FI64676B - FOERFARANDE FOER FRAMSTAELLNING AV EN LIMBLANDNING - Google Patents

Description

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Ma lJ '' UTLÄGGNINGSSKRI FT 040/6 «Sfi c (45) .rn 1C: .7: 3 ^ (51) K, jk.Wi.3 D2-Th 3/08, 5/12, 5/36 ENGLISH- FINLAND <*) Ptt * n «lh * ktmu * - P» t * nt »nsöknlnj 8008ll (22) H» k * ml »pllvl— AnsBknlngsdag 1¾. 03.80 (23) Primary Cloud - Glltlghetidtg lU.03.80 (41) Become Public - Bllvlt offentllg qq qq

Patent and Registration Office .... . , ,, „, * (44) Date of dispatch and of issue of the hearing. -

Patent and registration authorities AnsBkan utlagd oeh utUkrlften publlcerad 31.08.83 (32) (33) (31) Pyydetty etuoikeus — Begird prlorltet lU. 03. 79 USA (US) 020U80 (71) The Plasmine Corporation, 6l Bishop Street, Portland, Maine 0 ^ 103, USA (US) (72) Ralph Waldo Emerson, Boston, Massachusetts, USA (US) (7 ^) Leitzinger Oy (sl +) Method for preparing a gluing mixture - Förfarande för framställning av en limblandning

The present invention relates to a process for preparing an adhesive mixture having improved adhesive properties, which process comprises combining A) a first component forming both ammonia and ammonium salt in combination with a second component of the adhesive mixture, wherein the ammonia-ammonium salt-forming agent is ammonia or ammonium salt or a precursor thereof; the reaction product of urea and at least one Lewis acid, which Lewis acid can sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzenesulfonyl chloride, benzenesulfonic acid, ortho-toluenesulfonic acid, para-toluenesulfonic acid, ortho-toluenesulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulf or a mixture of these substances; and B) a second component which is a saponified, partially saponified or unsaponifiable resin modified with an organic acidic α material which is a (3-unsaturated aliphatic carboxylic acid having about 3 to 10 carbon atoms, an anhydride thereof, or a mixture of these acids and an anhydride mixture comprising an adhesive mixture or a precursor thereof of adhesive amounts of said modified resin and adhesion enhancing amounts of ammonia or ammonium salt-forming material, wherein the amount of modified resin, ammonia and annonium salt is sufficient to form a total adhesive mixture having a total acidity of about

In principle, cellulosic products such as paper, kraft paper, cardboard, presses and the like are prepared by applying a dilute 2 64 6 7 6 fiber suspension or solution in an aqueous medium to a fine sieve through which the aqueous medium flows, leaving a thin non-fibrous matter. The mat is removed from the screen, more liquid is squeezed out, and the sheet or mat is dried to form the desired product. The fibrous raw materials used in this process are generally one or more commercially available pulp types. These pulps include mechanical pulps or bleached or unbleached wood chips as well as chemical pulps such as bleached, unbleached and semi-bleached sulphate and sulphite pulps and semi-chemical pulps. Other fibrous ingredients used in the manufacture of fibrous paper or paperboard include recovered waste papers, cotton fibers, inorganic and synthetic organic fibers, and mixtures of these materials.

The first step in the manufacture of a paper product is the manufacture of pulp. The pulps are treated as a suitable water to facilitate their mechanical handling, mixing of the non-fibrous additive and feeding to the paper machine. The pulps are fed to the paper machine as an aqueous slurry directly from the pulping step when both pulping and papermaking are performed at the same location; otherwise, the pulp is received in dry sheets or sheets and kept, put in a liquor before use. Sludge formation separates the fibers and disperses them in an aqueous medium so that as little harmful mechanical action as possible is continuously obtained to provide a uniform starting material. The pulp slurry is subjected to a mechanical action known as simplification or cleaning before the paper sheet is formed. During purification or refining, the fibers swell, are cut, soaked, or macerated and rubbed in a controlled and controlled manner to form small filamentous elements, thereby providing the desired effect on the physical properties of the final product. The unbleached pulp forms a light, fluffy, weak paper, while a well-bleached pulp yields a snowy, denser paper. During the refining or refining process, many non-fibrous materials are added to the pulp mixture. These include, for example, mineral pigments, such as kaolin, titanium oxide, calcium carbonate and other known fillers, in addition to the addition of color additives and colorants, sizing agents and other known simplifying additives.

