JPH0214477B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a sizing composition, and more particularly to a sizing composition that allows a sizing emulsion to be prepared very easily. Conventionally, substituted cyclic dicarboxylic acid anhydrides such as alkenyl succinic anhydride have been widely used as neutral paper sizing agents, and as emulsifiers for emulsifying these, cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, or Cationic starches are known (Japanese Unexamined Patent Publication No. 49-94907,
JP-A-50-160505, JP-A-58-87398, JP-A-58-87397). However, when a sizing agent such as alkenyl succinic anhydride is emulsified with these emulsifiers, expensive emulsification equipment such as a high-speed homomixer or high-pressure homogenizer is used, or a very complicated emulsification method called a phase inversion method is used. There was a problem with the emulsification process. Therefore, the present inventors conducted research to develop a composition that would allow the emulsification process to be carried out easily and with inexpensive equipment.The inventors found that they could achieve their goal by using a composition in which a specific acid was added to a sizing agent and an emulsifier. We have discovered that this can be achieved, and based on this knowledge, we have completed the present invention. That is, the present invention provides at least one of (A) a substituted cyclic dicarboxylic acid anhydride (hereinafter referred to as component (A)), (B) an anionic emulsifier, a cationic emulsifier, and an unmodified nonionic emulsifier. One type of emulsifier (hereinafter referred to as component (B)). and (C) at least one organic acid selected from fatty acids, dicarboxylic acids, and sulfonic acids (hereinafter referred to as component (C)). The substituted cyclic dicarboxylic acid anhydride, which is component (A) of the present invention, has the effect as a sizing agent and is the base of the composition of the present invention, and various compounds can be used, but usually the following compounds are used. Those represented by the general formula are preferred. In the above formula, R represents a dimethylene group or a trimethylene group, and R' represents an alkyl group, an alkenyl group, an aralkyl group, an aralkenyl group, etc., and those having 5 or more carbon atoms are particularly preferred.
Specific examples of R' include octyl, dodecyl, hexadecyl, octadecyl, 1-propyl-2-tridecenyl, 1-ethyl-2-tetradecenyl,
1-methyl-2-pentadecenyl, 1-ethyl-
Examples include 2-hexadecenyl, 1-hexyl-2-tetradecenyl, polypropylenyl, polyisobutynyl, polybutynyl, and styryl. Specific examples of component (A) include octyl succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, 1-propyl-2-tridecenyl succinic anhydride, and 1-ethyl-2-tetradecenyl succinic anhydride. , 1-methyl-2-pentadecenyl succinic anhydride, 1-ethyl-2-hexadecenyl succinic anhydride, 1-hexyl-2-tetradecenyl succinic anhydride, polypropylenyl succinic anhydride, polyisobutynyl succinic anhydride, polybutynyl succinic anhydride, Styryl succinic anhydride, octyl glutamic anhydride, dodecyl glutamic anhydride, hexadecyl glutamic anhydride, octadecyl glutamic anhydride, 1-propyl-2-tridecenyl glutamic anhydride, 1-
ethyl-2-hexadecenyl glutamic anhydride,
Examples include 1-hexyl-2-tetradecenyl glutamic anhydride, polypropylenyl glutamic anhydride, polyisobutynyl glutamic anhydride, polybutynyl glutamic anhydride, styryl glutamic anhydride, and mixtures thereof. Next, as component (B), various emulsifiers such as anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers are used. Specifically, the anionic emulsifiers include alkaline earth metal salts of alkylbenzenesulfonic acid, such as calcium dodecylbenzenesulfonate and sodium undecylbenzenesulfonate; alkaline earth metal salts of α-olefin sulfonic acid, such as alkaline earth metal salts of α-olefin sulfonic acid, such as Usually 8 to 20 α-olefin sulfonic acid calcium or sodium salts; sulfosuccinate alkaline earth metal salts, such as 2-ethylhexylsulfosuccinate calcium salt, dicyclohexylsulfosuccinate calcium salt, etc.; (alkyl)naphthalene sulfone Formalin condensates of acid salts and (alkyl)naphthalene sulfonates, such as diisopropylnaphthalene sulfonate calcium salt; alkanesulfonates, such as tetradecyl sulfonate calcium salt; fatty acid amidosulfonic acid alkaline earth metal salts; alkyl sulfates Ester alkaline earth metal salts, such as decyl alcohol sulfate calcium salt, lauryl alcohol sulfate calcium salt, oxo alcohol sulfate magnesium salt;
