TWI321178B - Sizing of paper - Google Patents

Description

IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to sizing of paper, and more particularly to aqueous dispersions of cellulose-reactive sizing agents, and their preparation and use. [Prior Art] Cellulose-reactive sizing agents, such as alkenyl succinic anhydride (ASA), are widely used in papermaking at neutral or microalkali feedstock pH to impart paper and paperboard to wet and aqueous liquids. Penetrate to some degree of impedance. A paper pulp mainly composed of a cellulose-reactive sizing agent is usually supplied in the form of a dispersion containing an aqueous phase in which finely divided particles or droplets of the sizing agent are dispersed. The dispersion is typically prepared by the aid of a dispersion system that combines a high molecular weight zwitterionic or cationic polymer with an anionic compound (eg, sodium lignin citrate) (eg, cationic, polyamine, poly Hydramine or vinyl addition polymer. WO 96/17127 discloses an aqueous dispersion containing a cellulose-reactive sizing agent and an anionically modified slag particle. ^ 97/31152 discloses an aqueous dispersion containing a reactive slurry and an anionic particulate material. The dispersion may also contain no more than two weights of the reactive slurry based on the weight of the surfactant. The interfacial surfactant can be nonionic or anionic. WO 98/33979 A1 Dispersion and a dispersion system Anionic stabilizer. The invention discloses a cellulose-reactive sizing agent water, which comprises a cationic organic compound and a preparation of an aqueous dispersion of alkenyl succinic anhydride per U 1 shell, which has been improved in properties and performance. However, there are still some technical problems associated with the use of this dispersion (4). In general, the dispersion of the alkenyl-degraded field shows poor "^^ which significantly causes the treatment of the dispersion (for example, storage and use difficulties, another disadvantage is that the aqueous dispersion cannot be stored for a longer period of time) because of the thin base number The sour liver is easily hydrolyzed and thus becomes ineffective as a sizing agent. Therefore, the alkenyl succinic anhydride is usually transported in a liquid to the factory, and then dispersed before being used as a sizing agent, and the obtained dispersion is passed. f is used within 2 hours to avoid problems of insufficient stability and reduced efficacy. The equipment used to prepare the dispersion provides high shear and frees the surface and produces a dispersion with the right particle size. Because high shear is usually A large amount of energy is required, such equipment is often complicated and expensive. The object of the present invention is to provide an aqueous dispersion of cellulose-reactive upsets which can be easily used with low shear and low energy consumption. Preparation. The object of the present invention is to provide an aqueous dispersion of a cellulose-reactive superiority agent which exhibits improved stability and sizing efficacy. The present invention relates to an aqueous dispersion of a cellulose-reactive sizing agent comprising an anhydride, an anionic polyelectrolyte, and a nitrogen-containing organic compound, wherein the gas-containing organic compound has a molecular weight Less than the amine and/or one or more of the radicals of the radical group or its quaternary. The method of the present invention for the preparation of an aqueous dispersion of a cellulose-reactive upper violet agent is contained in an anionic polymerization. The monoacid anhydride is dispersed in the aqueous phase in the presence of an electrolyte and a nitrogen-containing organic compound 1321178, wherein the nitrogen-containing organic compound has less than 18 Å and/or one or more hydroxyl groups. The present invention also relates to the use of an aqueous dispersion of a cellulose-reactive sizing agent as a raw material sizing agent or a surface polymerization agent for producing paper. The present invention further relates to a method for producing paper, The method comprises the steps of: adding an aqueous dispersion of the cellulose-reactive superpolymerizing agent to an aqueous fiber suspension, and removing the obtained suspension from water on the net, and producing a crucible comprising cellulose -Reactive sizing agent The aqueous dispersion is applied to a fiber reel. [Embodiment] According to the present invention, it has been found that an improved aqueous pulp can be achieved by using the cellulose-reactive aqueous dispersion of the present invention. It has been found that the dispersion of the present invention exhibits better stability than conventional dispersions. This has been found in the preparation of the aqueous dispersion of the present invention as compared to the aqueous preparation of a conventional cellulose-reactive formulation. , lower / can be used. Therefore, the present invention makes it possible to create low shear by using devices that are simple and energy-saving and capital-saving (such as static bears, ^人^^~, /tc* s states). The present invention thus provides substantial economic and technical advantages. The cellulose-reactive sizing agent according to the present invention may be selected from the acid of the water in the art, and the sizing agent is a sparing agent. / The following general formula (1) is characterized in that each of them is independently selected from a saturated or unsaturated local system containing from. A carbon atom, or ... may form a 5 to 6 membered ring together with the heart and the appropriate portion. The substrate is optionally replaced by a hydrocarbon group containing up to 3 〇 1321178 carbon atoms. (I) 0 R1 - C - 〇ΟII C - R2 Examples of the acid anhydride include alkyl and alkenyl succinic anhydrides, for example, isooctadecenyl succinic anhydride, isostearyl succinic anhydride, n-hexadecenyl amber Anhydride, decyl-sodium sulphate, sulphate, octenyl sulphate, octene-based sulphonate, triisobutenyl-based anhydride, 1-octyl-2-nonenyl succinic anhydride,

