JPWO2010084786A1 - Sizing composition - Google Patents

Abstract

The present invention provides an alkenyl succinic anhydride sizing agent composition that is liquid at 25 ° C. in order to provide an alkenyl succinic anhydride sizing composition that has excellent water resistance, excellent emulsion stability, and is unlikely to cause soiling during use. An alkenyl succinic anhydride sizing agent characterized by being an emulsion obtained by emulsifying a mixture containing 60 to 95% by mass of a product and 5 to 40% by mass of a 2-oxetanone compound that is liquid at 25 ° C. An alkenyl succinic anhydride sizing composition in which the 2-oxetanone compound satisfies the following (1) and (2) is preferably used as a solution. (1) 2-Oxetanone compound (2) obtained by using, as a raw material, a fatty acid mixture having 8 to 20% by mass of fatty acids having 8 to 10 carbon atoms and 92 to 80% by mass of fatty acids having 12 to 18 carbon atoms 2-Oxetanone compound obtained by using, as a raw material, a fatty acid mixture in which the unsaturated fatty acid contained in the fatty acid mixture of (1) is 2% by mass or less

Description

  The present invention relates to a sizing composition, and more particularly to a sizing composition comprising alkenyl succinic anhydride as a main component.

  Alkenyl succinic anhydride (hereinafter sometimes abbreviated as ASA) is widely used as a sizing agent for imparting water resistance to paper in the papermaking field. Similarly, 2-oxetanone compounds typified by alkyl ketene dimers are also used as sizing agents, but ASA has better sizing immediately after papermaking than 2-oxetanone compounds and has a size effect on waste paper pulp and mechanical pulp. It has excellent characteristics. In an actual papermaking process, ASA is used as an emulsion emulsified and dispersed in an aqueous medium. Since ASA is an oily substance at room temperature or in a heated state, it can be emulsified by a conventionally known emulsification method using an emulsifying dispersant and a high-speed stirrer (for example, see Patent Document 1).

  As an emulsifying dispersant for emulsifying ASA, for example, a method using a cationized starch paste (for example, see Patent Documents 1 and 2), a method using a vinyl-based or (meth) acrylamide-based cationic polymer (for example, , Patent Documents 3 and 4), a method using grafted cationized starch obtained by graft polymerization of monomers containing (meth) acrylamide onto cationized starch (for example, see Patent Document 5), and using an amphoteric acrylamide polymer. (For example, refer to Patent Documents 6 and 7).

  However, even if the above emulsifying dispersant is used, ASA is prone to hydrolysis due to contact with moisture, and not only the size effect on paper is reduced, but also the ASA hydrolyzate causes soiling in the papermaking process. It was easy to become and was not yet satisfactory.

  As other methods for improving the quality of the emulsified dispersion, a method using ASA having a specific chemical structure (for example, see Patent Document 8), a method of mixing a hydrophobic substance compatible with ASA (for example, Patent Document) 9) and a method using a sizing dispersion containing ASA and a 2-oxetanone compound (for example, see Patent Document 10). In the above-mentioned Patent Document 10, “the size of the hydrophobic sizing agent includes not only AKD (註: alkyl ketene dimer) but also other sizing agents suitable for improving water repellency such as alkenyl succinic anhydride (ASA). It has also been found to be suitable for the use of paper sizing consisting of being added, however, because ... it becomes necessary to efficiently add ASA sizing in the papermaking process, resulting in a stain problem. This sizing method seems to be unfavorable. "(Refer to the 21st line to the 15th line from the bottom of page 7 of Patent Document 10) Thus, it can be understood that there was a finding that a sizing agent containing ASA at a high rate is not preferable. That is, the effect of imparting size to the paper is not sufficient, and the stain due to the hydrolyzate is not sufficiently eliminated.

  Patent Document 11 discloses a paper sizing agent containing a specific cationic starch, a liquid 2-oxetanone compound, ASA and water (see claim 1 of Patent Document 11). . The cationic starch in the paper sizing agent described in Patent Document 11 is effective as an emulsifier and a retention aid (see page 12 of Patent Document 11). In addition, the sizing agent described in Patent Document 12 is not sufficient for solving the problems of the above-mentioned ASA with respect to a technique for improving a sizing agent mainly composed of a 2-oxetanone compound.

US Pat. No. 3,812,069 (Japanese Patent Laid-Open No. 49-94907 corresponds) Japanese Examined Patent Publication No. 39-002305 JP-A-60-246893 Japanese Patent Publication No. 6-33597 Japanese Patent Laid-Open No. 9-111162 Japanese Patent Publication No. 3-4247 JP 58-45731 A JP-A-6-248596 (Patent No. 2915241) US Pat. No. 6,560,049 Japanese Patent No. 3834699 Special Table 2000-506941 Special Table 2002-517638

  It is an object of the present invention to provide a sizing agent composition that has excellent water resistance, excellent emulsion stability, and is less likely to cause dirt during use.

  As a result of intensive research, the present inventors have mixed water in a specific ratio with a 2-oxetanone compound synthesized from a fatty acid having a specific composition in an alkenyl succinic anhydride, resulting in excellent water resistance and stability of the emulsion. The inventors have found that a sizing composition excellent in the above can be obtained, and have completed the present invention.

That is, the means for solving the problem is as follows:
<1> An emulsion obtained by emulsifying a mixture containing 60 to 95% by mass of an alkenyl succinic anhydride which is liquid at 25 ° C. and 5 to 40% by mass of a 2-oxetanone compound which is liquid at 25 ° C. A sizing composition characterized by
<2> A 2-oxetanone compound is obtained using a fatty acid mixture in which a fatty acid having 8 to 10 carbon atoms is 8 to 20% by mass and a fatty acid having 12 to 18 carbon atoms is 92 to 80% by mass. It is a sizing composition according to the above <1>,
<3> The sizing composition according to <1> or <2>, wherein the 2-oxetanone compound is obtained using a fatty acid mixture having an unsaturated fatty acid content of 2% by mass or less as a raw material. ,
<4> In any one of the above items <1> to <3>, wherein the alkenyl succinic anhydride is an addition reaction product of an olefin having 16 to 24 carbon atoms including an internal isomerized olefin and maleic anhydride. A sizing composition as described,
<5> The alkenyl succinic anhydride that is liquid at 25 ° C., the 2-oxetanone compound that is liquid at 25 ° C., and the total of 100 parts by mass of the alkenyl succinic anhydride and the 2-oxetanone compound. The sizing composition according to any one of <1> to <4>, wherein the composition is an emulsion of a mixture containing 1 to 5 parts by mass of a surfactant.
<6> The sizing composition according to <1> to <5>, wherein an average particle size of the dispersoid in the emulsion is 0.5 μm or more and 1.5 μm or less.

  The present invention can provide a sizing composition having excellent water resistance, excellent dispersion stability of an emulsion, and hardly causing stains during use.

  The alkenyl succinic anhydride may be liquid at 25 ° C., but is preferably an addition reaction product of an olefin having 16 to 24 carbon atoms including an internal isomerized olefin and maleic anhydride. Here, the internal isomerized olefin is not an α-olefin (the olefin in which the double bond is located at the position connecting the first and second carbons of the olefin), but the double bond is more carbon than the α-position by some method. We will refer to the olefins present in the chain. In the present invention, if the double bond is not formed at the α-position in the internal isomerized olefin, the position of the carbon where the double bond is formed is not a problem to achieve the object of the invention. Don't be.

  Specifically, internal isomerization hexadecenyl succinic anhydride, internal isomerization octadecenyl succinic anhydride, internal isomerization icocenyl succinic anhydride, internal isomerization dococenyl succinic anhydride, internal isomerization tetracocete. Nyl succinic anhydride etc. are mentioned, These may be used independently and may be used in mixture of two or more. A mixture containing a plurality of types of internally isomerized alkenyl succinic anhydrides formed by reacting a plurality of types of α-olefins with succinic anhydride is also suitable as a suitable internal isomerized alkenyl succinate. It can be employed as an acid anhydride.

