at a speed which provides a shear agitation which is sufficient to comminute the second component being added into particles with an average diameter in the range of 10-1000 um. Por stirring the first component in which the second component is thus combined, one can e.g. used a Waring mixer at a speed of approx. 10000-25000 rpm.

When the two components are in liquid form, alternatively both components can be passed through spray nozzles and the two spray streams combined in a suitable container. In this way, both the first and the second component are broken up into small droplets of aerosol size. The nozzles used for the formation of small droplets advantageously have an average size of approx. 10-200 ym, preferably ca. 20-

125 µm. The second component can advantageously be sprayed from nozzle No. ^9^87650 (manufactured by Spray Engineering Company,

East Spit Brook Road, Nashua, N.H. 03060), while the first component is passed through a similar nozzle. Steam under pressure is one. suitable gas for conducting of. the other component through such a nozzle. The first component spray can be formed with or without the use of a pressurized propellant. Streams from the two nozzles can then be combined to effect component mixing, while both components are in a finely divided state.

When combining the first component with the second component to form the present gluing composition, sufficient amounts of each component are used to achieve effective gluing amounts, usually about 25-85% based on the total dry weight of the gluing composition, of the first component , and from about .. 7$- 15% of the second component,,, in the adhesive composition.. The prepared composition usually contains at least about 25% by weight and often about 40-60% by weight, water.

While the second component and possibly the first component are finely divided according to the present method into fine liquid or solid particles, the components can be mixed at room temperature. These components may less advantageously be mixed and heated to the boiling point of the mixture to ensure that all reactions are complete...

When the first and second components are combined at an elevated temperature, the modified rosin

.heated to or'maintained at a temperature at which the combination can be effected. This combination may include adding a diluted mixture of the first component reaction product that has been heated to the heated second component to effect chemical and physical mixing. The mixture of the first and second components can be heated to over 100°C

to boil off water, and is preferably kept at the boiling temperature until the cloudy solution becomes substantially clear. After the component combination is complete, possibly very small amounts of ammonium hydroxide can be used to adjust the product's pH value to the basic range, i.e. to above 7 if it has fallen to the acidic range, i.e. below 7" Amounts of ammonium hydroxide up to approx. 0.05% by weight of the mixture will usually raise the pH to the desired range. The choice of dilution concentrations for the first

and second component before component mixing is dependent on the desired relative amounts of first and second component and on the desired concentration in the resulting adhesive compositions. The choice of combination temperatures used is a function of processability and the desired degree of chemical and physical mixing, although in an embodiment of the present method temperatures of at least approx. 27°C

prevent precipitation during mixing.

After the first and second components have reacted, they can be contacted with an aqueous solution of one or both of sodium or potassium hydroxide to obtain a product of the desired pH value. These bases can preferably be added in order, especially KOH followed by NaOH. The addition of the aqueous base may serve to terminate the reaction between the first and second components.

As mentioned above, ammonia, an ammonium salt and the specially modified rosin or a soap thereof can be combined at room temperature to obtain an adhesive. The specially modified rosin soap can be made by pouring the hot mixture of the rosin material and the rosin-modifying organic acid material into an aqueous solution of a saponification base, e.g., sodium hydroxide and/or potassium hydroxide, with slow stirring to saponify the modified rosin. Sufficient aqueous solution of the saponification base can be used to give an aqueous mixture of modified rosin soap containing from approx. 50 - approx. 70% by weight solids. Based on the total weight of ammonia, ammonium salt and rosin as well as the modifying organic acidic material on a dry basis, the sizing agent can have from approx. 3 - approx. 30% ammonia, from approx. 4 - approx. 72% ammonium salt and from approx. 93 - approx. 25% rosin plus modifying organic acid material, using an ammonium salt to ammonia ratio of over approx. 1:1. The term "dry" is used in the present context in the sense of excluding any water that is present. The ammonia can be formed in situ by e.g. reaction between the rosin material, the modifying organic acid material and the ammonium salt by using from approx..4 - approx. 75% rosin plus modifying organic acid material based on the total weight of the ammonium salt and the rosin material. as well as modifying organic acidic material on a dry basis.

The amount of ammonia used depends on whether the ammonia is the only saponification agent used.