After the pulp slurry has been purified and refined and the additives mixed with it, this pulp slurry or "feed" is delivered to a continuous sheeting apparatus, which may be, for example, a cylinder or Fourdrinier, from which it discharges into a fine sieve through which a liquid carrier or aqueous medium flows. fiber mat. For example, the nonwoven mat or sheet contains about 80% water as it exits the screen and is therefore passed through one or more turret presses to continue dewatering, after which it is fed through a drying system, e.g., steam heated rotating cylinders, to produce the finished product. Compressed pulp products are manufactured in different devices by a similar method, whereby the devices form, dry and compress individual compressed products, such as paper plates and the like.

As mentioned above, sizing agents are added to the pulp slurry in the papermaking process to make the final product impermeable to liquid. Alternatively, the sizing agents can be omitted from the pulp additives and can be applied to the paper after it has been dried, thus very effectively preventing the ingress of liquid. In this method, the dry sheet is passed through an adhesive solution or over a roller irrigated with an adhesive solution. In the corresponding order, such sheets are referred to as "pool glued" or "surface glued".

Examples of sizing agents used today include resin, various hydrocarbon and natural waxes, starches, adhesives, casein, asphalt emulsions, synthetic resins and cellulose derivatives. Resin is one of the most widely used and effective adhesives. The extracted resin is often saponified with alkaline soda and treated to give a thick paste with about 70-80% solids, of which up to about 30-40% is free, unsaponifiable resin. Dry (unsaponifiable) resin and fully saponified resin are also used as sizing agents. All of these resins can be further modified, for example, by the addition of maleic anhydride or some other excipient. In a paper mill, the resin paste is dissolved or emulsified by diluting it with hot water to a solids content of about 15% and then further diluting it with cold water with vigorous stirring to a solids content of about 5% or less. The solution or dispersion is either used for surface sizing or is added to the pulp, for example about 0.1 or 0.5 to 4% of sizing based on dry fiber, usually before, but sometimes simultaneously with, aluminum sulphate (as a papermaking substrate) and, for example, about 1 to 3 times aluminum. - 4 64676 amount of sulphate. Aluminum sulfate is believed to form an ionically charged precipitant with a resin adhesive that adheres to the oppositely charged fiber. Recently, it has been found that it is possible to produce new sizing compositions which are more effective than known types and which are compatible with the abrasive and pulp material and additives currently used. Certain such sizing compositions are disclosed in U.S. Patent 4,022,634, issued May 10, 1977 to Emeron et al., Which is incorporated herein by reference. These sizing compositions contain a specially modified resin, ammonia and ammonium salt. Other such adhesive compositions with improved properties are disclosed in U.S. Patent 4,141,750, issued February 27, 1979 to Emerson et al., Which is incorporated herein by reference. These sizing compositions also contain a specially modified resin, ammonia, ammonium salt, and further include a Lewis acid-derived urea reaction product such as sulfuryl chloride, paratoluenesulfuryl chloride, and the like, which urea reaction product may form part of the ammonia and ammonium salt substantially present in the mixtures.

It has now been found that it is possible to obtain sizing compositions such as those disclosed in U.S. Pat. Nos. 4,022,634 and 4,141,750, which have considerably better sizing properties even compared to compositions made by the technique disclosed in said publications. These improved sizing compositions are obtained by the process of the invention by combining the first component and the second component with the second component in finely divided form to form its sizing composition or precursor and controlling the reaction time of the first and second components to form the improved sizing composition. Combining the blend components in this way clearly accelerates the chemical reaction between the materials in the two components and thus results in blends that are surprisingly effective sizing agents.

The first mixture component includes one or more materials that form both ammonia and an ammonium salt when combined with the other components of the sizing composition. This ammonia / ammonium salt-forming material is selected from the group consisting of ammonia or its precursor; ammonium salts or their precursors; as well as urea reaction products and at least one Lewis acid selected from sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzene sulfonyl chloride, benzenesulfonic acid, orthotoluenesulfonyl sulfone acid and paratoluenesulfonyl sulfonic acid / paratoluenesulfonic acid. Mixtures of these ammonia / ammonium salt-forming materials can also be used. Ammonia, for example ammonium hydroxide in aqueous ammonia and ammonium salt can be used as such in the first component, or precursors which form, for example, in situ ammonia and / or ammonium salt in the sizing mixture can also be used in the first component. As further disclosed in U.S. Patent 4,022,634, ammonia and ammonium salt can be prepared, for example, as a reaction product of urea and an acid, and optionally additional ammonia or ammonium salt can be added to the urea / acid reaction product, ammonia can be reacted with resin salt-forming ingredients, e.g., acids to form ammonium salt can be reacted with the ammonia-forming components of the resin to produce ammonia. Acids that can be used to react with urea to form an ammonium salt and that may be present in the first or second component include sulfamic acid and phosphoric acid, as well as oxalic acid, methanesulfonic acid, trichloroacetic acid, nitric acid, sulfuric acid, hydrochloric acid, and stearic acid.