  When the olefin has 16 or more and 24 or less carbon atoms, the size imparting effect of the sizing composition on paper is excellent. In addition, alkenyl succinic anhydride, which is an addition reaction product of an olefin containing an internal isomerized olefin and maleic anhydride, makes ASA difficult to hydrolyze. This is preferable because the decrease is reduced.

Regarding the internal isomerized olefin, the presence of a double bond inside the α-position of the olefin (position connecting the carbon at the 1st position and the carbon at the 2nd position) is 5.4 ppm in ¹ H-NMR analysis of the olefin. This can be confirmed by the presence of a peak derived from an internal isomerized olefin in the vicinity. Conversely, when α-olefin is contained, it can be confirmed by the presence of α-olefin-derived peaks in the vicinity of 5.0 ppm and 5.8 ppm in the analysis by ¹ H-NMR of the olefin. It is also possible to obtain the ratio of α-olefin and internal isomerized olefin based on the integrated value of the peak.

  The internal isomerized olefin can be synthesized by an ordinary organic synthesis method, and can be obtained, for example, by internal isomerization of an α-olefin using a silica / alumina catalyst. Internally isomerized olefin obtained by internal isomerization of α-olefin by a general organic synthesis method is a mixture of internal olefins in which double bond positions are formed at various positions such as 2-position and 3-position of the carbon chain. However, in this invention, in the internal isomerized olefin, which is a mixture of internal olefins formed by isomerization reaction, the position of the specific double bond of the internal olefin is not specified. As long as it is a mixture of internal olefins, each internal olefin may not be specified, and an α-olefin may be included as long as the object of the present invention is not impaired. In the internal isomerized olefin containing various internal olefins, the allowable α-olefin content is 10% by mass or less.

  As a method for obtaining alkenyl succinic anhydride by adding maleic anhydride to the olefin, a general organic synthesis method can be applied. For example, alkenyl succinic anhydride can be obtained by gradually adding maleic anhydride to an olefin heated to 210 ° C. in a nitrogen atmosphere and stirring for 6 to 10 hours.

The 2-oxetanone compound used in the present invention may be liquid at 25 ° C. under normal pressure. 2-Oxetanone compounds that do not become liquid at 25 ° C. under normal pressure need to be heated and stirred for a long time in order to mix with ASA. -The problems of the present invention cannot be achieved due to the disadvantage that the oxetanone compound tends to precipitate as a solid or the emulsion of the mixture with ASA tends to be unstable and causes aggregation or separation. Preferred 2-oxetane compounds include saturated monocarboxylic acids having 8 to 30 carbon atoms, unsaturated monocarboxylic acids having 8 to 30 carbon atoms, saturated dicarboxylic acids having 6 to 44 carbon atoms, and unsaturated dicarboxylic acids having 6 to 44 carbon atoms. A mixture of at least one, preferably two or more selected from the group consisting of these fatty acids and liquid at 25 ° C. under normal pressure, preferably a mixture of fatty acids. And a 2-oxetanone compound mixture that is liquid at 25 ° C. under normal pressure. More preferably, an alkenyl ketene dimer produced from a fatty acid containing an unsaturated fatty acid such as oleic acid or linoleic acid, an alkyl ketene dimer produced from a fatty acid containing a branched fatty acid such as isostearic acid, and a C8 fatty acid and carbon Manufactured using fatty acids that are a mixture of fatty acids of 8 to 20% by mass of fatty acids of several tens and 92 to 80% by mass of fatty acids having 12 to 18 carbon atoms and 2% by mass or less of unsaturated fatty acids. A 2-oxetanone compound that is liquid at 25 ° C. under normal pressure.
These can be easily mixed uniformly with a gentle stirring for a short time when mixed with ASA, and can be kept in a uniform state over a long period of time even when the mixture is stored at 25 ° C. This is preferable because of the advantage that the emulsion has excellent storage stability.

  Specific examples of the raw material include caproic acid, caprylic acid, capric acid, pelargonic acid, stearic acid, isostearic acid, myristic acid, palmitic acid, pentadecanoic acid, undecanoic acid, lauric acid, tridecanoic acid as saturated monocarboxylic acid, Nonadecanoic acid, arachidic acid, and behenic acid, and mixtures thereof may be mentioned, and oleic acid, linoleic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecadiene as unsaturated monocarboxylic acids Acid, octadecatrienoic acid, eicosenoic acid, engineered icosatetraenoic acid, docosenoic acid and docosapentaenoic acid, and mixtures thereof can be mentioned, 8 to 20% by mass of C8 and C10 fatty acids, Fatty acid mixture in which the fatty acid of 12 to 18 is 92 to 80% by mass It is is a liquid at 25 ° C., also preferable because of excellent size properties. Among these, caprylic acid having 8 to 18 carbon atoms (8 carbon atoms), capric acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms) It is preferably made of a fatty acid such as stearic acid (18 carbon atoms), oleic acid (18 carbon atoms), linoleic acid (18 carbon atoms), and contains lauric acid and myristic acid in an amount of 50 to 80% by mass. It is preferable. 8 to 20 mass% of C8 and C10 fatty acids, 3 to 10 mass% of C8 fatty acids, 3 to 12 mass% of C10 fatty acids, C12 and carbon It is more preferable that the number 14 fatty acid is 54 to 78% by mass, and the number of carbon atoms 16 and 18 is 6 to 37% by mass. In order to satisfy the above conditions, it is more preferable to use a fatty acid obtained by converting an alkenyl group of a coconut oil fatty acid into an alkyl group by a hydrogenation reaction.

  The reaction of hydrogenating the raw material containing unsaturated rubonic acid is a reduction reaction using a general hydrogen gas as a reducing agent, and is usually mainly nickel, copper chromium monoxide, ruthenium, palladium, rhodium, platinum, etc. Metal fine powders or those obtained by adsorbing them on an insoluble carrier such as activated carbon, alumina, diatomaceous earth, etc. can be carried out by a general method using a catalyst.

The 2-oxetanone compound can be synthesized by the usual organic synthesis method using the above-mentioned raw materials, and there are also those that can be easily obtained as commercial products. For example, stearyl ketene dimer can be obtained by reacting stearic acid with a chlorinating agent such as phosgene, phosphorus trichloride, thionyl chloride to stearic acid chloride, then dehydrochlorinating with triethylamine, and then removing triethylamine hydrochloride. .
In addition, since the suitable 2-oxetanone compound in this invention can be made to react a fatty-acid mixture as mentioned above, it is a mixture of several 2-oxetanone compounds.

  Among the fatty acids used in the 2-oxetanone compound, the unsaturated fatty acid ratio within 2% by mass can prevent double bond oxidation, and the storage stability, dispersion stability and This is preferable because it contributes to size performance.

  In the present invention, by using the mixture obtained by emulsifying a mixture of the alkenyl succinic anhydride and the 2-oxetanone compound having the mixed composition in a specific ratio, the size effect can be improved, and the aqueous dispersion can be used. Stability improvement and dirt reduction effect can be obtained. As a mixing ratio of the alkenyl succinic anhydride and the 2-oxetanone compound having the above-mentioned mixed composition, a range of alkenyl succinic anhydride: 2-oxetanone compound having the mixed composition = 60: 40 to 95: 5 70:30 to 90:10 is more preferable. When the amount of 2-oxetanone compound is larger than the above range, the size effect is inferior to that of the case of alkenyl succinic acid alone, and when the amount of 2-oxetanone compound is less than the above range, the size effect, stability, and stain reduction are seen. This is not preferable.