When ammonia is used alone to saponify the modified

rosin, can be used from approx. 10 - approx. 75% ammonia,

from approx. 25 - about, 90% rosin plus modifying organic acid material based on the total weight of ammonia and rosin plus said modifying material on a dry basis, to prepare the sizing agent. When ammonia is reacted with a soap of the specially modified rosin, the mixture can usually be prepared with from approx. 4 -. about. 60% ammonia, and from approx. 96 - 40% rosin plus modifying organic acid material, based on the total weight of ammonia and rosin plus said modifying material on a dry basis.

Methods involved in the preparation of the adhesive compositions in question are, apart from the feature of combining the components, while the other component and possibly both components are in a finely divided state, set forth in U.S. Patents No. 4,022,634 and No. 4,141,750 ..

Available adhesives have a pH value usually in the range of at least approx. 6.6 - approx. 10 or 12. and a total acidity of at least approx. 1000ppm. The pH value is preferably at least approx. 8,. e.g. about. 9-H« This total degree of acidity is measured as the amount of sodium hydroxide, expressed as equivalent parts by weight of calcium carbonate, required to

give a pink color to a ppm phenolphthalein-containing adhesive composition according to the invention, and can be determined under, using

else of "Hach Chemical Company Total Acidity Test (Hach Chemical Co., Ames, Iowa, Model. AC-5 Acidity Test Kit)". The preferred purpose of each of the embodiments of the present,

end composition is to achieve the highest possible total acidity without lowering the pH value to a level which. do. the sizing agent insoluble in papermaking water. The proportions of the components in the adhesive compositions according to the invention

the treatment may thus vary in accordance with this

target and are thus appropriately defined by means of the pH value and total acidity that they provide in the adhesives.

The improved adhesive compositions exhibit superior adhesive properties compared to conventional adhesives used in the same quantity, and equivalent properties

creates can be achieved when they are used in smaller amounts than.de

conventional adhesives, and the user can thus satisfy existing standards with less adhesive than has been necessary up to now, and therefore at a lower price. Products resulting from the use of the present adhesive compositions can be brighter and stronger than those obtained using previously available adhesives. The new sizing compositions also help the drying of the sheet, when used as a pulp additive so that the paper machine can be run faster to form a sheet with the same moisture content. Alternatively, more water can be added to the pulp to give the fibers on the paper machine wire a better orientation and thus produce a stronger paper. The sizing compositions are normally used alone as an adhesive with paper-making alum for pulp sizing or surface sizing, but can be combined with various adhesives to replace a significant part of these known agents.

The improved sizing compositions can be used as mass additives. or as surface adhesives in the manufacture of cellulose products. The exact amount to be used to achieve optimal results can vary depending on the type of pulp used and the desired properties in the finished product. Quantities of usually less than those used up to now with known adhesives can usually be used to obtain substantially equivalent or superior products. While known rosin adhesives are usually used in amounts of from approx. 0.1 or 0.5% and.

up to approx. H% solids based on the weight of fibers in the pulp slurry, can thus e.g. present compositions are used in amounts as low as approx. 0.05 or 0.25%• From approx. 0.05 - 0.25 and up to approx. 4% of the compositions, dry weight based on the weight of fibers in the pulp slurry,

can thus be used. When 1% known rosin adhesive is used, typically 0.5% of the present composition can be used to achieve substantially equivalent or superior results.

Production of the gluing compositions on

the method specified here also provides cheaper compositions*

This can be achieved because less of the relatively more expensive components (e.g. the modified rosin) are used to produce the gluing compositions which have an efficiency substantially equivalent to compositions produced in a known manner and which contain more of the relatively more' costly compo-. nents.

Methods according to the invention are illustrated

in the following examples.

Example_l

The first component of an adhesive is prepared by placing 4,000 g of commercially available urea, 200 g of sulfamic acid and 4,200 g of water in a boiling container and then heating with slow stirring of the contents until the reaction mixture boils at atmospheric pressure. When the temperature hair approx. 103°C, boiling stops, water loss ceases and the pH value of the solution, determined using a pH meter, rises to approx. 8. The resulting first component-

is a clear solution with a total acidity of 86,000

ppm determined with "Hach Chemical Company's Acidity Test Kit Model AC-5.

To form the second component, namely the modified rosin, 3•000 g of commercially available tall oil rosin is melted in a boiling vessel. The following ingredients are slowly added to the melted rosin while stirring: 360 g of fumaric acid plus 100 g of 37% formaldehyde and 3 g of para-toluenesulfonic acid as rosin crystallization inhibitors. The reaction mixture is then heated

with continuous stirring until approx. 205°C and kept at this temperature for 2-10 hours.