The first component may also contain a reaction product of urea and at least one selected Lewis acid, as further described in U.S. Patent 1,41,750. To form the reaction product, urea and at least one Lewis acid are mixed together and reacted, which Lewis acid is selected from the group consisting of sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzenesulfonyl chloride, benzenesulfonic acid, ortho- or paratoluenesulfonylsulfonyl or paratoluenesulfonyl chloride. Preferred Lewis acids are sulfuryl chloride, chlorosulfonic acid, benzenesulfonyl chloride and benzenesulfonic acid, and the most preferred acids are ortho- or paratoluenesulfonyl chloride and ortho- or paratoluenesulfonic acid. If water is present, it is preferably present in an amount by weight approximately equal to urea plus Lewis acid, although urea can be reacted with Lewis acid using even more water or with less water or even without water. If the Lewis acid is solid, the reaction with urea can be performed at a temperature somewhat above the melting point of the acid.

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The urea is generally reacted with the Lewis acid in such amounts and at a sufficient temperature to cause the pH of the mixture to change from an acidic pH prior to the onset of the reaction to a basic pH at the end of the reaction. This is determined with a pH meter. This temperature is generally in the range of about 100 to 215 ° C and depends to some extent on the water content of the mixture, and may generally be higher for mixtures with a low water content.

Although the change in pH is an important sign that the urea acid reaction is complete, a more important sign is the complete acidity of the first component of the reaction product. This total acidity is measured as the amount of sodium hydroxide, expressed in equal parts by weight of calcium carbonate, required to give a pink color to one million parts of a 50% by weight aqueous solution of phenolphthalate in the reaction product, and can be determined using the Hach Chemical Company Total Acidity Chemical Test. , Ames, Iowa, Model AC-5 Acid Test Kit). When an acid is reacted with urea, ammonia and an ammonium salt are formed and not only does this reaction raise the pH, it also affects the overall acidity of the mixture. Although this is not entirely clear, it is believed that the higher acidity of this first component (greater than that of pure urea) contributes to the ultimate yield of a better sizing composition.

In this case, the amount of acid relative to urea is an important factor and can best be defined as its final total acidity (ppm). The desired minimum total acidity is at least about 100 ppm and preferably at least about 4000 ppm. The actual amounts of acid reacted with urea are generally at least about 0.1% and preferably about 0.2 to about 8% based on the weight of the urea, although more may be used, for example 15 to 20% acid based on the weight of the urea to achieve the desired results.

The reaction of urea with an acid is preferably carried out in the absence of a resin and the modification of the resin in the absence of an organic acidic material used for sex. However, if desired, urea can be reacted with Lewis acid in admixture with the modified resin, as described in more detail below.

Optionally, additional ammonia, for example up to about 6% by weight of the total mixture of ammonia, water and urea acid reaction product, may be added to the mixture of urea acid reaction product and water after cooling to room temperature to improve the sizing results obtained in combination with the specially modified resin. For example, 20 parts of 29% aqueous ammonia can be mixed at room temperature with 80 parts of a mixture of urea acid reaction product and water. This mixture can then be combined with the second component of the modified resin, as explained in more detail below.

In another embodiment, the additional ammonium salt is 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-toluenesulfonyl chloride and p- to provide the sizing agents of the invention. In addition to the ammonium salt, the additional ammonium salt is obtained by the reaction between urea and selected Lewis acids of the invention, and at least substantially all, e.g., at least about 90% by weight of the ammonium sludge formed by the urea-acid reaction is preferably obtained by reaction with selected Lewis acids. The ratio of urea by weight to any additional ammonium salt used is often in the range of about 2: 1 to about 1: 4, and preferably about 1: 1 to 1: 4. This first component of the reaction product can then be combined with the modified resin and not only with the urea acid reaction product to obtain a sizing agent.

The ammonium salt used in the first component of the present invention may be a salt of an ammonium salt-forming acid which reacts with ammonia to form an ammonium salt such as sulfamic acid, chlorosulfonic acid, phosphoric acid, oxalic acid, styrene acid, p-toluenesulfonic acid, trichloroacetic acid, chloroacetic acid, chloroacetic acid, chloroacetic acid , acetic acid and sulfuryl chloride. Solid preformed ammonium salts may be used or alternatively the salt may be formed by reacting the desired acid with ammonia. In this case, for example, the dry powders of ammonium sulfate, urea and chlorosulfonic acid are heated together to about 160 ° C, at which temperature the pH of the mixture changes from acidic to basic pH of about 8 to give a first component containing ammonia / ammonium salt.