And 1-hexyl-2-octenyl-succinic anhydride. Examples of anhydrides include those disclosed in U.S. Patent Nos. 31G2 () 64; 3 821 G69; 3 96 Μ () 5; 4' 040, 900 ' 4, 522, 686; and Re 29 96 其, which are incorporated herein by reference. The cellulose-reactive sizing agent according to the invention may contain one or more acids

Anhydride, for example, one or more alkyl and/or alkenyl anhydrides. Generally, the anhydrides of the present invention are liquid at room temperature. S The dispersion according to the present invention contains a dispersing agent, or a dispersing agent system, which contains an anionic polyelectrolyte and a nitrogen-containing organic compound. Although the anion? The κ electrolyte and the ruthenium nitrogen organic compound may not be effective when the ruthenium is used as a dispersant alone. However, when used in combination, these compounds are effective as a dispersant for the acid needle polymerization agent. Preferably, the dispersant is anionic, i.e., the dispersant or dispersant system has a combined negative charge. The anionic polyelectrolyte according to the present invention may be selected from organic and inorganic compounds and may be derived from natural or synthetic sources. The anionic polyelectrolyte has two or more anionic groups which may be the same or different types. Examples of suitable anionic groups (ie, anions that are anionic or produce anions in the aqueous phase: 丄丄: 丄丄/δ groups), A > sulphate sulphate, Wei salt, phosphonate, a ^ a salt, a sulfonic acid and a (iv) group and a salt thereof or an alkali metal (one 舻逋* is an ammonium cerium) salt. The anionic polyelectrolyte may be water-soluble 1 '1 1 such as a linear and branched anionic polyelectrolyte, or water. Dispersed, such as 'anionic and/or particulate anionic polyelectrolytes. Preferably, the water can be divided into: the anionic polyelectrolyte of the microparticles is gelatinous, i.e., small in the gelatinous range. Suitably the colloidal particles have a particle size 'from i(10) to 100(10)' preferably from 2 to 7 〇 nm and most preferably from 2 to nm. The water-dispersible and particulate anionic polyelectrolyte may contain aggregated and/or unaggregated particles. Examples of suitable organic anionic polyelectrolytes include anionic multi-flavors such as, temple powder, guar gum, cellulose, chitin, chitosan, poly, polygalactose, polydextrose, xanthan gum, and nectar. And dextrin. Suitable organic anthracite polyelectrolytic niobium includes synthetic anionic polymers: such as condensation polymers such as polyamine phthalates and naphthalene-based and melamine-based polymers such as condensed naphthaldehyde sulfonates And a polymer based on a melamine-sulfonic acid; and a vinyl addition polymer prepared from an ethylenically unsaturated monomer (including an anion or a latent anion), such as acrylic acid, methyl Phosphate esters of acrylic acid, maleic acid, itaconic acid, crotonic acid, ethylene sulfonic acid, sulfonated styrene and hydroxyalkyl acrylates and mercapto acrylates, optionally copolymerized with ethylenically unsaturated monomers The monomers are, for example, alkyl acrylates 'styrene and acrylonitrile' and derivatives of these monomers, vinyl esters and the like. Further examples of suitable organic anionic polyelectrolytes include water soluble branched 10 polymers and water dispersible crosslinked polymers by a monomer mixture or potential anionic monomer containing one or more ethylenically unsaturated anions, It is obtained by polymerization in the presence of one or more other lyo-unsaturated monomers in the presence or absence of other ethylenically unsaturated monomers. The presence of a polyfunctional crosslinking agent in the monomer mixture provides for the possible preparation of water-dispersible branched polymers, micro-crosslinked polymers, and highly cross-linked polymers. Examples of suitable polyfunctional crosslinking agents include compounds having at least two ethylenically unsaturated bonds, for example, N,N-methylene_bis-(meth)acrylamide, di(meth)propene. Acid polyethyl (meth) propylene (tetra), diphenyl benzene, tripropyl propyl salt and N-methyl propyl propyl (meth) propylene amine; having a weak bond unsaturated bond and a a reactive group compound, for example, (meth)propionic acid propylene glycol vinegar, 2 acid and methyl alcohol (meth) acrylamide; and having at least two reaction two::, for example, diacid, like It is 'Ethylene, epoxide and chloropropanol. :: Machine anionic polyelectrolytes usually have from. (9) to the anion of Μ (DSa), suitably from 0' 丨 to 丨 2, and preferably the anion 啻 并 and π a 丄 ^ ι · 电解 Electrolytic shell may contain one or more cationic groups, Just 1 city: for:::. The molecular weight of the anionic polyelectrolyte can be in the wide range of two, often more than 20°, and suitably higher than 5°, and the upper limit* is 10 million and preferably 2 million. Examples of the inorganic anionic polyelectrolyte f include an anion group, for example, an ion-based material prepared from tannic acid and expanded stone type n. These anionic polyelectrolytes f I [is an aluminosilicate or a hydroxyl group. Examples of suitable s-, s-alkanol, phantom, and anionic polyelectrolytes 1321178 include polydecanoic acid, polyphthalate 'polyaluminum silicate, particles based on phthalic acid, such as cerium particles, aluminizing (Aluminum modified) bismuth and alumino citrate, polycaprate microgel, polyaluminum citrate microgel, Fangsheng sand rubber and precipitated bismuth, bentonite clay, for example, Monte Stone, bentonite, hectorite, beidelite, nontronite and saponite. Preferred anionic polyelectrolytes include materials based on Shixia, such as those based on tannic acid gum.