  The 2-oxetanone compound and alkenyl succinic anhydride in the present invention are excellent in compatibility with each other and can be mixed under any temperature conditions as long as both are liquid, but it is preferable to mix by heating at 100 ° C. or lower. When the temperature is higher than 100 ° C., there is a risk of discoloration due to alteration due to heat or a decrease in the effect as a sizing agent. When mixing, in order to prevent both alkenyl succinic anhydride and 2-oxetanone compound from being hydrolyzed or denatured with moisture in the air during stirring, moisture such as dry air, nitrogen and argon is used. It is preferable to mix in the atmosphere which does not contain.

  In the sizing agent composition according to the present invention, an effect that the size performance is superior to that of using each of the alkenyl succinic anhydride and the 2-oxetanone compound alone is seen. This is thought to be due to the synergistic effect of improving the hydrophobicity when both molecules are mixed and oriented in addition to the effect of inhibiting hydrolysis of the alkenyl succinic acid.

  Since the sizing composition of the present invention is liquid at room temperature, it can be applied as it is, or it can be dissolved in a solvent such as toluene and applied as a varnish, but it can be used as an aqueous dispersion because of workability. preferable. The aqueous dispersion can be prepared by emulsifying and dispersing by a known emulsification method using a surfactant or various aqueous polymer dispersants. The aqueous dispersion is prepared for the purpose of minimizing performance degradation due to hydrolysis of alkenyl succinic anhydride, and is dispersed immediately before use, or continuously sent to an emulsifier by a pump to prepare an aqueous dispersion. It is preferable to use them continuously.

  In the present invention, it is preferable to emulsify a mixture obtained by further mixing a surfactant with a mixture of an alkenyl succinic anhydride and a 2-oxetanone compound, because it improves emulsifiability and stains hardly adhere to the papermaking tool. . As described above, the amount of the surfactant added to the mixture of the alkenyl succinic anhydride and the 2-oxetanone compound (hereinafter sometimes abbreviated as a surfactant for mixing) is the same as that of alkenyl succinic anhydride and 2 -0.01-10 mass parts is preferable with respect to a total of 100 mass parts with an oxetanone compound, and 0.1-5 mass parts is more preferable. If the amount of the surfactant for mixing is too large, the mixture easily absorbs moisture in the air during storage of the mixture of alkenyl succinic anhydride, 2-oxetanone compound and surfactant. Hydrolysis may be accelerated, and the alkenyl succinic acid that is a hydrolyzate may cause soiling of the papermaking tool and decrease in size performance. If the amount of the surfactant for mixing is too small, the above-mentioned advantages due to mixing may not be sufficiently exhibited.

  As the surfactant for mixing, a conventionally known cationic surfactant, amphoteric surfactant, anionic surfactant, or nonionic surfactant can be used. These may use 1 type (s) or 2 or more types.

  Examples of the cationic surfactant include a long-chain alkylamine salt, a modified amine salt, a tetraalkyl quaternary ammonium salt, a trialkylbenzyl quaternary ammonium salt, an alkylpyridinium salt, an alkylquinolium salt, and an alkylsulfonium salt. It is done.

  Examples of the amphoteric surfactant include various betaine surfactants.

  Examples of the anionic surfactant include alkyl sulfonates, alkyl sulfates, alkyl phosphates, polyoxyalkylene alkyl sulfates, polyoxyalkylene alkylaryl sulfates, polyoxyalkylene aralkyl aryl sulfates. , Alkyl-aryl sulfonates, polyoxyalkylene alkyl phosphates, and various sulfosuccinate surfactants.

  Examples of the nonionic surfactant include fatty acid sorbitan ester and its polyalkylene oxide adduct, fatty acid polyglycol ester, various polyalkylene oxide type nonionic surfactants (polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide, polyoxy Ethylene aliphatic amine, polyoxyethylene aliphatic mercaptan, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene aralkyl aryl ether, polyoxyethylene distyrenated phenol ether phosphate ester, etc.) .

  Among these, anionic surfactants and nonionic surfactants are preferred, and specifically, sulfosuccinic acid dialkyl sodium salts or polyoxyalkylene alkyl ether phosphates are preferred.

  The mixing surfactant may be mixed at the same time when the alkenyl succinic anhydride and the 2-oxetanone compound are mixed, or may be continuously mixed into the mixture of the alkenyl succinic anhydride and the 2-oxetanone compound immediately before emulsification. However, it is preferable to mix in advance with a mixture of an alkenyl succinic anhydride and a 2-oxetanone compound.

  As an emulsifying device, a dispersion of a sizing composition is prepared from an alkenyl succinic anhydride and a 2-oxetanone compound used in the present invention, a surfactant used as necessary, various aqueous polymer dispersants, and water. Can be used, and various types of emulsifiers and emulsifiers such as a static mixer, a venturi mixer, a blender, a homomixer, a high-pressure / high-speed discharge homogenizer, an ultrasonic emulsifier, and a high shear rotary emulsifier can be used. is there.

  When obtaining a sizing composition by emulsification in the present invention, it is preferable to use an aqueous polymer dispersing agent because the dispersion stability of the sizing composition which is an emulsion is excellent.

  Examples of the aqueous polymer dispersant include various water-soluble synthetic polymers and natural polymers. Specifically, starches, acrylamide polymers, starch graft acrylamide polymers, polyvinyl alcohols, carboxymethyl celluloses, gums. And casein. Among these, starches, acrylamide polymers, starch graft acrylamide polymers, carboxymethyl celluloses, and polyvinyl alcohols are preferable.

  The weight average molecular weight of the aqueous polymer dispersant is preferably 10,000 or more and 10,000,000 or less. If the weight average molecular weight is less than 10,000, the emulsifiability and dispersion stability may be reduced. When the weight average molecular weight is larger than 10,000,000, the viscosity of the aqueous polymer dispersant increases, which may make handling difficult.

As the starch, for example, raw starch such as corn, wheat, potato, rice, tapioca and the starch, at least one selected from the group consisting of primary, secondary and tertiary amino groups and quaternary ammonium groups And cationic starch containing basic nitrogen. Also, amphoteric starch obtained by introducing an anionic group (for example, phosphate group) into the cationic starch can be used. Other examples include oxidized starch, dialdehyde starch, alkyl etherified starch, phosphate starch, urea phosphate starch, and hydrophobically modified starch. In the present invention, the object of the present invention can be achieved even if liquid cationic starch is not contained.

  Examples of the acrylamide polymers include water-soluble polymers containing 50 mol% or more of acrylamide and / or methacrylamide, that is, (meth) acrylamide, and may have a cationic group and / or an anionic group. . This acrylamide polymer can be obtained, for example, by a modification method in which an ionic group is introduced by modifying a water-soluble polymer containing (meth) acrylamide as a main component, or (meth) acrylamide and, if necessary, a cationic monomer or anion. It can be obtained by a copolymerization method in which a monomer mixture containing a polymerizable monomer and another vinyl monomer is polymerized by a conventionally known method, or by a combination of both methods.

  In the case of the modification method, a Hoffmann modification reaction, a Mannich reaction, and an amide exchange reaction with a polyamine are used for introducing a cationic group, while a hydrolysis reaction or the like can be used for introducing an anionic group.

  Examples of the cationic monomer include mono- or di-alkylaminoalkyl acrylate, mono- or di-alkylaminoalkyl methacrylate, mono- or di-alkylaminoalkyl methacrylamide, vinyl pyridine, vinyl imidazole, mono- or di-allylamine. And mixtures thereof, and quaternary ammonium salts thereof.

  Examples of the anionic monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, and various other known polymerizable monomers having a sulfonic acid group or a phosphoric acid group. Can be exemplified.

  Examples of the other vinyl monomers include cross-linkable vinyl monomers such as N-methylolacrylamide, methylene (bis) acrylamide, bifunctional monomer, trifunctional monomer, and tetrafunctional monomer that can be copolymerized with (meth) acrylamide. Also, nonionic vinyl monomers such as (meth) acrylic acid ester, styrene, and vinyl acetate can be used in combination.