Polyoxyalkylene alkyl sulfate alkaline earth metal salts, e.g. decyl alcohol EO(1)
Sulfate ester calcium salt (EO indicates ethylene oxide, and the number in parentheses indicates the number of moles.Hereinafter,
Display the same. ), lauryl alcohol EO(4) sulfate ester calcium salt, cetyl alcohol EO
(8) Sulfate ester calcium salt, etc.; polyoxyalkylene alkylaryl ether sulfate ester alkaline earth metal salt, such as nonylphenol
EO(2) sulfate ester calcium salt, etc.; alkaline earth metal sulfate esters of higher fatty acid esters, such as coconut oil fatty acid monoglyceride sulfate ester calcium salts. As a cationic emulsifier, tetraalkylammonium halide,
Examples include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and distearyldimethylammonium chloride. In addition, as the unmodified nonionic emulsifier in the present invention, polyoxyalkylene alkylaryl ethers, such as nonylphenol EO (8), octylphenol EO (10), dodecylphenol EO
(10), nonylphenol EO(10), etc.; polyoxyalkylene styrenated aryl ether, such as styrenated phenol PO(10) (PO indicates propylene oxide. Hereinafter, the same will be indicated), EO
(25) PO(3), styrenated phenol EO(10), etc.; polyoxyalkylene polyhydric alcohol fatty acid ester, such as sorbitol laurate EO(10),
Castor oil EO (30), etc.; polyoxyalkylene alkyl ethers, such as 6-20 carbon atoms Ziegler alcohol EO (8), octyl alcohol EO (10), coconut oil reduced alcohol EO (5), etc.; polyoxyethylene polyoxypropylene Block copolymer; polyoxyalkylene fatty acid ester, such as oleic acid and polyethylene glycol (molecular weight 600)
Mono- or diester with stearic acid EO
(15), lauric acid EO (10), etc.; polyoxyalkylenealkylamines, such as stearylamine
EO(10) etc; polyoxyalkyl mercaptan,
For example, cetyl mercaptan EO (10), etc.; Alkylolamide nonionic surfactants, such as lauric acid diethanolamide EO (4), etc.; polyhydric alcohol fatty acid esters, such as lauric acid monoglyceride, sorbitan stearate, sorbitan oleate ester , sucrose stearate, and the like. As the emulsifier, the various compounds listed above may be used as a mixture. The present invention is characterized by the addition of at least one organic acid selected from fatty acids, dicarboxylic acids, and sulfonic acids as component (C), and by adding the organic acid, high-speed mixers, etc. It is possible to easily produce a sizing emulsion having a small particle size without using a sizing emulsion. Here, specific examples of organic acids include fatty acids such as stearic acid, alkenyldicarboxylic acids such as alkenylsuccinic acid, α-olefin sulfonic acids such as sulfonated products of _C16 to _C18 α-olefins, alkylbenzene sulfonic acids, and aromatic acids. These include group sulfonic acids. The composition of the present invention can be obtained by blending the above components (A), (B) and (C). There is no particular restriction on the amount to be blended, but if component (A) is 100 parts by weight,
Component (B) is usually used in an amount of 5 to 15 parts by weight, and component (C) is used in an amount of 1 to 15 parts by weight. When the amount of component (B) is less than 5 parts by weight, it becomes impossible to adjust the emulsion, and when it exceeds 15 parts by weight, the sizing performance of the resulting sizing agent composition deteriorates, which is not preferable. Furthermore, if component (C) is outside this range, a good emulsion cannot be obtained. The composition of the present invention is used to produce a sizing emulsion by adding it to water, but it does not require conventional emulsification equipment such as a high-speed mixer or a high-pressure homogenizer, and it also does not require the use of a phase inversion method. A sizing emulsion having a sufficiently satisfactory sizing degree can be obtained with simple equipment using a simple propeller stirring blade or the like. When the emulsion state was measured using an optical microscope, it was found that the emulsion made using a high-speed mixer etc.
An emulsion with a particle size of about 3μ was obtained, and emulsions with a particle size of about 5 to 15μ could only be obtained using propeller stirring blades, but the sizing agent composition of the present invention was able to obtain emulsions with a particle size of about 1 to 5μ by propeller stirring blades. The particle size can be obtained. In addition, industrially, even if the sizing agent composition of the present invention is fed into a paper machine without being emulsionized,
Since the emulsion is formed in a pumping process, there is an advantage that no special emulsification equipment is required. As described above, the sizing agent composition of the present invention allows a size emulsion having a sufficient sizing degree to be easily obtained using inexpensive equipment, and is extremely useful for the paper manufacturing industry. Next, the present invention will be explained in detail with reference to examples. Production example 1 Isobutylene oligomer (1 mole) having 11 to 18 carbon atoms and maleic anhydride (1 mole) were reacted at 230°C for 5 hours using an autoclave, and then distilled under reduced pressure at a vacuum degree of 1 mmHg to a boiling point of 140 to 190. C. alkenyl succinic anhydride (0.6 mol) was obtained. This is designated as compound A. Production Example 2 Alkenyl succinic anhydride (0.1
acetone (100 ml) in water (0.3 mol) and water (0.3 mol)
was added and reacted at 100℃ for 8 hours using an autoclave, alkenyl dicarboxylic acid (0.09 mol)
I got it. This is designated as compound B. Production Example 3 Using a thin film reactor, α-olefin having 16 to 18 carbon atoms (average molecular weight 238) (1 mol) and sulfur trioxide (3 mol) diluted to a nitrogen concentration of 4% by weight were reacted at a reaction temperature of 45°C. The reaction was carried out for a contact time of 1 minute to obtain a sulfonated product (0.9 mol). This is designated as compound C. Production Example 4 After adding 1.7 g of a 53% by weight aqueous sodium hydroxide solution to 0.3 mol of a nonionic emulsifier ("Noogen EA167", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), the mixture was heated at 120°C for 3 hours to dehydrate it. Summer. Thereafter, the inside of the system was heated to 160° C. and 0.92 mol of propylene oxide was gradually added to obtain a nonionic emulsifier (0.29 mol) to which propylene oxide was added. This is designated as compound D. Examples 1 to 14 and Comparative Examples 1 to 9 220 ml of water was placed in a beaker with a capacity of 300 ml, stirred with a propeller type stirring blade, and 3 g of the composition shown in Table 1 was injected with a syringe. A sizing emulsion was obtained at room temperature. Next, the pH was adjusted to 7.5 with sodium bicarbonate.
Cationic starch in 0.5% pulp suspension,
0.8% by weight, 20% by weight and 0.03% by weight of ground calcium carbonate and cationic polyacrylamide, respectively.
% by weight (based on the solid content of the pulp), and further added the sizing emulsion obtained above in the amount shown in Table 2 (based on the solid content of the pulp).
P8209) was used to produce paper sheets. The degree of size of the obtained paper sheets was measured. The results are shown in Table 2.

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[Table] *Additional amount of sizing emulsion (relative to pulp solid content)

Claims (1)

[Scope of Claims] 1 (A) a substituted cyclic dicarboxylic acid anhydride, (B) at least one emulsifier selected from anionic emulsifiers, cationic emulsifiers, and unmodified nonionic emulsifiers; and (C) A sizing agent composition containing at least one organic acid selected from fatty acids, dicarboxylic acids, and sulfonic acids. 2 The substituted cyclic dicarboxylic acid anhydride has the general formula The composition according to claim 1, which is a compound represented by the formula (wherein R represents a dimethylene group or trimethylene group, and R' represents an alkyl group, an alkenyl group, an aralkyl group, or an aralkenyl group).