The nitrogen-containing organic compound according to the present invention is a face amine or a quaternary ammonium salt thereof. Suitable nitrogen-containing organic compounds include primary, secondary, and = π-amines and their quaternary ammonium. Suitable nitrogen-containing organic compounds further include monoamines, diamines and polyamines and their quaternary ammonium salts. Suitable quaternary ammonium salts include protonated, alkylated, alkarylated amines of the above type which are reacted with an amine such as an acid such as hydrochloric acid, methyl chloride, dimethyl sulfate and gaseous toluene. And formed. In a preferred embodiment of the invention, the nitrogen-containing organic compound is an amine having one or more hydroxyl groups or a quaternary ammonium thereof. Preferably, one or more hydroxyl groups are present in the nitrogen-containing

The terminal of one or more substituents of the compound, i.e., the hydroxyl terminated amine or its quaternary ammonium. Examples of suitable nitrogen-containing organic compounds include the following amines and their quaternary ammonium salts: diethylenetriamine, triethylenetetramine, hexamethylenediamine, diethylamine, dipropylamine, diisopropylamine, cyclohexane Amine, pyrrolidine, hydrazine, triethanolamine, monoethanolamine, diethanolamine, 2-methoxyethylamine, aminoethylethanolamine, alanine and lysine. Further examples of suitable nitrogen-containing organic compounds include Choline hydroxide, tetradecyl ammonium hydroxide, and tetraethylammonium hydroxide. Preferred nitrogen-containing organic compounds include triethanolamine and its four-stage. The molecular weight of the nitrogen-containing organic compound can vary within wide limits. At 12 1J21178

In a preferred embodiment of the invention, the amine or its quaternary ammonium has a molecular weight of less than 180, suitably up to 17 Å and preferably up to 16 Å. The molecular weight is usually >, and is 30. The molecular weight of the fourth stage of the amine as described herein means the molecular weight of the cationic portion of the quaternary ammonium halide, meaning that the anionic portion of the quaternary ammonium compound is not included in the molecular weight given above. For a nitrogen-containing organic compound selected from the group consisting of an amine having one or more hydroxyl groups and its quaternary ammonium, although the above molecular weight is also suitable for such a compound, the molecule 1 may be higher, for example, less than 500. And usually less than 300. In the aqueous dispersion or emulsion of the present invention, the acid anhydride may be present in an amount of from about 〇 to about 5% by weight, suitably from 0.1 to about 30% by weight, based on the weight of the aqueous dispersion, and preferably from From about i to about 2% by weight. Based on the weight of the anhydride, the anionic polyelectrolyte is typically present at a level of up to about 1% by weight of 'generally from 〇i" i 5% by weight, suitably from 〇$ to 10% by weight, and preferably from i to 7 wt%. The nitrogen-containing organic compound may be present in an amount of up to 2% by weight, usually from 0.1 to 15% by weight, suitably from 〇5 to 1% by weight, and preferably from 1 to 7 by weight, based on the weight of the anhydride. In addition to the acid anhydride, the anionic polyelectrolyte, and the nitrogen-containing organication, it may be present in the dispersion. In addition to the poly-anionic and non-ionic interfacial materials, examples of additional compound compounds that are not necessary include mono-, di- and active agents with dispersing agents, stabilizers, and scorpion dredging 4~Βί^丨Lining agents and preservatives, for example, hydrolyzed acid anhydrides, for example, such as μ-mail U, such as the hydrolyzed alkyl and alkenyl acid if mentioned above, preferably hydrolyzed alkenyl a (d) Liver, for example, a hydrolyzed acid needle in the form of a tickic acid and/or a slow (tetra) derivative; an anionic surfactant such as an acid-filled (eg, ethoxylated dish vinegar), burned sulphuric acid vinegar, 13