  The acrylamide polymer used in the present invention can be produced by various conventionally known methods. For example, a reaction vessel equipped with a stirrer and a nitrogen gas introduction tube is charged with vinyl monomer and water as constituents, and as a polymerization initiator, peroxide such as hydrogen peroxide, ammonium persulfate, potassium persulfate, ammonium hydroperoxide, etc. Or any redox initiator comprising a combination of these peroxides and a reducing agent such as sodium bisulfite, and further a water-soluble azo initiator such as 2-2'azobis (aminopropane) hydrochloric acid. Etc. can be used and reacted at a reaction temperature of 40 to 80 ° C. for 1 to 5 hours to obtain acrylamide polymers.

  The starch graft acrylamide polymer used in the present invention is prepared by graft polymerization of monomers capable of forming the acrylamide polymer in the presence of starch.

  For example, it can be obtained by copolymerizing a monomer mixture containing (a) a cationic group-containing monomer, (b) an anionic group-containing monomer, and (c) (meth) acrylamide in an aqueous cationic starch solution.

  Specific examples of the cationic monomer (a) include mono- or di-alkylaminoalkyl acrylate, mono- or di-alkylaminoalkyl methacrylate, mono- or di-alkylaminoalkyl acrylamide, mono- or di-alkyl. Examples thereof include aminoalkyl methacrylamide, vinyl pyridine, vinyl imidazole, mono- or di-aryl amines and mixtures thereof, and quaternary ammonium salts thereof. Examples of the anionic monomer (b) include various known α-, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, as well as various sulfonic acid groups and phosphoric acid groups. Polymerizable monomers can be used. The above modification and copolymerization reactions follow known reaction procedures, and appropriate reaction conditions can be arbitrarily selected.

  As other water-soluble polymers, carboxymethyl celluloses, polyvinyl alcohols, dextrins, chitosans and the like can also be used.

  The concentration and addition amount of the aqueous polymer dispersant are not particularly limited, and the addition amount and concentration can be changed according to the use, but the solid content ratio with respect to the size composition of the present invention is 0.1 to 4 times. Is preferably added.

  Furthermore, when obtaining a sizing agent composition by emulsification, it is preferable to use a surfactant (hereinafter sometimes abbreviated as an emulsifying surfactant) in order to further improve emulsifiability and stability.

  As the surfactant for emulsification, the conventionally known cationic surfactants, anionic surfactants, amphoteric surfactants or nonionic surfactants can be used. These may use 1 type (s) or 2 or more types.

  Among the surfactants, nonionic surfactants and anionic surfactants are preferable as the surfactant for emulsification of the present invention.

  The concentration and addition amount of the surfactant for emulsification are not particularly limited, and the addition amount and concentration can be changed according to the use, but the solid content ratio with respect to the sizing agent composition of the present invention is 0.3 to 3 The use of mass% is preferable because emulsification and stability of the obtained emulsion are improved.

  The surfactant for emulsification may be mixed with the aqueous polymer dispersant in advance, or may be continuously mixed with the aqueous polymer dispersant at the time of emulsification. Is preferred.

  Hereinafter, the effects of the present invention will be specifically described with reference to production examples and examples, but the present invention is not limited to these examples.

(Alkenyl succinic anhydride)
(Production Example 1) Production of alkenyl succinic anhydride (A1) 1-octadecene was isomerized using a silica-alumina catalyst. The obtained internal isomerized octadecene mixture was confirmed to contain no α-olefin by analysis by ¹ H-NMR. 200 g of this internally isomerized octadecene mixture and 86 g of maleic anhydride were reacted at 215 ° C. for 8 hours in an autoclave under a nitrogen atmosphere. Unreacted maleic anhydride and olefin were removed from the reaction solution by distillation under reduced pressure to obtain 235 g of internally isomerized octadecenyl succinic anhydride (A1) which was liquid at 25 ° C. under normal pressure and was a mixture. . Table 1 shows the number of carbon atoms of the isomerized octadecenyl succinic anhydride, the state at 25 ° C., and the content of α-olefin contained in the olefin subjected to the isomerization reaction.

(Production Example 2) Production of alkenyl succinic anhydride (A2) In Production Example 1, 1-hexadecene was used instead of 1-octadecene, and an internal isomerization reaction was carried out in the same manner as in Production Example 1, and ¹ H-NMR Analysis gave an internal isomerized hexadecene mixture free of α-olefins. Further, 243 g of internally isomerized octadecenyl succinic anhydride (A2), which was a liquid at 25 ° C. under normal pressure and was a mixture, was obtained in the same manner as in Production Example 1 except that 96 g of maleic anhydride was used. Table 1 shows the number of carbon atoms of this isomerized hexadecenyl succinic anhydride, the state at 25 ° C., and the content of α-olefin contained in the olefin subjected to the isomerization reaction.

Production Example 3 Production of Alkenyl Succinic Anhydride (A3) In Production Example 1, 1-icosene / 1-docosene / 1-tetracocene = 70/20/10 (mass ratio) instead of 1-octadecene α -Internal isomerization reaction was performed using the olefin mixture in the same manner as in Production Example 1, and an internal isomerized olefin mixture containing no α-olefin was obtained by analysis by ¹ H-NMR. Further, 231 g of internal isomerized alkenyl succinic anhydride (A3) as a mixture was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was changed to 75 g and in a liquid state at 25 ° C. under normal pressure. Table 1 shows the number of carbon atoms of this isomerized alkenyl succinic anhydride, the state at 25 ° C., and the content of α-olefin contained in the olefin subjected to the isomerization reaction.

(Production Example 4) Production of alkenyl succinic anhydride (A4) In Production Example 1, 1-dodecene was used instead of 1-octadecene, and an internal isomerization reaction was carried out in the same manner as in Production Example 1, and ¹ H-NMR Analysis gave an internal isomerized dodecene mixture free of α-olefins. Further, 259 g of internally isomerized dodecenyl succinic anhydride (A4) as a mixture was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was changed to 128 g and in a liquid state at 25 ° C. under normal pressure. Table 1 shows the number of carbon atoms of the isomerized dodecenyl succinic anhydride, the state at 25 ° C., and the content of α-olefin contained in the olefin subjected to the isomerization reaction.

(Production Example 5) Production of alkenyl succinic anhydride (A5) 200 g of propylene tetramer (confirmed to be 7% α-olefin by analysis by ¹ H-NMR) and 128 g of maleic anhydride in a nitrogen atmosphere in an autoclave The reaction was carried out at 215 ° C. for 8 hours. Unreacted maleic anhydride and olefin were removed from the reaction solution by distillation under reduced pressure, and 230 g of branched dodecenyl succinic anhydride (A5) that was liquid at 25 ° C. under normal pressure and contained internal isomerized olefin was obtained. Table 1 shows the number of carbon atoms of this isomerized branched dodecenyl succinic anhydride, the state at 25 ° C., and the content of α-olefin contained in the olefin subjected to the isomerization reaction.

(Production Example 6) Production of alkenyl succinic anhydride (A6) 1-octadecene (confirmed that α-olefin is 100% by analysis by ¹ H-NMR) and 200 g of maleic anhydride were added to nitrogen in the autoclave. The reaction was performed at 215 ° C. for 8 hours under an atmosphere. Unreacted maleic anhydride and 1-octadecene were removed from the reaction solution by distillation under reduced pressure to obtain 239 g of octadecenyl succinic anhydride (A6) which was a solid at 25 ° C. under normal pressure and was not solidified internally. Table 1 shows the number of carbon atoms of the non-internally isomerized octadecenyl succinic anhydride, the state at 25 ° C., and the content of α-olefin contained in the olefin subjected to the isomerization reaction. .