Another component of the sizing compositions of the invention is a resin which is modified with an organic carboxylic acid material which may be α, β-unsaturated organic acid, anhydride of such acid or mixtures of such acids and anhydrides, α, δ-unsaturated acid or derivative may be, for example, β-unsaturated aliphatic acid, which generally contains about 3 to 10, preferably about 3 to 6 carbon atoms, which may be, for example, acrylic acid, and further preferred acids are maleic acid, maleic anhydride and fumaric acid.

The resin is a mixture of rosin acids (including abiethyl, pimaric and levopimaric acids), hydrocarbons and high molecular weight alcohols obtained from a variety of sources. Gum resin is the waste remaining after the distillation of turpentine oil from crude turpentine resin obtained from live pine trees, wood resin is the waste remaining after the distillation of the volatile fractions of the solvent extract product (usually using naphtha as solvent) m , and tall oil resin is a by-product of tall oil fractionation (an oily mixture of rosin 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 except that tall oil resin often contains 1 to 5% of the fatty acids remaining after fractionation, whereas rubber resin and wood resin do not. As mentioned above, the resin can be used in sizing agents in "floating" form or can be partially or completely saponified. Rubber resin, wood resin, tall oil resin or mixtures thereof can be used in the sizing compositions of the present invention. However, tall oil resin is preferred because it generally gives the best results, possibly due to the fatty acids it contains, although this is not entirely clear.

As mentioned above, the organic acidic materials that can be used to modify the resin are α, β-saturated organic acids and anhydrides and mixtures thereof. The amount of organic acidic material used to achieve the desired results is generally about 5 to 50% or more by weight of the resin, but preferably about 5 to 30%, especially about 15% is a suitable amount. The modified resin can be formed into a soap by known methods, for example, by adding sodium hydroxide, potassium hydroxide or ammonium hydroxide to form an alkaline metal or ammonium soap of rosin acids. In general, the resin can be saponified after 64676 it has been modified. In any case, the saponification need not be complete, but is preferably sufficient to make the final sizing mixture water-soluble. With respect to the embodiment of the present invention using a reaction product of ammonia and a modified resin, ammonia is preferably used as a single saponification base.

According to the present invention, the first and second mixture components are combined as described below 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 liquids and solids. The second component and optionally the first component can be finely divided into particles, which can be solid or liquid, i.e. droplets, this division being carried out by devices known to those skilled in the art. Preferably, such liquid or solid particles have a mean diameter in the range of about 10 to 100 microns, preferably about 20 to 250 microns.

In the invention, the reaction between the first and second components can be controlled to obtain products with better properties. Such control can occur using relatively short reaction times. The reaction time may be in the order of up to 1 minute, preferably at most about 30 seconds, for example about 15 to 30 seconds. The reaction time can often be about 10 seconds. A particularly effective way to control the reaction time and to provide adequate mixing of the first and second components is to co-spray these materials in the desired particle size range.

It has been found that the conversion of the second component into fine particles can be accomplished by adding a liquid or solid second component to the first component by subjecting the first component in liquid form to strong shear mixing or agitation in a mixing or agitator. The addition of the second component to the mixed liquid first component divides the second component into fine particles as it comes into contact with the mixed liquid. The agitator element of the mixing device can be operated at a rate that enables shear mixing sufficient to finely divide the added second component into particles having a mean diameter in the range of 10 to 1000 microns.

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For example, a Waring mixer having a mixing element speed of about 10 to 25 to 25,000 rpm can be used to mix the first component when combining the second component thereto.

Alternatively, when the two components are liquid, both components can be forced through the spray nozzles and the two jets from a suitable container can be connected. In this way, both the first and second components are divided into aerosol-sized droplets. Preferably, the nozzles used form droplets having an average size of about 10 to 200 microns, preferably about 20 to 125 microns. As an example of a nozzle that can be used successfully, the second component can be sprayed from a nozzle No. 49487650 manufactured by Spray Engineering Company, East Spit Brook Road, Nashua, N.H. 03060, while the first component is sent through a similar full-cone center nozzle manufactured by Spray Engineering Company. The pressurized steam is a suitable gas to force the second component through such a nozzle. The first component jet can be formed with or without the use of pressurized propellant. The jets from these two nozzles can then be combined to mix the components with both components in a finely divided state.

When combining the first component with the second component to form the sizing composition of the present invention, sufficient amounts of each component are used to provide effective amounts of sizing agent, generally about 25 to 85% of the total dry weight of the sizing composition is the first component and about 75 to about 15% of the second component in the sizing composition. The sizing composition prepared by this method generally contains at least 25% by weight, often about 40-60% water.