嶒醆Sa and phosphates, alkylaryl sulfates, sulfonates and phosphates, for example, sodium dodecyl sulfate and ethoxylated, phosphorylated isotridecyl alcohol. The amount of this additional compound, if any, in the dispersion may be from < 0 to 15% by weight, suitably from 1 to 10 liters per liter, and preferably from 2, based on the weight of the anhydride. Up to 7 wt%. Water may also be present in the dispersion and constitute the remainder of the dispersion up to 100% by weight. The dispersion according to the present invention can be produced by forming a mixture containing an anion polyanhydride and a nitrogen-containing organic compound as defined above, and dispersing the mixture in the presence of water. The ingredients in the dispersion may be mixed in any order. 'But it is preferred to mix the anionic polyelectrolyte f with the gas-containing organic port and dilute with water to an appropriate concentration, and then disperse the acid anhydride therein. The mixture can be dispersed by using a dispersing device that provides sufficient dispersion (e.g., a static mixer that provides relatively low shear). The obtained dispersion contains anhydride droplets usually having a droplet size from hydrazine to the aqueous sizing dispersion according to the present invention, 1 ο μιη diameter. A conventional method can be used for the production of paper of various types of cellulose fibers, and it is destroyed internally. As used herein, the term "paper" means not only the paper including the various types of sheets and reel forms of the cellulosic product including, for example, 'plates and paperboard. The fiber suspension and finished paper may also contain a mineral filler and are based on a dry fiber suspension or finished paper, typically having a cellulose fiber content of at least 50% by weight. Examples of conventional types of mineral fillers include kaolin, earth, ceria, gypsum, talc, and natural and synthetic calcium carbonates such as white [milled marble and precipitated carbonic acid per. The invention is also directed to a method of producing paper wherein the aqueous 1321178 sizing dispersion of the present invention is added to an aqueous fiber suspension or to a fibrous sheet or roll. Suitably, the fiber suspension is added to form a paper on the web for drainage, or is usually applied as a slurry to the surface of the fiber sheet or roll as a surface-polymerized cellulose-reactive sizing agent to dry. Based on the fibrous suspension and, optionally, the filler, from 〇〇1 to 1% by weight, preferably from 0.05 to 0.5% by weight, wherein the dosage is mainly based on the amount of sizing or paper and desired Depending on the degree of pulp.

The aqueous sizing dispersion according to the present invention is particularly useful in the production of paper from aqueous fibers having high electrical conductivity. The conductivity of the suspension on the web can range from 0.3 mS/cn^1 〇 mS/cm. According to this invention, good results are obtained when the conductivity is at least 2.0 ms/cm, especially at least 35 ms/cm, especially at least 5.0 mS/cm and even at least 7 5 claws. The conductivity can be made by; I»淮^.,, 3, for example, by, for example,

The WTW lf 33〇 instrument supplied by Christian Berner is used for measurement. The values mentioned above are suitably determined by measuring the conductivity of the fiber suspension, which is fed to or appearing in # or by measuring the removal of water from the suspension. White;: decided. The high degree of conductivity refers to a high level of salt (electrolyte), which is derived from the material used to form the raw material, which is derived from the incoming material, derived from the fresh water provided by the method, etc., and is not sought. In addition, the method of sleeping in which the white water system is recycled on a large scale is in the middle of the process of causing a large amount of salt to accumulate in the cycle of the process, which may be conventionally added to the fiber suspension in papermaking. The auxiliaries, aluminum compounds, dyes, wet-strength resins, and pre-products, such as the retaining element, the whitening agent, etc., can be used when 15 1321178 can be used in combination with the present dispersion. Examples of the compound include aluminized aluminate and a polyaluminum compound such as polyaluminum chloride and polyaluminum sulfate. Examples of suitable apricot retention aids include cationic polymers, anionic inorganic materials 2, combinations of organic polymers, for example, combination of bentonite and cationic polymers, ruthenium-based sols and cationic polymers or cationic and anionic poly-characters Combine. Particularly good sizing can be obtained when using the dispersion of the present invention in combination with a retention aid containing a cationic polymer. Suitable cationic polymers include cationic starch, acrylate-based and acrylamide-based polymers, polyethyleneimine, polyamines, polyamidoamines, and poly(diallyldimethyl chloride). Ammonium) and combinations thereof. Preferred retention aids include cationic starch and polymers based on cationic acrylamide. In a preferred embodiment of the invention, the dispersion and the retention system comprising at least a cationic polymer and an anionic shibei material are used in combination with 'the anionic enamel material such as f 八: 矽 based particles or swell earth. It is possible to premix the component or components of the present invention with a retention aid such as an anionic ♦f material before the resulting mixture is introduced into the fiber suspension. Therefore, the κ I· raw sizing dispersion is just introduced into the fiber suspension by an acid anhydride and a nitrogen-containing organic compound 16 and an anionic polyelectrolyte. For example, the aqueous stone material is, for example, a sol or a bentonite slurry based on Shixia. The invention is further illustrated in the following examples, however, it is the same as that of the invention. Unless otherwise stated, the sum is. The system is divided into heavy injuries and weights of 0/0. 16 1321178 Example 1 The aqueous dispersion according to the present invention is obtained by anionic polymerization of an alkenyl succinic anhydride (AS A) mainly containing an olefin fraction containing #16- and octadecyl succinate. It is prepared by dispersing a mixture of an electrolyte and an amine in a static mixer. The aqueous dispersions used in this and other examples were prepared in a similar manner except that no amine was used, no phthalic acid gum was used, a high molecular weight amine and/or an amine having no radical group was used. The anionic polyelectrolyte used in this embodiment is a silicate gel (Eka NP 590) in the form of an aqueous sol having a weight % content of Si 〇 2 and containing cerium particles having a specific surface area of 850 m 2 /g, which is via aluminum. Qualitative. The amine used in this example was triethanolamine (TEA) having a molecular weight of 149. The anionic polyelectrolyte and the amine were mixed in the presence of water to form a mixture which was poured into a terminal of the conduit at a flow rate of 3 · 17 Torr/min, and the concentrated ASA system was poured from the end at a flow rate of 0.167 Ι/min. . The pressure drop in this mixing unit is 3.4 bar. The obtained dispersion has an ASA content of 5% by weight, an anionic polyelectrolyte content of 5.0% by weight based on ASA (in this embodiment, Si〇2 content), and from 0 to 2.0% by weight based on ASA. Amine content. The dispersions 1 to 4' were prepared as shown in Table 1. The contents of si 〇 2 and amines given therein were based on ASA. ..S :: 17 1321178 Table 1 Dispersion No. Si02(°/〇) TEA(%) 1 5 0 2 5 0.5 3 5 1.0 4 5 2.0