(Production Example 1) Production of 2-oxetanone compound (B1) 200 g of thionyl chloride was placed in a four-necked flask, and the temperature was set to 80 ° C. (thionyl chloride reflux condition). Next, hydrogenation in which the mass composition ratio is caprylic acid / capric acid / lauric acid / myristic acid / palmitic acid / stearic acid / oleic acid = 7/7/51/18/9/8/0 (containing no unsaturated fatty acid) 205.8 g of coconut oil fatty acid (a1) was added dropwise over 2 hours. Thereafter, stirring is continued at 80 ° C. for 1 hour, and thionyl chloride is further distilled off at 80 ° C. under normal pressure to obtain a mixture of caprylic acid chloride, capric acid chloride, lauric acid chloride, myristic acid chloride, palmitic acid chloride and stearic acid chloride. 212.7 g of fatty acid chloride was obtained. Next, 200 g of the above fatty acid chloride and 200 ml of toluene were put in a new four-flask and cooled to 20 ° C., and 108.4 g of triethylamine was added dropwise over 3 hours while maintaining 20 ° C. After completion of the dropwise addition, the temperature was raised to 30 ° C. and the reaction was continued for 3 hours. Next, 200 ml of 3% dilute hydrochloric acid aqueous solution was added and stirred for 10 minutes, and then allowed to stand for 1 hour to separate the lower aqueous phase, and then toluene was distilled off under reduced pressure to obtain a mixture of 2-oxetanone having different carbon numbers. 141.5 g of 2-oxetanone compound (B1) was obtained. The obtained 2-oxetanone compound (B1) was liquid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 2) Production of 2-oxetanone Compound (B2) The hydrogenated coconut oil fatty acid (a1) in Production Example 1 was converted to caprylic acid / capric acid / lauric acid / myristic acid / palmitic acid / stearic acid / oleic acid = 7. The reaction was carried out in the same manner by changing to 205.8 g of hydrogenated coconut oil fatty acid (a2) which was / 7/51/18/9/7/1 (unsaturated fatty acid 1% by mass) to obtain 210.4 g of fatty acid chloride. Next, using 200 g of the obtained fatty acid chloride and 208.4 g of triethylamine, the reaction was carried out in the same manner as in Production Example 1 to obtain 144.7 g of 2-oxetanone compound (B2). The obtained 2-oxetanone compound (B2) was liquid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 3) Production of 2-oxetanone Compound (B3) The hydrogenated coconut oil fatty acid (a1) in Production Example 1 has a mass composition ratio of caprylic acid / capric acid / lauric acid / myristic acid / palmitic acid / stearic acid / Oleic acid = 7/7/51/18/9/6/2 (unsaturated fatty acid 2% by mass) Hydrogenated coconut oil fatty acid (a3) 205.8 g was reacted in the same manner to react with fatty acid chloride. 5 g was obtained. Next, 200 g of the obtained fatty acid chloride and 108.4 g of triethylamine were reacted in the same manner as in Production Example 1 to obtain 142.3 g of 2-oxetanone compound (B3). The obtained 2-oxetanone compound (B3) was liquid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 4) Production of 2-oxetanone Compound (B4) The hydrogenated coconut oil fatty acid (a1) in Production Example 1 was converted to caprylic acid / capric acid / lauric acid / myristic acid / palmitic acid / stearic acid / oleic acid = 7. / 7/51/18/9/1/7 (unsaturated fatty acid 7% by mass) unhydrogenated coconut oil fatty acid (a4) 205.8 g, reacting in the same manner, 210.6 g of fatty acid chloride Obtained. Next, 200 g of the obtained fatty acid chloride and 108.4 g of triethylamine were used in the same manner as in Production Example 1 to obtain 140.3 g of 2-oxetanone compound (B4). The obtained 2-oxetanone compound (B4) was liquid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 5) Production of 2-oxetanone Compound (B5) Hydrogenated coconut oil fatty acid (a1) in Production Example 1 was converted to caprylic acid / capric acid / lauric acid / myristic acid / palmitic acid / stearic acid / oleic acid = 11. / 11/47/14/9/8/0 (unsaturated fatty acid 0% by mass) The fatty acid mixture (a5) was changed to 200.3 g and reacted in the same manner to obtain 204.8 g of fatty acid chloride. Subsequently, using the obtained fatty acid chloride 200g and triethylamine 111.2g, it was made to react like the manufacture example 1, and 142.1g of 2-oxetanone compounds (B5) were obtained. The obtained 2-oxetanone compound (B5) was liquid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 6) Production of 2-oxetanone compound (B6) The hydrogenated coconut oil fatty acid (a1) in Production Example 1 was changed to oleic acid (unsaturated fatty acid 100% by mass) (a6) 282.5 g and reacted in the same manner. 279.1 g of fatty acid chloride was obtained. Next, using 200 g of the obtained fatty acid chloride and 80.8 g of triethylamine, the reaction was conducted in the same manner as in Production Example 1 to obtain 149.6 g of 2-oxetanone compound (B6). The obtained 2-oxetanone compound (B6) was liquid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 7) Production of 2-oxetanone compound (B7) The hydrogenated coconut oil fatty acid (a1) in Production Example 1 was changed to 280.3 g of isostearic acid (a7) and reacted in the same manner to obtain 277.7 g of fatty acid chloride. Obtained. Next, using 200 g of the obtained fatty acid chloride and 81.3 g of triethylamine, the reaction was conducted in the same manner as in Production Example 1 to obtain 146.8 g of 2-oxetanone compound (B7). The obtained 2-oxetanone compound (B7) was liquid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 8) Production of 2-Oxetanone Compound (B8) The hydrogenated coconut oil fatty acid (a1) in Production Example 1 is a fatty acid having a mass ratio of palmitic acid / stearic acid = 60/40 (unsaturated fatty acid 0 mass%). It changed to 267.0g of mixture (a8), and it reacted similarly except heating at 80 degreeC and dripping, and 274.2g of fatty acid chloride was obtained. Subsequently, using the obtained fatty acid chloride 200g and triethylamine 85.1g, it was made to react like the manufacture example 1, and 152.5g of 2-oxetanone compounds (B8) were obtained. The obtained 2-oxetanone compound (B8) was a waxy solid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Production Example 9) Production of 2-oxetanone compound (B9) for Comparative Example 3 Hydrogenated coconut oil fatty acid (a1) in Production Example 1 was converted to lauric acid / paltimic acid / stearic acid = 50/25/25 (unsaturated fatty acid). The reaction was performed in the same manner except that the mixture was changed to 229.9 g of the fatty acid mixture (a9) having a mass ratio of 0% by mass and heated to 80 ° C. and dropped to obtain 228.3 g of fatty acid chloride. Next, using 200 g of the obtained fatty acid chloride and 97.9 g of triethylamine, the reaction was conducted in the same manner as in Production Example 1 to obtain 147.7 g of 2-oxetanone compound (B9). The obtained 2-oxetanone compound (B9) was a waxy solid at 25 ° C. under normal pressure. Table 2 shows the types and blending ratios of the raw fatty acids used to produce the 2-oxetanone compound.

(Surfactant)
Polyoxyethylene distyrenated phenol ether (Daiichi Kogyo Seiyaku Co., Ltd. Neugen EA-167) (D1) as a nonionic surfactant as a surfactant, dioctyl sodium sulfosuccinate (D2) as an anionic surfactant ), Polyoxyethylene distyrenated phenol ether phosphate ester (Pricesurf AL) (D3), a phosphoric acid-based nonionic surfactant, phosphoric acid-based nonionic surfactant Polyoxyethylene alkyl ether phosphate (Pricesurf A208N manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (D4) was used.