With the second component and optionally the first component being divided according to the process into fine liquid or solid particles, the component can simply be mixed at room temperature. It is more disadvantageous to mix these components and heat the mixture to boiling point to ensure that all reactions are complete.

When the first component and the second component are combined at an elevated temperature, the modified resin can be heated or maintained at a temperature at which the combination can be performed. This combination can be accomplished by adding a dilute mixture of the heated reaction product of the first component to the heated second component to effect chemical and physical mixing. The mixture of the first and second components may be heated above 100 ° C to boil off the water and is preferably maintained at the boiling temperature until the cloudy solution becomes substantially clear. Optionally, after the combination of components has been completed, very small amounts of ammonium hydroxide can be used to adjust the pH of the product back to the basic range, i.e. above 7 if it has fallen to the acidic range below 7. Amounts of ammonium hydroxide up to 0.05% by weight increase the pH. usually to the desired reading. The choice of dilution concentrations of the first and second components prior to mixing of the components depends on how much of the first and second components is desired relative to each other and the desired concentration of the resulting sizing compositions. The choice of composite temperatures used is a function of workability and the desired degree of chemical and physical mixing, although in one embodiment of the invention, temperatures of at least about 27 ° C may prevent precipitation during mixing.

After the first and second components have been reacted, they can be contacted with either sodium or potassium hydroxide, or an aqueous solution of both, to provide a product having the desired pH. These bases can advantageously be added in sequential order, in particular so that NaOH follows KOH. The addition of the aqueous base actually completes the reaction of the first and second components.

As previously mentioned, ammonia, an ammonium salt, and in particular a modified resin or a soap of a specially modified resin can be combined at room temperature to provide an adhesive. In particular, a modified resin soap can be prepared by pouring a hot mixture of the resin and an organic acidic resin modifier into an aqueous solution of a saponification base, such as sodium hydroxide and / or potassium hydroxide, while slowly mixing the saponification of the modified resin. An aqueous solution of the saponification resin can be used in an amount sufficient to form an aqueous mixture of the modified resin soap containing from about 50% to about 70% by weight solids. Based on the total weight of ammonia, ammonium salt and resin and acid modified organic dry matter, the sizing agent may contain from about 3 to 30% ammonia, from about 4 to 72% ammonium salt and from about 93 to about 25% resin plus a modifying organic acidic material, wherein the ratio of ammonium salt to ammonia is greater than about 1: 1. The term "dry" is used in this description of the invention to mean any material other than the water present. Ammonia can be prepared in situ, for example, by the reaction between a resin, a modifying organic acidic material and an ammonium salt using about 4 to about 75% resin plus an organic modifying acidic material based on the total weight of the ammonium salt and the resin and the modifying organic acidic material on a dry basis.

The amount of ammonia used depends on whether ammonia is the only saponifier used. When only ammonia is used to saponify the specifically modified resin, from about 10% to about 75% ammonia and from about 25% to about 90% resin plus modifying organic acidic material based on the total weight of ammonia and resin plus modifying organic acidic material on a dry basis can generally be used to prepare the sizing agent. When ammonia is reacted with a specially modified resin soap, the mixture can generally be prepared with about 4 to about 60% ammonia and 96 to 40% resin plus modifying organic acidic material based on the total weight of ammonia and resin plus modifying organic acidic material on a dry basis.

The steps involved in preparing the sizing compositions, other than combining the components with the other component and optionally both components in finely divided form, are not disclosed in U.S. Patents 4,022,634 and 4,141,750, both of which are incorporated herein by reference.

The sizing agents of the present invention generally have a pH in the range of at least about 6.6 to about 10 or 12 and a total acidity of at least about 1000 parts per million. The pH is preferably at least about 8, for example about 9-11. Total acidity is measured as the amount of sodium hydroxide, expressed as parts by weight of calcium carbonate, required to impart pink color to one million parts of the phenol-phthalene-containing lily 64676 flavor mixture of the present invention, and this total acidity can be determined by the Hach Chemical Company Total Acid Chemical Test. .,

Arnes, Iowa, Model AC-5 acidity test kit). A preferred object of each embodiment of the sizing agent of the present invention is to provide the highest possible total acidity without lowering the pH to such an extent that the sizing agent becomes insoluble in the water of the paper mill. The proportions of the ingredients of the sizing compositions of the present invention may vary according to this object and in this case may be suitably defined as the pH values and the total acidity which they impart to the sizing agents.

The bonding properties of these improved sizing compositions are better than those used with the same amount of conventional sizing agents and equally good with lesser amounts, allowing the user to achieve current Constants with less sizing agent than hitherto required and therefore at lower cost.