The particle size of the ASA droplets was measured with a Malvern Mastersizer Microplus after diluting the dispersion with water to an ASA content of 0.5% by weight. The results are shown in Table 2. D(v 〇. 1), 〇(v 0.5), and D(v 0·9) respectively mean that 10, 50, and 90% of the particles have a diameter smaller than a given size. Table 2 Dispersion 趟 big λ!, (哗) No. D (v0.1) D(v 0.5) D(v 0.9) 1 0.43 4.64 12.42 2 0.82 2.32 6.88 3 0.50 1.78 5.40 4 0.59 1.43 5.30

As can be seen in Table 2, 'Dispersion according to the present invention, dispersion Nos. 2 to 4 produced a larger particle size than the dispersion for the dispersion No. 1 used for comparison by SCAN-C26: 76 according to the standard method. Handmade paper was prepared for evaluation, and the sizing was measured by Cobb-60 value according to the standard method Tappi Ding 441. The paper is prepared according to a method in which a dispersion is added to an aqueous fiber suspension containing recycled pulp, wherein the pulp has a fiber concentration of 〇5 g/丨, a conductivity of 0.7 mS/cm, and a conductivity of about 7 〇. pH value. The dispersion was added in an amount of 0.5, 1 〇 and [5 kg/t in terms of asa and based on the weight of the 18 dry fiber suspension. The retention system used contained 6_ cationic potato starch (Perlbc) nd 97〇) and 〇 5 kg/t (4) (Eka NP 442), which was calculated as dry matter on a dry fiber suspension. The Cobb-60 values and results of the test are shown in Table 3. A lower c〇bb value means that a smaller amount of water is absorbed and thus achieves better sizing. r~~------ Table 3 Dispersion Cobb-60 _ No. 1.5 kg/t 1 164 144 95 2 142 42 29 3 145 38 26 ----- 48 24 21 ^ As seen in Table 3, phase The dispersion liquid No. 2 to 4 produced improved sizing efficacy according to the dispersion of the present invention, compared to the dispersion liquid for the dispersion No. 1 for comparison. . In Example 2, in addition to the change in the amount of ruthenium used and the constant amine content, the dispersion was prepared according to the usual procedure of the implementation and the sizing effect of the dispersion was evaluated. Based on the 4 settings of Knife Liquid, the dispersion had an ASA content of 5% by weight. Table 4 shows this result. ----Table 4 Dispersion No. Si02 (%) TEA (%) Cobb-60(lkg/t) 5 0 2 29 6 1 2 25 7 3 2 23 8 4 2 21 L 9__ A 5 ___2 — 25 Cut 1178 As can be seen in Table 4, the dispersions Nos. 6 to 9 produced improved sizing efficacy compared to the dispersion for dispersion No. 5 for comparison, according to the dispersion of the present invention. Example 3 A dispersion was prepared according to the general procedure of Example 1 and evaluated. A comparison of the dispersions was carried out in an aqueous fiber suspension having an increased conductivity by the addition of calcium chloride. The conductivity of the suspension was measured by using a WTW LF 3 30 instrument from Christian Berner. The results are shown in Table 5. Dispersion No. ASA (%) Si02 (%) TEA (%) Conductivity mS/cm Cobb-60 0.5 kg/t 1.0 kg/t 1.5 kg/t 10 5 0 2 4 128 123 117 11 5 5 2 4 126 108 48 10 5 0 2 8 146 141 135 11 5 5 2 8 125 105 47 As can be seen in Table 5 'When the conductivity of the suspension increases, the dispersion according to the invention' dispersion number 11 shows a significant comparison compared to the use The dispersion is liquid, the dispersion number is 10, and the sizing effect is better. Example 4 • A dispersion was prepared and evaluated according to the general procedure of Example 1 except that different amines were used. The obtained dispersion had an ASA content of 5% by weight, an Si〇2 content of 5% by weight based on ASA, and an amine content of 2.0% by weight based on aSa. The amine used is triethanolamine (TEA) having a molecular weight of 丨49, diethylenetriamine (Deta) having a molecular weight of 103, 20 1321178 distillate coconut fatty acid having a molecular weight of about 200, and dihydrogenation having a molecular weight of about 530. Animal fat diammonium vaporized ammonium (DTDMAC). The particle size is shown in Table 6. Table 6 Amine particle size in dispersion number dispersion (nm) D(vO.l) D(v 0.5) D(v 0.9) 12 DTDMAC 0.34 2.05 9.79 13 FCA 0.41 33.2 211.0 14 DETA "0.13 0.41 1.86 15 TEA 0.11 0.27 0.67 The results of the evaluation of the sizing efficacy are shown in Table 7. Table 7 Amine Cobb-60 in the dispersion number dispersion 0.5 kg/t l.Okg/t 1.5 kg/t 12 DTDMAC 106 44 29 13 FCA 114 83 39 14 DETA 广87 26 23 15 Γ TEA 51 26 21 As can be seen in Tables 6 and 7, the dispersion according to the invention contains an amine having a molecular weight of less than 180 (dispersion numbers 14 and 15) and having a hydroxyl group (dispersion) Dispersion Nos. 14 and 15 of No. 15) produced a smaller particle size and significantly improved sizing efficacy than the dispersion numbers 12 and 13 used for comparison. This also means that less energy is required to free the surface in accordance with the present invention. Example 5 A dispersion was prepared and evaluated according to the general procedure of Example i except that a different anionic polyelectrolyte was used. The obtained dispersion had a 5% content of ASA based on ASA and a content of 5 % by weight based on ASA and Based on ASA 2. 〇% by weight of triethanolamine containing The use of the anion 21 1321178 submerged electrolyte is shown in Table 8. Table 8 Anionic polyelectrolyte description Trade name First-order particle size (nm) A Colloidal aluminized enamel EkaNP590 3 B phthalic acid Eka ΒΜΑ-0 5.5 C Tannic acid Bindzil 50/80 34 D benton Hydrocol sheet structure E bent soil Opazil AV sheet structure muddy in the water (5 wt% bentonite) and stored for 5 days to reach | to sufficient expansion And stratification. Determine particle size and evaluate stability. Stability was measured 2 hours after preparation. If it remained stable after 24 hours, the particle size was determined again. The term "sep." refers to separation. The results are shown in Table 9. Table 9 Dispersion No. Anionic Polyelectrolyte Amine Content (%) Particle Size (μιη) Stability/Separation (2h) D(v0_5) (24 h) D(v0.1) D(v 0.5) D(v 0.9) 16 A - 0.21 1.21 8.29 small amount of sep. - 17 A 2 0.10 0.27 0.83 stable 0.27 18 B - 0.25 1.26 6.69 small amount of sep. 19 B 2 0.16 0.33 0.80 stable 0.27 20 C - 0.27 1.99 13.24 small amount of sep. - 21 C 2 0.10 0.27 0.70 Stable 0.27 22 D - 0.20 1.74 10.67 Separation - 23 D 2 0.1 0 0.25 0.66 Stable 0.23 24 E - 14.32 24.5 38.8 Separation - 25 E 2 0.11 0.27 0.64 Stable 0.25