To form the adhesive, the first component in an amount of 600 g and 300 g of water is placed in

a "high-speed" mixer, e.g. a Waring mixer. The second component (300 g), either in a molten state or in the form of solid particles, is added to the contents of the mixer and stirred for approx. 10-60 seconds, and preferably approx. 20-30 seconds. Adding the second component in this way ensures that this second component is crushed when it enters

contact with the stirred first component.'

.Potassium hydroxide (60-120 g) in the form of a 50% by weight water solution is then added and mixing is carried out for 5-10 seconds. The solution's pH value is then adjusted with sodium hydroxide to a value in the range from 9.0 - approx. 10.0, and sufficient water is added to bring the total solids content of the solution to approx. 50% by weight.

The first neutralization can be carried out with sodium hydroxide, but if this is done, the second neutralization should be carried out with potassium hydroxide. Example_el_2_

A first component in an adhesive is prepared in the same way as stated in example 1.

Por formation of the second component, 3,000 g of commercially available tall oil rosin is melted in a. cooking container. To this rosin, slowly add 360 g of fumaric acid with moderate stirring. The reaction mixture is then heated to approx. 205°C and held at this temperature for 2-14 hours. The hot reaction product is then added. f0^siXtis...-tALjsn.-_-hot solution of 700. g of sodium hydroxide dissolved in 4.032 g of water. The pH value of the final solution of the second component: is approx. 10.0.

To form the adhesive, the second component and additional water are mixed in the following quantities:

This mixture is then combined with 190 g of the first component to form a total of 420 g of adhesive.

Eczema Gel_3_

The first and second components of an adhesive are prepared in the same way as stated in example 1.

To form the sizing agent, the first component in an amount of 600 g and 300 g of water is placed in a "high-speed" mixer, for example a Waring mixer. 300 g of the second component, either in a molten state or in the form of solid particles, is added to the contents of the mixer and stirred for from about 10-60 seconds, and preferably about 20-30 seconds..

Potassium hydroxide (60-120 g) in the form of a 50% by weight water solution is then added, and the solution is stirred for a few seconds. The pH value of the solution is then adjusted with sodium hydroxide to 9.0-10.0 and sufficient water is added to bring the total solids content of the solution to approx. 50% by weight.

Sodium hydroxide can be used for the first neutralization, but if this is done, potassium hydroxide should be used before. the second neutralization.

Example_4

In one apparatus as shown in the accompanying drawing, the second component is produced as indicated in example 1 in a quantity of 1,000 parts, formed into a spray 1 by passing it through an adjustable nozzle 2 (e.g. nozzle No. 49487650). The spray or shower 1 is injected into a pipe 3, where it meets a spray 4 of the first component, also

set as indicated in example 1, and comes out of the nozzle 5..' The temperature of the second component is approx. l82°C and the nozzle 2 through which it passes is heated by means of jacket 6 filled with steam at a pressure of approx. 10.85 kg/cm manometer pressure and at a temperature of approx. 182°C. The quantity of the first component is 2.0.00 parts of a 50% by weight solids product.

Water from pipe 7 in an amount of 1,000 parts minus the steam

which comes from the openings in the jacket 6 around the nozzle 2 for the second component. is introduced into the device through openings 8 to wash the walls of the pipe 3 and prevent the build-up of solids. The reaction product encounters a spray .9 of 50% by weight potassium hydroxide solution containing 200-400 g of potassium hydroxide introduced into the pipe 3 through the opening 10 in the channel 11. The resulting solution 12 is then pumped to a storage tank (not shown) by means of a pump 13 through

channel 14, where the pH value is set, to from 9.0 - approx. 10.0 with either KOH or NaOH.

The two nozzles 2 and 5 are shown in such a configuration that the two streams of droplets, i.e. sprays 1 and 4 of the second and the first component are moved side by side. Other placements of the nozzles 2 and 5 can be used including one where the nozzles are placed horizontally on a diameter of the pipe 3 so that the streams of drops are directed in the opposite direction to each other.

The drawing shows that water is led down the inside of the pipe to prevent the build-up of solids. Another method would be to have a series of water jets arranged around the inner periphery of the tube. Eczema gel_5

In order to test the adhesives prepared by the present process, samples of the products of Examples 1, 2 and 3 are processed as follows. The sizing agents are mixed with papermaking alum in bleached hardwood pulp to compare their performance. Hand sheets are made using 5.7 g of fiber diluted in water to a 1.0% by weight slurry. The fibers and water are mixed in a Waring mixer for approx. 1 minute and then the gluing agents are added in a quantity of 4.5 kg per tonnes of fiber and mixed for approx. 45 seconds.