The products obtained by using the sizing compositions according to the present invention are brighter and stronger than those obtained with the sizing agents available hitherto. The new sizing compositions also promote sheet drying when used as a pulp additive so that the speed of the paper machine can be accelerated and still obtain a sheet with a similar moisture content. Alternatively, more water can be added to the pulp to better orient the fiber on the paper machine wire, resulting in a stronger paper and better structure. The new sizing compositions are normally used alone as a sizing agent with the pulp mill in the pulp or in surface sizing, but it can also be combined with many other sizing agents, thus replacing a considerable part of these known materials.

The improved sizing composition can be used as a pulp additive or as a surface sizing agent in the manufacture of cellulosic products. The exact amount used to obtain the best possible results may vary depending on the type of pulp used and the desired properties of the finished product. In general, lesser amounts than are currently used with known sizing agents can be used to produce products that are substantially as good or better. For example, when known resin sizing agents are generally used in an amount of about 0.1 or 0.5% to about 4% solids by weight of the fibers in the pulp slurry, the sizing compositions of this invention can be used in as little as 0.05% or 0.25%.

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Thus, about 0.05 to 0.25 or even about 4% of the sizing compositions of the invention may be used on a dry weight basis based on the weight of the fibers in the pulp slurry. Typically, when 1% of a known resin sizing agent is normally used, 0.5% of the novel agent of this invention may be used to achieve substantially equal or better results.

The preparation of sizing compositions as described in this specification of the invention also allows for cheaper compositions. This can be achieved by using less relatively expensive ingredients (e.g., modified resin) while still providing adhesive compositions that are substantially as good as those prepared in a known manner that contain more relatively expensive components.

The methods of the present invention are explained in more detail below by the following examples.

Example 1

The first component of the sizing agent is prepared by placing 4000 g of commercially available urea, 200 g of sulfamic acid and 4200 g of water in a cooking vessel and then heating it slowly while stirring the contents until the reaction mixture boils at atmospheric pressure. When the temperature reaches a reading of about 103 ° C, the water loss ceases and the pH of the solution, as determined by a pH meter, rises to a reading of about 8. The first component product obtained is a clear solution with a size of 86,000 ppm as determined by Hach Chemical Company's acid test kit 11a model AC-5 .

To form the second component of the modified resin, 3000 g of commercially available tall oil resin is melted in a cooking vessel. The following ingredients are slowly added to the molten resin: 360 g of fumaric acid plus 100 g of 37% formaldehyde and 3 g of paratoluenesulfonic acid as resin crystallization inhibitors. The reaction mixture is then heated to about 205 ° C with constant stirring and maintained at this temperature for 2-10 hours.

To form the sizing agent, 600 g of the first component and 300 g of water are placed in an instant mixer, which may be, for example, a Waring-64676 mixer. The second component (300 g), either as molten or solid particles, is added to the contents of the mixer and mixed for about 10 to 60 seconds, and preferably about 20 to 30 seconds. The addition of the second component in this way ensures that the second component is finely divided upon contact with the mixed or agitated first component. Potassium hydroxide (60-120 g) is then added as a 50% by weight aqueous solution and stirred for 5-10 seconds. The pH of the solution is then adjusted to 9 to about 10 with sodium hydroxide and sufficient water is added to bring the total solids content of the solution to about 50% by weight.

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

Example 2

The first component of the sizing agent is prepared in the same manner as in Example 1.

To prepare the second component, 3000 g of commercially available tall oil hat are melted in a cooking vessel. 360 g of fumaric acid are added slowly and moderately to this resin with stirring. Thereafter, with constant moderate stirring, the reaction mixture is heated to about 205 ° C and maintained at this temperature for 2-14 hours. The hot reaction product is then carefully and carefully added to a warm solution of 700 g of sodium hydroxide dissolved in 4032 g of water. The pH of the final second component solution is about 10.0.

To form the sizing agent, the second component and the additional water are mixed in the following proportions:

The second component is 115 g

Additional water 115 g

A total of 230 g The mixture is then combined with 190 g of the first component to form a total of 420 g of adhesive.

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Example 3

The first and second components of the sizing agent are prepared in the same manner as in Example 1.

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

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

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

Example 4

In the apparatus shown in the drawing, 1000 parts of the second component prepared as in Example 1 are formed into a spray 1 by forcing it through an adjustable conical nozzle 2 (e.g. nozzle No. 49487650 manufactured by Spray Engineering Co., East Spit Brook Road, Nashua, N.H., 03060). The jet 1 is sprayed into a pipe 3, where it also encounters a jet 4 of a first component made according to Example 1, coming from a central cone nozzle 5. The temperature of the second component is about 182 ° C and the nozzle 2 through which it passes is heated by a steam 6 filled with steam. , and a pressure of about 155 psig and a temperature of about 182 ° C. The amount of the first component is 2000 parts of a 50% by weight solid product. The amount of water coming from the channel 7 is about 1000 parts, which is less than the amount of steam coming from the openings of the jacket 6 around the nozzle 2 of the second component, and water is fed to the device 8 from the openings 8 to wash the walls of the pipe 3 and prevent solids. The reaction product encounters a jet 9 of a 50% by weight potassium hydroxide solution containing 200 to 400 g of potassium hydroxide fed to the tube 3

II

17 64676 through the opening 10 in the channel 11. The resulting solution 12 is then pumped to a storage tank (not shown) by a pump 13 through a channel 14 in which the pH is adjusted to 9.0 to about 10.0 with either KOH or NaOH.

The two nozzles 2 and 5 of the drawing are shown in such a way that the two droplet streams, i.e. the jets 1 and 4 of the second and first components, move in parallel. Other arrangements of the nozzles 2 and 5 can be used, including one in which the nozzles are placed horizontally on the diameter of the pipe 3 so that the droplet flows are directed against each other.

The drawing shows that water flows downwards inside the pipe to prevent the accumulation of solids. An alternative method would be to arrange a series of water jets in the inner circumference of the pipe.

Example 5 To test the sizing agents prepared by the method of the present invention, samples of the products of Examples 1, 2 and 3 are treated as follows. The sizing agents are mixed with a papermaking tray in bleached kraft paper ... to compare their performance. Hand towels are prepared using 5.7 g of fiber diluted in water to a 1% by weight slurry.

The fiber and water are mixed in a Waring mixer for about 1 minute and then the sizing agents are added at about 4.5 kg per ton of fiber and mixed for about 45 seconds. Alum is then added in an amount of about 6.7 kg per ton of fiber.

The slurries are then further diluted with water to a fiber solids content of about 0.1% by weight of the slurry. Wipes are then formed with a device called a Willimas Handsheet Former and made from slurries made with the sizing agents shown in the examples. The towels are placed between two blotting papers and dried in a hot press at a temperature of about 110 ° C at a pressure (about 22 kg per square inch) of about 3.4 kg / cm 3. The towels or sheets are then treated for 24 hours at 50% relative humidity and 22 ° C and tested with the TAPPI Hot Ink Float test.

18 64676 "Ink float test" used to compare the effectiveness of different sizing agents uses an acid ink with the following composition: 1000 ml distilled water 5 g gallic acid 7.5 g FeSO 4 1.0 g tartaric acid 1.0 g sodium benzoate 3.5 g blue aniline 50.9 g formic acid placed on the surface of the liquid ink and recording in seconds the time required for 50% of the surface to color from the ink. In general, the greater the number of seconds recorded in a particular experiment, the more effective the sizing agent used in that experiment.

The results obtained are shown in Table I. Each series of experiments is performed on one day with the same fiber and the same type of water. Comparative results vary from day to day depending on the fiber used, water quality and possibly other factors.

li 19 64676

Table I

Scratch color tests for leaching agents 4.5 kg of glue per tonne of paper (second component fine)

Experiment Description of the experiment The method used for preparing the sizing agent was used for 1 second. The new method was obtained as in Example 1. The second component was mixed for 20 seconds. Second component added as solid particles 924 2 Comparison Old method as in Example 2 612 3 Saima as experiment 1 New method 1284 4 Same as experiment 2 Comparison - old method 888 5 Same as experiment 1 New method 1284 6 New method As in Example 1. Second component added as melted product at 205 ° C 1236 7 Old method Comparison as in Example 2 708 8 New method As in Example 3 1666 9 Old method Comparison as in Example 2 976 10 Old method Comparison as in Example 2 except saponification carried out KOH: 11a 960 11 New method As in Example 1. Repeat the component mixed for 30 seconds.

KOH stirred for 30 seconds 795 12 Old method Comparison as in Example 2 480

The averages of the experiments in Table I were as follows: Neither component was finely divided (old method): 771 seconds; second component finely distributed (new method): 1206 seconds.

This shows that the new method is better than the old one with the formula ------- x 100% = 56% 771 20 64676

The values of the ink color tests presented in Table I for comparison are generally higher than the values obtained in the previous experiment. This is due to the following reasons: (a) the second component is saponified with KOH and not NaOH, (b) a small amount of NAOH is added to the sizing agent after the addition of the second component, and (c) a higher grade of tall oil resin is used to react with fumaric acid to prepare the second component.