22 1321178 The results of evaluating sizing efficacy are shown in Table l〇 矣 1 Λ

As can be seen in Tables 9 and 10, in the dispersion according to the present invention, the dispersions containing both the anionic polyelectrolyte and the nitrogen-containing organic compound σ are shown in the ratios of 1, 7, 21, 23 and 25. As a dispersion of nitrogen-containing organic compounds, the dispersions Nos. 16, 18, 2, 22 and 24 have better agglomeration efficiency, better stability and produce smaller particles. size. Example 6

The particle size and sizing efficacy of the dispersion were prepared and evaluated according to the general procedure of Example 1, except that different levels of interfacial activity and different surfactant levels were used. The anionic polycondensate used is a ceric acid gel (Eka NP 780) in the form of a hydrosol having a 7.5 weight percent bismuth Si 〇 2 containing 5 and containing cerium particles having a specific surface area of about 9 〇〇 m 2 /g. It is modified by aluminum. The amine used is triethanolamine (TEA). The dispersion obtained had an ASA content of 5% by weight based on ASA 5 里 里. SiO 2 contains 1, and ASA based 2.0% by weight of triamine containing dan 23 1321178 ^ No surfactant incorporated into dispersion No. 26, hydrolyzed ASA is incorporated as an surfactant into dispersion Nos. 27 and 28 in. The surfactant used in the reference liquid No. 29 is a phosphate (poly(oxy-indene, 2·ethylene) α-isotridecyl-ω-hydroxy phosphate). The content of the surfactant in the dispersion is based on AS Α. The particle size measurement results are shown in Table 丨丄. Table 11 Intervenant surfactant content in dispersion number dispersion Particle size (nm) - (%) D(v 0.5) D(v 0.9) - - 0.33 4.67 14 si 27 Hydrolyzed ASA 1 0.29 2.42 7 63 28 Hydrolyzed ASA 2.5 0.12 0.45 1 83 29 Phosphate 1 0.17 1.05 4.16 Evaluate the sizing efficacy of the dispersion and contain 70% pulp (8〇/2〇 birch/pine veneer) and 30% filler (CaC) A comparison of the dispersions was carried out in an aqueous fiber suspension of 〇3). Table 12 Dispersion No. Conductivity mS/cm Cobb-60 0.5 kg/t 0.75 kg/t 1.0 kg/t 26 0.4 91 84 70 27 0.4 81 69 54 28 0.4 72 48 31 29 0.4 76 49 41 26 0.7 87 78 75 27 0.7 81 64 54 28 0.7 76 47 31 29 0.7 73 52 37 As can be seen in Tables 11 and 12, the dispersions containing the surfactants numbered 27, 28 and 29 produced more than the dispersion without the surfactant. Small particle size and good sizing efficacy. ώ 24 1321178 Example 7 The sizing efficacy of the dispersion of Example 6 was evaluated when unbleached kraft pulp having various electrical conductivities was used. The results are shown in Table 13. Table 13 Dispersion No. Conductivity mS/cm Cobb-60 0.5 kg/t 0.75 kg/t 1.0 kg/t 26 0.4 100 72 37 27 0.4 86 42 27 28 0.4 40 28 23 29 0.4 49 28 22 28 0.7 44 27 22 26 4.0 97 100 76 27 4.0 89 52 28 28 4.0 44 27 23 29 4.0 102 98 76