The alum is then added in a quantity of 6.75 kg per ton. fiber.

The slurries are then further diluted with water to a fiber solids content of approx. 0.1% based on the weight of the slurry. Sheets are then formed with a Williams Handsheet Former from slurries prepared with the sizing agents as indicated in the Examples. The sheets are placed between two tracing papers and then dried in a hot press at a temperature of approx. 110°C and a pressure on

about. 3j5kg/cm 2. The sheets are then conditioned for 24 hours at 50% relative humidity and 22°C and tested using the Tappi swimming test. The swim test used to compare the effectiveness of different adhesives uses an acidic ink with the following composition:

In the swimming test, paper squares of a given size are placed on the surface of the liquid ink, and the time in seconds for 50% of the surface to be colored by the ink is noted. In general, the more seconds recorded for a given attempt, the more effective is the adhesive used therein.

The results obtained are given in Table I. Each set of experiments is carried out on one day with the same fiber and the same type of water. Control results will vary from day to day depending on the fiber used, water quality and possible other factors.

The average values for the trials in Table I are as follows: None of the components comminuted (old method): 7Y1 seconds; Second component finely divided (new method): 1,206 seconds.

This shows an improvement on it. new method-in relation, to the old method of 1. 206-771

The values for the swim test on the control samples reported in Table I are generally higher than the values obtained in previous work. This is due to the following: (a) the second component is saponified with KOH instead of with NaOH, (b) a small amount of NaOH is added to the sizing agent after the addition of the second component, and (c) a better quality of tall oil^rosin is used for reaction with fumaric acid in the preparation of the second component.

Example_el_6.

Por to test the adhesives produced according to the present method and in which both first and second compo-

nent is finely divided, samples of products prepared in example 4 are tested using the swimming test. The hand-sheet production and swimming test method used are essentially identical

with what is described in example 5 - The obtained results

tater are indicated in Table II. As before, each set of tests is carried out over the course of a day with the same fiber and the same type of water. Control results will vary from day to day.

depending on hand sheet size, fiber used, water quality and possible other factors.

The average values for the first six trials

in Table II is as follows: Neither component finely divided (old method): 372 seconds Both components finely divided (new method): 5^7 seconds

This shows one improvement in the new method compared to the old method of 5^7-372 „ inv • .

—3~7~2— xiuu/o-H//»

Experiments 7 and 8 in Table IT demonstrate that a sizing composition prepared according to the present invention is about as effective a sizing agent as a similar agent prepared in a conventional manner using twice as much of the rosin-modifying fumaric acid material.

Claims (24)

1. Method for producing a gluing composition with improved gluing properties, characterized by. that you combine A) a first component, comprising a material which yields both ammonia and an ammonium salt when combined with the other components of the adhesive composition, the ammonia-ammonium salt-yielding material being selected from the group consisting of ammonia or its precursor, ammonium salts or its precursor , the reaction product of urea and at least one Lewis acid selected from sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzenesulfonyl chloride, benzenesulfonic acid, ortho.o-toluenesulfonic acid, para-toluenesulfonic acid, ortho-toluenesulfonyl chloride and para-toluenesulfonyl chloride, and mixtures of these materials, and B) another component comprising a saponified, partially saponified or unsaponified rosin modified with an organic acidic material selected from α,,3-unsaturated aliphatic carboxylic acids with approx. 3-10 carbon atoms, anhydrides thereof and mixtures of said acids and anhydrides, - where the combination of -first and second component is carried out while the second component is in finely divided form to thereby provide a gluing composition.or precursor thereof, and that one regulates the reaction time foi? said first and second components for providing the improved gluing composition, the composition or its precursor comprising gluing-effective amounts of said modified rosin, and gluing-promoting amounts of. ammonia and ammonium salt is such that a gluing composition is provided with a total acidity of at least approx. 1,000 ppm. 2. Method according to claim 1, characterized in that the second component/is converted into fine particles when it is added to the first component, while subjecting the first component to high shear agitation which is sufficient to form particles of said second component with an average diameter of approx. 10-1,000 etc. 3.. Method according to claim 1, characterized in that the first component is also finely divided into fine particles, while said first and second components are combined, both components having an average diameter of approximately 10-200 ym. 4. Method according to claim 3, characterized in that the first and second components are converted into fine droplets by passing the components through spray nozzles, and that the two spray streams are mixed in a suitable container. 5. Method according to claim 2 or 4, characterized in that the rosin material is modified with an organic acid material selected from the group consisting of maleic acid, maleic anhydride, fumaric acid and mixtures thereof. 6.., Process according to claim 1, characterized in that the ammonium salt is the salt of an acid selected from the group consisting of sulfamic acid, phosphoric acid, oxalic acid, methanesulfonic acid, trichloroacetic acid, nitric acid, sulfuric acid, hydrochloric acid, stearic acid and acetic acid. 7. Method according to claims 1-6, characterized in that a gluing composition is produced with approx. 3-30% ammonia, approx. 4-72% ammonium salt and approx. 93-25% rosin plus organic acid material, based on the total weight of ammonia, ammonium salt and rosin plus organic acid material on a dry basis, and using a ratio between ammonium salt and ammonia of over approx. 1:1. 8. Method according to claim 7, characterized in that a rosin material is used which has been modified with approx. 5-30% by weight, of the rosin material, of the organic acid material and which is at least partially saponified, the ammonium salt being formed in situ after combining the first and second components such as the reaction product of ammonia and the salt-forming acid, and that' the composition consists of an aqueous mixture. 9. Method according to claim 6, characterized in that the ammonia is provided in situ by reaction between rosin, the rosin-modifying organic acid material and the ammonium salt, and that the rosin material is at least partially saponified. 10. Method according to claim 9, character. cert by producing a gluing composition with approx. 4-75$ ammonium salt and approx. 96-25$ rosin plus modifying organic acid material based on the total weight of the ammonium salt and rosin material plus modifying organic acid material on a dry basis. 11. Method according to claim 5, characterized in that the ammonium salt is provided in. situ by reaction between the rosin material, the organic acid material and ammonia after the combination of. first and second component. 12. Method according to claim 11, characterized in that a gluing composition is produced with approx. 10-75$ ammonia and approx. 90-25$ rosin plus modifying organic acidic material based on the total weight of ammonia and rosin plus modifying organic acidic material on a dry basis. 13.. Method according to claim T-12, characterized in that the gluing composition contains approx. 4-60$ ammonia and approx. 96-40$ rosin plus modifying organic acid material, based on the total weight of ammonia and rosin' plus modifying organic acid material on a dry basis. 14. Procedure according to requirements. 5, characterized in that tall oil rosin is used as rosin, which is at least partially saponified. 15. Method according to claim 5, characterized by . that the first component comprises approx. 25-85% by weight and that the second component comprises approx. 75-15 wt-$ of their mixture on a dry weight basis. 16. Method according to claim 15, character. - i s e',r t in that the composition contains a reaction product between urea and Lewis acid and that the Lewis acid reacted with urea comprises from approx..0.2 - approx. 8 wt-$ urea. 17" Method according to claim 16, characterized in that the composition contains at least approx. 25% by weight water. •• 18.. Method according to claim 17, characterized in that the Lewis acid is selected from para-toluenesulfonic acid and para-toluenesulfonyl chloride. 19. Method according to claim 17, characterized in that the ammonium salt is ammonium sulfate and is added to the composition to provide a weight ratio between ammonium salt and urea of from approx. 4:1 to approx. 1:2. 20.. Method according to claim 17, characterized in that the gluing composition contains approx. 3-30$ ammonia, .approx. 4-72% ammonium salt and approx. 93-25% rosin plus modifying organic acidic material, based on the total weight of ammonia, ammonium salt and rosin plus modifying organic acidic material on a dry basis. and that • the composition is prepared using a ratio between ammonium salt and ammonia of over approx. 1:1. 21. Method according to claims 1-20, characterized in that a reaction time of up to approx. 1 minute, preferably approx. 10-30 seconds. 22. Method according to claim 1, characterized in that the first and second components are combined to form one. concurrent spray of said components, and that this spray is brought into contact with an aqueous solution of potassium hydroxide and/or sodium hydroxide to regulate the reaction time. 23. Method according to claims 1-22, characterized in that the gluing composition has a pH value of approx. 9-12. 24. Method according to claim 2, characterized in that the combined first and second components are brought into contact with an aqueous solution of potassium hydroxide and/or sodium hydroxide in order to regulate the reaction time.