(Aqueous polymer dispersant)
Preparation Example 1 <Acrylamide-based polymer aqueous solution>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 335.7 parts of 50% acrylamide aqueous solution, 16.2 parts of N, N-dimethylaminopropylacrylamide, and 80% by weight methacrylic acid aqueous solution 11 2 parts, 4.1 parts of sodium methallylsulfonate, 2.6 parts of normal dodecyl mercaptan, 215.6 parts of ion-exchanged water, 199.8 parts of isopropyl alcohol, and adjusted to pH 4.5 with 20% sulfuric acid It was adjusted. The mixture was heated to 60 ° C. in a nitrogen gas atmosphere while stirring. As a polymerization initiator, 14.8 parts of a 2% aqueous solution of ammonium persulfate was added, and the temperature was raised to 80 ° C. and held for 3 hours. Next, isopropyl alcohol was distilled off, ion-exchanged water was added, and the mixture was cooled to room temperature to obtain an aqueous polymer dispersant solution (C1) having a solid content concentration of 20% by mass, a viscosity of 190 mPa · s, and pH 4.2. Table 3 shows the correspondence between the aqueous polymer dispersant solution and the preparation examples.

Preparation Example 2 <Acrylamide-based polymer aqueous solution>
By adding 75 parts of ion-exchanged water to 25 parts of amphoteric acrylamide-based paper strength agent DS4388 (manufactured by Seiko PMC Co., Ltd.), stirring and diluting, an aqueous solution of acrylamide-based polymers having a solid content of 5.0 mass% (C2) Got. Table 3 shows the correspondence between the aqueous polymer dispersant solution and the preparation examples.

Preparation Example 3 <Starch Grafted Acrylamide Polymer Aqueous Solution>
By adding 66.7 parts of ion-exchanged water to 33.3 parts of starch graft acrylamide paper strength agent DG4204 (manufactured by Seiko PMC Co., Ltd.), stirring and diluting the starch graft acrylamide system having a solid content of 5.0% by mass An aqueous polymer solution (C3) was obtained. Table 3 shows the correspondence between the aqueous polymer dispersant solution and the preparation examples.

Preparation Example 4 <Starch Paste>
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 57 parts of cationized starch Cato304 (manufactured by NSC Japan, water content measured value 13%) was charged, and then 943 parts of water was charged and stirring was started. Dispersed. Next, the temperature was raised to 95 ° C., and stirring was continued for 20 minutes, followed by cooling to 40 ° C. to obtain a cationized starch paste liquid (C4) having a solid content of 5.0% by mass. Table 3 shows the correspondence between the aqueous polymer dispersant solution and the preparation examples.

Preparation Example 5 <Polyvinyl alcohol>
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 20 parts of polyvinyl alcohol “PVA-117” (manufactured by Kuraray Co., Ltd.) was charged, and then 980 parts of water was charged and stirring was started and dispersed. Subsequently, the temperature was raised to 95 ° C., and stirring was continued for 20 minutes, followed by cooling to 40 ° C. to obtain 1000 parts of a polyvinyl alcohol aqueous solution (C5) having a solid content of 2.0% by mass, a viscosity of 10 mPas and pH 6.1. Table 3 shows the correspondence between the aqueous polymer dispersant solution and the preparation examples.

Preparation Example 6 <Water-soluble celluloses>
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 20 parts of carboxymethylcellulose “Serogen 5A” (Daiichi Kogyo Seiyaku Co., Ltd.) was charged, and then 980 parts of water was charged and stirring was started and dispersed. Next, the temperature was raised to 95 ° C., and stirring was continued for 20 minutes, followed by cooling to 40 ° C. to obtain 1000 parts of a carboxymethyl cellulose aqueous solution (C6) having a solid content of 2.0% by mass, a viscosity of 10 mPas and pH 6.1. Table 3 shows the correspondence between the aqueous polymer dispersant solution and the preparation examples.

  The particle size measurement, stability test, and water resistance test were performed as follows.

<Particle size measurement>
About the emulsion obtained by emulsification, the weight average particle diameter was measured using laser light scattering type particle size distribution analyzer LA-910 (made by Horiba Ltd.).

<Water resistance test 1>
Bleached kraft pulp (mixed pulp with softwood to hardwood pulp ratio of 1 to 9) is diluted with water for dilution with a conductivity of 35 mS / m so that the pulp concentration is 2.5 mass%, and a Canadian standard using a beater Beat up to Freeness 430. Next, 1.2 liters of the obtained pulp slurry was weighed in a disaggregator, kept at 40 ° C., and with stirring, 5% by weight of light calcium carbonate (Tama Pearl 121 manufactured by Okutama Kogyo Co., Ltd.) was added to the sulfuric acid band. After adding 0.5% by mass of pulp and 0.7% by mass of cationic starch (Cato304 manufactured by Nippon SC Co., Ltd.) to pulp, 0.1% by mass of the sizing composition was added. Thereafter, the obtained pulp slurry is diluted with diluted water having a pH of 8 and an electrical conductivity of 35 mS / m to a concentration of 0.8% by mass, and the light calcium carbonate is further added to 15% by mass of the pulp, a cationic retention agent (manufactured by Hymo Co., Ltd.). (Yield agent NR12MLS) was added to 0.01% by weight of pulp sequentially, hand-made with a paper machine manufactured by Noble and Wood to a basis weight of 65 g / m ^2, and the moisture content in the wet paper was measured with a lab roll press. After adjusting to 55%, it was dried using a drum dryer at 100 ° C. for 80 seconds. The resulting paper was placed at 23 ° C. and 50% R.D. H. After adjusting the humidity in a constant temperature and humidity chamber for 24 hours, the water resistant performance was evaluated by measuring the Stekkite sizing degree according to JIS P-8122. It means that it is excellent in water resistance provision, so that this measured value is large. This papermaking condition corresponds to fine paper.

<Water resistance test 2>
The test was carried out in the same manner as in the water resistance test 1 except that the pulp slurry was kept at 40 ° C. for 1 hour under stirring before adding the cationic retention agent. In this test, the time during which the sizing emulsion is dispersed in the moisture of the pulp slurry is longer than that of the water resistance test 1 and the hydrolysis of the sizing proceeds. It is.

<Water resistance test 3>
The used corrugated paper was diluted with dilution water having an electric conductivity of 100 mS / m so that the pulp concentration was 2.5% by mass, and beaten to Canadian Standard Freeness 330 using a beater. Next, 1.2 liters of the obtained pulp slurry was weighed in a disaggregator, kept at 40 ° C., and 0.3% by mass of a dry paper strength agent (DS4416 manufactured by Seiko PMC Co., Ltd.) was added with stirring. Thereafter, 0.14% by mass of the sizing agent composition was added to the pulp. Thereafter, the obtained pulp slurry is diluted to a concentration of 0.8 mass% with diluted water having a pH of 7.5 and an electric conductivity of 100 mS / m, and a dry paper strength agent (DH4160 manufactured by Seiko PMC Co., Ltd.) is added to 0.05 mass of pulp. %, And hand-made to a basis weight of 80 g / m ² with a paper machine manufactured by Noble and Wood, and adjusted the moisture content in the wet paper to 58% with a lab roll press, and then used a drum dryer. Drying was performed at 100 ° C. for 80 seconds. The resulting paper was placed at 23 ° C. and 50% R.D. H. After adjusting the humidity in a constant temperature and humidity chamber for 24 hours, the water absorption performance (120 seconds) was measured according to JIS P-8140 to evaluate water resistance. It means that it is excellent in water resistance provision, so that this measured value is small. This papermaking condition corresponds to a paperboard such as a liner.

<Water resistance test 4>
Before adding the dry paper strength agent DH4160, the test was conducted in the same manner as the water resistance test 3 except that the pulp slurry was kept at 40 ° C. for 1 hour under stirring. In this test, the time during which the sizing emulsion is dispersed in the water of the pulp slurry is longer than that of the water resistance test 3, and the hydrolysis of the sizing agent proceeds. It is.

<Dirt test 1>
Instead of adding chemicals to bleached kraft pulp as in the water resistance test 1 and conducting a hand-making test, the slurry is filtered through a 60 mesh stainless steel mesh, and the filtration residue is brought into close contact with the stainless steel plate and 4.2 kgf / cm ^2. The stainless plate was pressed for 2 minutes at a pressure of 2 mm and peeled, and the stainless steel plate was observed for four-stage evaluation. As the emulsion becomes unstable and the fixing property to the pulp fiber becomes worse, the transfer to the stainless steel plate becomes easier, and as the hydrolysis of the alkenyl succinic acid proceeds, the tackiness increases and the transfer to the stainless steel plate becomes easier. In this evaluation, the greater the amount of dirt, the more likely it is to cause dirt even under actual use conditions. The criteria for evaluation are as follows.
A: No dirt adhesion is observed.
○: Slight adhesion is observed.
Δ: A small amount of adhesion is observed.
X: A large amount of adhesion is observed.

<Dirt test 2>
As in the water resistance test 2, the preparation of the pulp slurry was conducted in the same manner as in the soil test 1 except that it was kept in a stirred state at 40 ° C. for 1 hour before the retention agent was added.

Example 1
In a sealed container equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 70 g of alkenyl succinic anhydride (A1) is charged, and then 30 g of 2-oxetanone compound (B1) is charged at 25 ° C. for 1 hour in a nitrogen atmosphere. Stirring was continued to obtain 100 g of a mixture having a ratio of A2 / B1 = 70/30. Next, 15 g of the obtained mixture and 15 g of acrylamide polymer (C1) having a solid content of 20% by mass were stirred for 30 minutes at 15000 rpm with a rotary homomixer (manufactured by Nippon Seiki Seisakusho), An emulsion was obtained. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 2
An emulsion was obtained in the same manner as in Example 1, except that the alkenyl succinic anhydride (A1) was changed to the alkenyl succinic anhydride (A2). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 3
An emulsion was obtained in the same manner as in Example 1 except that the alkenyl succinic anhydride (A1) was changed to the alkenyl succinic anhydride (A3). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 4
An emulsion was obtained in the same manner as in Example 1 except that the alkenyl succinic anhydride (A1) was changed to the alkenyl succinic anhydride (A4). Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 5
An emulsion was obtained in the same manner as in Example 1 except that the alkenyl succinic anhydride (A1) was changed to the alkenyl succinic anhydride (A5). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 6
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B2). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 7
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B3). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 8
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B4). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 9
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B5). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 10
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B6). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 11
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B7). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 12
In Example 1, 70 g of alkenyl succinic anhydride (A1) and 30 g of 2-oxetanone compound (B1) were changed to 85 g of alkenyl succinic anhydride (A1) and 15 g of 2-oxetanone compound (B1), respectively. In the same manner as in Example 1, an emulsion was obtained. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 13
In Example 1, 70 g of alkenyl succinic anhydride (A1) and 30 g of 2-oxetanone compound (B1) were changed to 95 g of alkenyl succinic anhydride (A1) and 5 g of 2-oxetanone compound (B1), respectively. In the same manner as in Example 1, an emulsion was obtained. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 14
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the mixture was stirred at 10000 rpm for 1 minute with a rotary homomixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 15
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the mixture was stirred at 15000 rpm for 3 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Comparative Example 1
In Example 1, the emulsion was prepared in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B8) and the temperature during stirring was changed from 25 ° C. to 50 ° C. When 10 minutes passed, the waxy 2-oxetanone compound (B8) was precipitated and separated in the obtained dispersion, and therefore, the particle size measurement and the water resistance test could not be performed. The emulsion prepared in this comparative example is out of the scope of the present invention because the emulsion state is destroyed in a short time.

Comparative Example 2
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the 2-oxetanone compound (B1) was changed to the 2-oxetanone compound (B9), but the emulsion separated after 1 hour had passed. A stable emulsion could not be obtained. Therefore, the particle size measurement and the water resistance test could not be performed.

Comparative Example 3
In Example 1, 70 g of alkenyl succinic anhydride (A1) and 30 g of 2-oxetanone compound (B1) were changed to 50 g of alkenyl succinic anhydride (A1) and 50 g of 2-oxetanone compound (B1), respectively. Otherwise, an emulsion was obtained in the same manner as in Example 1. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Comparative Example 4
In Example 1, 70 g of alkenyl succinic anhydride (A1) and 30 g of 2-oxetanone compound (B1) were changed to 98 g of alkenyl succinic anhydride (A1) and 2 g of 2-oxetanone compound (B1), respectively. Otherwise, an emulsion was obtained in the same manner as in Example 1. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Comparative Example 5
In Example 1, an emulsion was obtained in the same manner as in Example 1 except that the alkenyl succinic anhydride (A1) was changed to the alkenyl succinic anhydride (A6). Separated and stable emulsion was not obtained. Therefore, the particle size measurement and the water resistance test could not be performed.

Comparative Example 6
A total of 30 g of 15 g of alkenyl succinic anhydride (A1) and 15 g of acrylamide polymer (C1) having a solid content of 20% by mass was stirred at 15000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho). An emulsion of alkenyl succinic anhydride (A1) was obtained. For this dispersion, 0.1% by weight of the sizing composition dispersion was added to the pulp in all of <Water resistance test 1>, <Water resistance test 2>, <Stain test 1>, and <Stain test 2>. Instead, each test was performed after adding 0.1% by weight of an alkenyl succinic anhydride (A1) emulsion to the pulp. Table 6 shows the performance evaluation results.

Comparative Example 7
A total of 30 g of 15 g of alkenyl succinic anhydride (A1) and 15 g of acrylamide polymer (C1) having a solid content of 20% by mass was stirred at 15000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho). An emulsion of alkenyl succinic anhydride (A1) was obtained. Separately, 15 g of 2-oxetanone compound (B1) and 15 g of acrylamide polymer (C1) having a solid content of 20%, 30 g in total, were rotated at 15000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho). The mixture was stirred to obtain an emulsion of a 2-oxetanone compound (B1). 21 g of emulsion of alkenyl succinic anhydride (A1) and 9 g of emulsion of 2-oxetanone compound (B1) were rapidly stirred and mixed, and 70 pairs of alkenyl succinic anhydride (A1) and 2-oxetanone compound (B1) were mixed. A mixture of emulsions having a mass ratio of 30 was obtained. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.
This comparative example is “emulsification obtained by emulsifying a mixture containing 60 to 95% by mass of alkenyl succinic anhydride which is liquid at 25 ° C. and 5 to 40% by mass of 2-oxetanone compound which is liquid at 25 ° C. Since it is not a "product", it is outside the scope of this invention.

Comparative Example 8
A total of 30 g of 15 g of alkenyl succinic anhydride (A1) and 15 g of acrylamide polymer (C1) having a solid content of 20% by mass was stirred at 15000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho). An emulsion of alkenyl succinic anhydride (A1) was obtained. Separately, 15 g of 2-oxetanone compound (B1) and 15 g of acrylamide polymer (C1) having a solid content of 20%, 30 g in total, were rotated at 15000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho). The mixture was stirred to obtain an emulsion of a 2-oxetanone compound (B1). With respect to these two types of dispersions, in all of <Water resistance test 1>, <Water resistance test 2>, <Stain test 1>, and <Stain test 2>, the dispersion of the sizing composition was 0.1 Each test after separately adding 0.07% by mass of an emulsion of alkenyl succinic anhydride (A1) to pulp and 0.03% by mass of an 2-oxetanone compound (B1) to pulp instead of adding% by mass Went. Table 6 shows the performance evaluation results.

Example 16
70 g of alkenyl succinic anhydride (A1) is charged into a sealed container equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube, then 30 g of 2-oxetanone compound (B1) and 0 of an anionic surfactant (D2) .5 g was charged and stirring was continued at 60 ° C. for 1 hour under a nitrogen atmosphere, followed by cooling to 25 ° C., thereby obtaining 100.5 g of a mixture of A1 / B1 = 70/30 containing 0.5% by mass of a surfactant. Next, 15 g of the obtained mixture and 15 g of acrylamide polymer (C1) having a solid content of 20%, 30 g in total, were stirred at 15000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain an emulsion. Got. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 17
In Example 16, an emulsion was obtained in the same manner as in Example 16 except that alkenyl succinic anhydride (A1) was replaced with alkenyl succinic anhydride (A2) and 1.1 g of surfactant (D2) was further charged. . This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 18
In Example 16, an emulsion was prepared in the same manner as in Example 16 except that alkenyl succinic anhydride (A1) was replaced by alkenyl succinic anhydride (A3) and 6.4 g of surfactant (D2) was further added. Obtained. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 19
In Example 16, an emulsion was obtained in the same manner as in Example 16 except that 5.3 g of the surfactant (D2) was charged. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation.

Example 20
70 g of alkenyl succinic anhydride (A1) is charged into a sealed container equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, then 30 g of 2-oxetanone compound (B1) and 1.1 g of surfactant (D2) The mixture was charged and stirred at 60 ° C. for 1 hour under a nitrogen atmosphere, and then cooled to 25 ° C. to obtain 101.1 g of a mixture of A1 / B1 = 70/30 containing 1.0% by mass of a surfactant. Next, 10 g of the obtained mixture and 20 g of acrylamide polymer (C2) diluted with water to a solid content of 5% by mass were mixed at 15000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusho). Stir to obtain an emulsion. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 21
In Example 20, 42 g of a total of 42 g of 2 g of a mixture of A1 / B1 = 70/30 containing 1.0% by mass of a surfactant and 40 g of starch graft polymer (C3) having a solid content of 5% by mass were mixed with a rotary homomixer. (Nippon Seiki Seisakusho Co., Ltd.) was stirred at 15000 rpm for 2 minutes to obtain an emulsion. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 22
In Example 20, 42 g of a total of 42 g of a mixture of A1 / B1 = 70/30 containing 1.0% by mass of a surfactant and 40 g of starch paste (C4) having a solid content of 5% by mass were mixed with a rotary homo The mixture was stirred at 15000 rpm for 3 minutes with a mixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain an emulsion. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 23
In Example 20, a total of 42 g of 2 g of a mixture of A1 / B1 = 70/30 containing 1.0% by mass of a surfactant and 40 g of a polyvinyl alcohol aqueous solution (C5) having a solid content of 5% by mass was mixed with a rotating homopolymer. The mixture was stirred at 15000 rpm for 3 minutes with a mixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain an emulsion. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 24
In Example 20, 2 g of a mixture of A1 / B1 = 70/30 containing 1.0% by mass of a surfactant and 40 g of a carboxymethyl cellulose aqueous solution (C6) having a solid content of 5% by mass were combined in a total of 42 g. The mixture was stirred at 15000 rpm for 3 minutes with a mixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and this emulsion maintained an emulsion state stably for 6 hours or more. An emulsion was obtained. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 25
In Example 20, the 2-oxetanone compound (B1) is changed to the 2-oxetanone compound (B2), the acrylamide polymer (C2) is changed to the acrylamide polymer (C1), and the surfactant (D2) is changed to the surfactant. An emulsion was obtained in the same manner as in Example 20 except for changing to (D1). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 26
In Example 20, the 2-oxetanone compound (B1) is changed to the 2-oxetanone compound (B3), the acrylamide polymer (C2) is changed to the acrylamide polymer (C1), and the surfactant (D2) is changed to the surfactant. An emulsion was obtained in the same manner as in Example 20 except for changing to (D3). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 27
In Example 20, the 2-oxetanone compound (B1) is changed to the 2-oxetanone compound (B3), the acrylamide polymer (C2) is changed to the acrylamide polymer (C1), and the surfactant (D2) is changed to the surfactant. An emulsion was obtained in the same manner as in Example 20 except for changing to (D4). This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 28
70 g of alkenyl succinic anhydride (A1) is charged into a sealed container equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube, then 30 g of 2-oxetanone compound (B1) and 1.1 g of surfactant (D1) The mixture was charged and stirred at 60 ° C. for 1 hour under a nitrogen atmosphere, and then cooled to 25 ° C. to obtain 101.1 g of a mixture of A1 / B1 = 70/30 containing 1.0% by mass of a surfactant. Separately, 195 g of an acrylamide polymer (C1) having a solid content of 20%, 1 g of a surfactant (D2), and 604 g of water were added and stirred at 25 ° C. for 1 hour, followed by acrylamide polymer (C1) / surfactant ( D2) An aqueous solution having a solid content of 5% and a solid content mass ratio of 97.5 / 2.5 was obtained. Subsequently, 10 g of the obtained mixture and 20 g of the aqueous solution, 30 g in total, were stirred for 2 minutes at 10,000 rpm with a rotary homomixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain an emulsion. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Example 29
In a sealed container equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 70 g of alkenyl succinic anhydride (A1) is charged, and then 30 g of 2-oxetanone compound (B1) is charged at 25 ° C. for 1 hour in a nitrogen atmosphere. Stirring was continued to obtain 100 g of a mixture of A1 / B1 = 70/30. Separately, 195 g of acrylamide polymer (C1) having a solid content of 20% by mass, 1 g of surfactant (D2), and 604 g of water were added and stirred at room temperature for 1 hour, followed by acrylamide polymer (C1) / surfactant ( D2) An aqueous solution having a solid content of 5% and a solid content mass ratio of 97.5 / 2.5 was obtained. Subsequently, 10 g of the obtained mixture and 20 g of the aqueous solution, 30 g in total, were stirred at 12000 rpm for 2 minutes with a rotary homomixer (manufactured by Nippon Seiki Seisakusyo Co., Ltd.) to obtain an emulsion. This emulsion maintained the emulsion state stably for 6 hours or more. Table 5 shows the particle diameter of the obtained dispersion, and Table 6 shows the results of performance evaluation. Table 4 shows the correspondence between the symbol indicating the surfactant and the type of the surfactant.

Explanation of abbreviations in Table 1 C18: 18 carbon atoms,
C16: 16 carbon atoms
C22 / C22 / C24 = 70/20/10: the ratio of carbon numbers 20, 22, 24 is 70, 20, 10,
C12: 12 carbon atoms
Indicates that

Explanation of Abbreviations in Table 5 Note 1: A1 emulsion and B1 emulsion were separately prepared and then mixed.
Note 2: Particle size of mixed emulsion Note 3: A1 emulsion and B1 emulsion were separately prepared and added separately.

Claims (6)

It is an emulsion obtained by emulsifying a mixture containing 60 to 95% by mass of an alkenyl succinic anhydride which is liquid at 25 ° C. and 5 to 40% by mass of a 2-oxetanone compound which is liquid at 25 ° C. A sizing agent composition. The 2-oxetanone compound is obtained using a fatty acid mixture in which a fatty acid having 8 to 10 carbon atoms is 8 to 20% by mass and a fatty acid having 12 to 18 carbon atoms is 92 to 80% by mass, as a raw material. The sizing composition of claim 1. The sizing composition according to claim 1 or 2, wherein the 2-oxetanone compound is obtained from a fatty acid mixture containing 2% by mass or less of an unsaturated fatty acid as a raw material. The alkenyl succinic anhydride is an addition reaction product of an olefin having 16 to 24 carbon atoms including an internal isomerized olefin and maleic anhydride. Sizing composition. 0.1 to 5 parts per 100 parts by mass in total of the alkenyl succinic anhydride which is liquid at 25 ° C., the 2-oxetanone compound which is liquid at 25 ° C., and the alkenyl succinic anhydride and the 2-oxetanone compound. The alkenyl succinic anhydride sizing composition according to any one of claims 1 to 4, wherein the composition is an emulsion of a mixture containing part by mass of a surfactant. The alkenyl succinic anhydride sizing composition according to any one of claims 1 to 5, wherein an average particle size of a dispersoid in the emulsion is 0.5 µm or more and 1.5 µm or less.