As can be seen in Table 13, dispersion numbers 27, 28 and 29 containing the surfactant showed better destructive efficacy than dispersion No. 26 which did not contain the surfactant. [Simple description of the diagram] None [Key component symbol description] None 25

Claims (1)

/ X. Patent application scope: an aqueous dispersion of a seed fiber, a quasi-reactive sizing agent, which contains an acid needle, an anionic polyelectrolyte, and a gas-containing organic compound, wherein the nitrogen-containing organic compound has a molecular weight of less than 18 . Amine or its quaternary ammonium. An aqueous dispersion of a cellulose-reactive sizing agent comprising an acid, an anionic polyelectrolyte, and a nitrogen-containing organic compound, wherein the gas-containing organic compound is an amine having - or a plurality of radical groups or Four levels. An aqueous dispersion of a cellulose-reactive sizing agent containing a cerium-anhydride thief-containing nitrogen-containing organic compound, wherein the nitrogen-containing organic compound has a hydroxyl group of 180 and one or more hydroxyl groups Amine or its quaternary & beta amine and its quaternary line, selected from the group consisting of diethylenetriamine, triethylenetetramine, hexamethylenediamine, ethylamine, dipropylamine, diisopropylamine, ring Hexylamine, pyrrole oxime, vein, oxime oxime 0^2 〇σ and amine, early amylamine, diethanolamine, 2-methoxyethylamine, aminoethyl f-private, alanine, a group consisting of aminic acid, choline (Ch〇nne ydroxide), tetramethylammonium hydroxide, and tetraethylammonium hydroxide. According to the aqueous dispersion of any one of the first to third aspects of the invention, the nitrogen-containing organic compound has a molecular weight of up to 170. According to the fourth aspect of the invention, the aqueous dispersion contains the 'nitrogen compound The aqueous dispersion having a molecular weight of up to 160. The aqueous dispersion according to claim 1, wherein the one or more thiol groups are contained. 7. The aqueous solution according to any one of claims 2, 3 and 6 Substituting liquid ^, complex φ _ , ,. 〃 - or 夕 hydroxy group appears at the terminal of one or more substituents of one of the nitrogen-containing compounds. The gas compound is an amine, and the water content of any of the items is in accordance with the first dispersion of the patent application scope, wherein the water-containing component LG of any one of the characters is a four-level classification. Dispersion, 1t1a > and 3 of the watery hexamethylene-η*-diamine, tri-ethylenetetramine, pyridine, hydrazine, -7 propylamine, monoisopropylamine, cyclohexylamine, pyrrole fox , diethanol face, ^ monoethanolamine, diethanolamine, 97 glycoside Ethanolamine, 0-dactylamine, 2-methyllactylethylamine 'Q- ylamine, alanine, ammonium, or tetraethylamine, amidoxime, choline, tetradecyl hydroxide, ammonium sulfonate, ammonium oxide. The patent application scope], the dispersion liquid, wherein the water-based, medium-anion polyelectrolyte of any of the 5 _ 3 items is an inorganic material, wherein the 2 _ 梠 · according to the patent application age m $ 11 items of aqueous dispersion ^ from m decomposed w material. Among them π · according to the scope of the patent application π dangerous j? · another X juice * 尺 ruler knife month liquid ^ green ΧΚ electrolyte for expansion According to the scope of the patent application, the nth anion polyelectrolytic 皙 亡 往 刀 刀 刀 政 政 政 含有 含有 含有 含有 含有 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. Any one of the water, X - is isooctadecenyl succinic acid, amber phthalic anhydride, n + 丄 pa Α anhydride isostearyl decyl, alkenyl carboxylic anhydride, deca-, alkenyl amber Anhydride, de-hydrazine-alkenyl amber anhydride, anthraquinone group anhydride, r: ridin into octyl-2- Alkene-isobutenyl succinic anhydride, succinyl-succinic acid m-hexyl-2. octyl-succinyl (iv) needle. 27 1321178 Aqueous dispersion according to any one of claims 1, 2 and 3 '叾 is based on the weight of the aqueous dispersion, which is present in (M to 30% by weight. / 〇. The water of any of the items 1, 2 and 3 of the patent scope: The anionic polyelectrolyte is present in an amount of 0.5 to 1% by weight based on the weight of the sulphonic acid needle. 8. The aqueous dispersion '', 4 according to any one of claims 1, 2 and 3 of the patent application scope. The nitrogen-containing organic compound is present in an amount of from 0.5 to 10% by weight based on the weight of the phthalic anhydride. An aqueous dispersion according to any one of claims 1, 2 and 3 wherein the dispersion further comprises an anionic surfactant. 20. The aqueous dispersion according to claim 19, wherein the anionic surfactant is a hydrolyzed acid needle. The fiber of any one of the 20's is used for the production of paper 2 1 · an internal sizing or surface sizing for the use of an aqueous dispersion of the first to the vitamin-reactive upper incineration according to the patent application. 