Example 6

To test the sizing agents prepared by the method of the invention, wherein both the first and second components are finely divided, samples of the products prepared as described in Example 4 are tested by an ink color test. The manufacture of hand towels and the ink color methods used are substantially similar to those shown in Figure 5. The results obtained are shown in Table II. As before, each set of tests is performed using the same fiber and the same type of water on the same day. Comparison results vary from day to day depending on the size of the hand towel, the fiber used, water quality, and possibly other factors.

il 21 64676

Table II

Ink color tests for adhesives 4.5 kg of adhesive per ton of paper Both components are finely divided

Experiment Description of the experiment Method used to prepare the liquid (No.) for the preparation of the soil (seconds) 1 New method As in Example 4.

The resin is 12% fortified with fumaric acid 530 2 Comparison Old method as in Example 2. The resin is 12% fortified with fumaric acid 360 3 Same as Experiment 1 New method 558 4 Same as Experiment 2 Comparison - old method 376 5 Same as Experiment 1 New Method 552 6 Same as Experiment 2 Comparison - Old Method 379 7 New Method As in Example 4. The resin is 6% fortified with fumaric acid 384 8 Same as Experiment 2 Comparison - Old Method 386

The averages of the first six experiments in Table II are as follows: Neither component was finely divided (old method): 372 seconds; both components finely distributed (new method): 547 seconds.

This shows that the superiority of the new method over the old method is 547-372 x 100% = 47% 372

Experiments 7 and 8 in Table II show that the sizing composition prepared in accordance with the present invention is approximately as effective as the sizing agent conventionally prepared using twice as much resin-modifying fumaric acid material.

Claims (6)

22 64676 A process for preparing a sizing mixture having improved sizing properties, which process comprises combining A) a first component which forms both ammonia and. an ammonium salt combined with another component of the sizing composition, wherein the ammonia-ammonium salt-forming agent is ammonia or an ammonium salt or a precursor thereof; reaction product of urea and at least one Lewis acid, which Lewis acid is sulfuryl chloride, chlorosulfonic acid, thionyl chloride, benzenesulfonyl chloride, benzenesulfonic acid, or-toluenesulfonic acid, para-toluenesulfonic acid, para-toluenesulfonic acid, ortho-toluenesulfonylsulf or a mixture of these substances; and B) a second component which is a saponified, partially saponified or unsaponifiable resin modified with an organic acidic material which is a tx, β-unsaturated aliphatic carboxylic acid having about 3 to 10 carbon atoms, an anhydride thereof, or an acid and anhydride thereof. a mixture comprising an adhesive mixture or a precursor thereof of adhesive amounts of said modified resin and adhesion enhancing amounts of ammonia or ammonium salt-forming material, wherein the amount of modified resin, ammonia and ammonium salt is sufficient to form a adhesive mixture having a total acidity of at least about 1000 million, that the combining of the first component and the second component is performed with the second component in finely divided form to form its sizing mixture or precursor, and the reaction time of the first and second components is controlled to form an improved sizing mixture. A method according to claim 1, characterized in that the second component is formed into fine particles by adding said second component to the first component while subjecting the first component to a strong shear mixture sufficient to form particles of the second component having a mean diameter of about 10 to 1000 microns. A method according to claim 1, characterized in that the first component is also divided into fine particles while the first and second components are combined, wherein the average diameter of the particles of both the first and second components is about 10 to 200 microns. A method according to claim 3, characterized in that the first and second components are converted into fine droplets by forcing these components through spray nozzles and in that the two spray streams are mixed in a suitable container. 1. A compound for the production of a limiting mixture with an auxiliary component, comprising the following components: en reaction products with urea and acetone in Lewis syrup, vilken Lewis syruryl sulfuryl chloride, chlorosulfonyl, thionyl chloride, benzenesulfonyl chloride, benzenesulfonyl, ortho-toluenesulfonyl-sulfonyl-sulfonyl-sulfonyl-sulfonyl-sulfonyl-sulfonyl ; and B) and the other component, which is an alphatic carboxylic acid of about 3 to 10 cholata, the anhydrous or anhydrous carboxylic acid of the circles 3-10 anhydrider; vilken limblandning eller dess precursor innehäller en limmande mängd av nämnda harts och en limningen förbättrande mängd av ammoniak eller ammoniumsalt bildande ämne, varvid mängden av det modifierade resin, ammoniaken och ammonialtaltet är till-räcklig för att bilda end 1000 million dollars, the amount of which is derived from the above components and the other components of the components and the final form of the form of the image or the precursor and the other components