22. An aqueous dispersion for preparing a cellulose-reactive sizing agent: a method comprising: an anionic polyelectrolyte and a nitrogen-containing organic compound: dispersing a perylene anhydride in an aqueous phase, wherein the nitrogen-containing organic The compound is and has an amine having a molecular weight of less than 180 or a quaternary ammonium thereof. 23: An aqueous dispersion for the preparation of a cellulose-reactive sizing agent is contained in an anionic polyelectrolyte and a nitrogen-containing organic compound 1 in which an acid is dispersed in an aqueous phase, wherein the nitrogen-containing organic compound An amine having or having a hydroxyl group or a quaternary ammonium thereof. 28 2 4 - an aqueous dispersion for preparing a cellulose-reactive sizing agent. The method is contained in an anionic polyelectrolyte and a nitrogen-containing organic compound. In the presence of the compound, the acid anhydride is dispersed in the aqueous phase and has a small molecular weight; the organic compound is an amine having a temperature of 180 and having a plurality of hydroxylammonium, or a four-stage amine. The amine and its quaternary money are selected from the group consisting of hexa-f-diamine, acetophenone-amine, diethylenetetramine, ' Μ ' - 7 - , amine, cyclohexylamine, etc. Ethanolamine, monoethylamine, Ar 7 1 ethoxylated amine '2, methoxyethylamine, earthy ethanolamine, alanine, ammonium, and tetraethylammonium sulfonamide, tetramethyl hydroxide a group consisting of ammonium telluride. 25' According to the scope of the patent application, the method, wherein the nitrogen-containing compound There are as many as 17. In the amount of the sub-item, the side of the item is 26. According to the method of claim 25, the compound has a molecular weight of up to 160. 〃中^鼠化27_ according to the 22nd item of the patent application scope The method composition has - or a plurality of fluorescene groups. , wherein the 3 nitriding 28 is a method according to any one or more of the above-mentioned patents 22 to 24, /, a hydroxyl group The terminal of the substituent of one of the nitrogen-containing compounds is present at the end of the substituent. 29. According to the scope of the patent application 22 to 24 wherein the nitrogen-containing compound is an amine, the method of the method of the item, 30. Scope 22 to wherein the nitrogen-containing compound is a four-stage method. The method, 31. according to the patent application range 22 to 24, the method of nitriding into the 铷& 呗中任-, Diethylenetriamine, triethylenetetramine, hexamethylenediamine, diethylamine, _:? propylamine, monoisoamine, cyclohexylamine, 0 piroxime, oxime, Α ^ % amine, 2-methoxyethylamine, aminoethyl ethyl epoxide ^ I test, tetramethyl hydride or four of them 3 yin 2 ^ Patented method of any one of a range of 22 to 24, = an inorganic material sub ♦ electrolyte. Wherein the anion wherein the anion is 33. The polyelectrolyte is a enamel material according to the method of claim 32. 34. According to the method of claim 32, the polyelectrolyte is benton. Wherein the anion 35. The polyelectrolyte is a ruthenium-based particle according to the method of claim 32. According to any one of the claims of the patent application, the anhydride, the positive V: is isooctadecenyl succinic anhydride, the iso-octadecyl succinic acid hexazone-based broken acid needle, and the twelve-dilute base J white acid needle, bismuth _, 辛稀酸酸针, triisobutyl sulphate station anhydride, octyl hydrazide-sodium sulphate liver, or hexyl _2 _ _ _ _ 5 white anhydride . The method according to any one of claims 22 to 24, wherein the acid anhydride is based on the weight of the aqueous dispersion. /. presence. The method according to any one of claims 22 to 24, wherein the anionic polyelectrolyte is present in an amount of 0.51% by weight based on the weight of the anhydride. 39. The method according to any one of claims 22 to 24, wherein the nitrogen-containing organic compound is present in an amount of from 0 5 to 10% by weight based on the weight of the acid anhydride. The method of any one of claims 22 to 24, wherein the dispersion further comprises an anionic surfactant. The method of claim 4, wherein the anionic surfactant is a hydrolyzed anhydride. 42. A method of producing paper comprising: adding a cellulose-reactive sizing-cut simmered knife solution to an aqueous fiber suspension, and hydrating the resulting suspension for 1 night on the web' or by application The cellulose-reactive (4) water: the surface of the sheet or the reel of the reel is the aqueous dispersion of the cellulose-reactive sizing agent according to any one of the items: Τ1 to 2〇. According to the patent application, the dad suspension has a conductivity of at least 2.0 mS/, the 42nd method, wherein the aqueous fiber. XI. Schema: