JPS61274735A - Preparation of emulsion for sizing - Google Patents

Abstract

PURPOSE:To enable emulsification by simple operation, by mixing a size agent with an aqueous emulsifier solution containing 20-70wt% of an emulsifier and mixing the resulting mixture with water to prepare an emulsion for sizing. CONSTITUTION:A size agent (A) and an aqueous emulsifier solution containing 20-70wt% of an emulsifier (B) are mixed and the obtained mixture (C) is subsequently mixed with water (D) to prepare an emulsion sizing. The wt. ratio of the aforementioned A-component/B-component is generally 20-4, pref., 8-15 and the wt. ratio of A+B/D is 0.01-10, pref., 0.1-1.0. As the size agent, a substituted cyclic dicarboxylic anhydride represented by formula I (wherein R<1> is a dimethylene group or a trimethylene group and R<2> is an alkyl group, an alkenyl group, an aralkyl group and an aralkenyl group) is pref. As an emulsifier, there is an anionic emulsifier or a cationic emulsifier.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an emulsion for size, and more specifically, it can be easily emulsified in a short time and has an excellent size effect. The present invention relates to a method for producing a sizing emulsion that can efficiently produce paper.

[Prior art and its problems] In a general paper manufacturing method, first, a sizing agent, an emulsifier, and optionally an emulsifying aid are mixed with water to obtain a sizing emulsifier.Then, this sizing emulsion is mixed with other The pulp suspension is mixed with additives, and the final step is papermaking, dehydration, and drying.

In this papermaking process, methods for producing emulsions for sizing generally include a method in which sizing agents, emulsifiers, etc. are blended with water and phase inversion emulsification is carried out, and a method in which forced emulsification is carried out using a high-speed mixer, high-speed homogenizer, etc. .

However, the phase inversion emulsification method is complicated to operate and requires a long time for emulsification. Furthermore, the high-speed emulsification method requires expensive equipment, and high-speed stirring requires a large amount of electric power.

This invention has been made based on the above circumstances.

That is, an object of the present invention is to solve the above-mentioned problems, and to provide a method for producing a size emulsion that can be emulsified in a short time and with a simple operation, and has an excellent size effect. .

[Means for solving the above problems] The outline of the present invention for solving the above problems is to mix a sizing agent and an emulsifier aqueous solution containing 20 to 70% by weight of an emulsifier, and mix the resulting mixture with water. This is a method for producing an emulsion for size, which is characterized by mixing the following:

The sizing agent is the base of the sizing emulsion in this invention, and various compounds can be used, but substituted cyclic dicarboxylic acid anhydrides represented by the following general formula are usually preferred. It is.

However, in the above general formula, R1 represents a dimethylene group or trimethylene group, and R2 represents an alkyl group, an alkenyl group, an aralkyl group, or an aralkenyl group, and those having 5 or more carbon atoms are particularly preferred. Specific examples of R2 include octyl group, dodecyl group, hexadecyl group, octadecyl group, 1-propyl-2-tridecenyl group, l-ethyl-2-tetradecenyl group, l-methyl-2
-pentadecenyl group, l-ethyl-2-hexadecenyl group, -hexyl-2-tetradecenyl group, polypropylenyl group, polyimbutynyl group.

Examples include polybutynyl group and styryl group.

Specific examples of the substituted cyclic dicarboxylic anhydride include octyl succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, l-propyl-2-tridecenyl succinic anhydride, l-propyl-2-tridecenyl succinic anhydride,
-ethyl-2-tetradecenyl succinic anhydride, l-methyl-2-pestadecenyl succinic anhydride, l-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, l-
Propyl-2-tridecenyl glutamic anhydride, 1-ethyl-2-hexadecenyl glutamic anhydride, l-hexyl-2-tetradecenyl glutamic anhydride, polypropylenyl glutamic anhydride, polyisobutynyl glutamic anhydride, polybutynyl glutamic anhydride, styryl glutamic anhydride, etc. or these Examples thereof include a mixture, and a reaction product of a butene oligomer having 16 to 24 carbon atoms containing isobutylene as a main component and maleic anhydride.

Among these substituted cyclic dicarboxylic acid anhydrides, reaction products of butene oligomers containing isobutylene as a main component and having a carbon number of 16 to 24 and maleic anhydride, and propylene oligomers having a carbon number of 15 to 21 as a main component containing propylene. and maleic anhydride are preferred.

As the emulsifier, various emulsifiers can be used, such as anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers.

Specifically, as anionic emulsifiers, for example, alkylbenzenesulfonic acid alkali metal salts such as sodium dodecylbenzenesulfonate, alkylbenzenesulfonic acid alkaline earth metal salts such as dodecylbenzenesulfonic acid calcium salt, undecylbenzenesulfonic acid sodium salt, etc.; Alkaline earth metal salts of α-olefin sulfonates, such as calcium or sodium equivalents of sulfonic acids of α-olefins usually having 8 to 20 carbon atoms; alkaline earth metal salts of sulfosuccinates, such as 2-ethylhexyl sulfosuccinate calcium salts. , dicyclohexylsulfosuccinate calcium salt, etc.; (alkyl)naphthalene sulfonate and formalin condensate of (alkyl)naphthalene sulfonate, such as diisopropylnaphthalene sulfonate calcium salt, etc.; alkanesulfonate, such as tetradecyl sulfonate calcium salt. etc; fatty acid amide sulfonic acid alkaline earth metal salt; alkyl sulfate ester alkaline earth metal salt such as decyl alcohol sulfate ester calcium salt, lauryl alcohol sulfate ester calcium salt,
Oxoalcohol sulfate magnesium salt etc.; polyoxyalkylene alkyl sulfate ester alkaline earth metal salt such as decyl alcohol E O(1) sulfate calcium ester, and the number in parentheses indicates the number of moles. The same information will be displayed below. ], lauryl alcohol E O (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 E O (2) sulfate ester calcium salt etc.: higher fatty acid x; z. Examples of alkaline earth metal sulfate esters include coconut oil fatty acid monoglyceride sulfate calcium salts, and among these, alkali metal salts of alkylbenzenesulfonates are preferred, and sodium dodecylbenzenesulfonate is particularly preferred.

Examples of the cationic emulsifier include tetraalkylammonium halides such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, and among these, lauryltrimethylammonium chloride is preferred.

Examples of nonionic emulsifiers include polyoxyalkylene styrenated aryl ethers, such as styrenated (2
) Phenol E O (12), Styrenated (2) Phenol E O (10), Styrenated (2) Phenol PO (10) [PO indicates propylene oxide.

The same information will be displayed below. ], EO (25) PO (3)
, polyoxyalkylene alkylaryl ethers such as nonylphenol EO (8), octylphenol EO (10), dodecylphenol EO (1
0), nonylphenol E O (10) etc.: polyoxyalkylene polyhydric alcohol fatty acid ester such as sorbitol laurate EO (10), castor oil E
O (30) etc.; polyoxyalkylene alkyl ether such as Ziegler alcohol EO having 6 to 20 carbon atoms
(8), octyl alcohol E O (10), coconut oil reduced alcohol E O (5), etc.: polyoxyethylene polyoxypropylene block copolymer; polyoxyalkylene fatty acid ester, such as oleic acid and polyethylene glycol (molecular weight 600). mono- or diester of stearic acid E O (15), lauric acid E
O (10), etc.: Polyoxyalkylene alkylamines, such as stearylamine E O (10), etc.; Polyoxyalkyl mercaptans, such as cetyl mercaptan E O (10), etc.; Alkylolamide nonionic surfactants, such as lauric acid jetanolamide E
O (4), etc.: Polyhydric alcohol fatty acid esters, such as lauric acid monoglyceride, sorbitan stearate, sorbitan oleate, sucrose stearate, etc.; Examples include compounds substituted with acyloxy groups, alkylcarbamoyl groups, etc. Among these, polyoxyalkylene styrenated aryl ethers are preferred, and styrenated (2) phenol E 2 O (12) is particularly preferred.

Further, as the emulsifier, the various compounds mentioned above may be used alone or in combination.

The aqueous emulsifier solution is an aqueous solution obtained by dissolving one or more of the various emulsifiers in water at a concentration of 20 to 70% by weight, preferably 25 to 40% by weight. When the emulsifier is in the concentration range, organic acids such as carboxylic acids,
Good emulsification of the emulsion for size can be achieved even without specifically blending sulfonic acid or the like. This is noteworthy considering that when a sizing agent and an emulsifier are dispersed in water to prepare a sizing emulsion, emulsification does not occur easily unless an organic acid is blended.

This sizing emulsion is prepared by first mixing the sizing agent (A) and an emulsifier aqueous solution (B) containing 20 to 70% by weight of an emulsifier, and then mixing the resulting mixture (G) and water (D). It can be obtained by By this procedure, it is possible to prepare a size emulsion in a good emulsified state for the first time. It is not possible to prepare a size emulsion with a good emulsification state.

The mixing ratio of the (A) component, the (B) component, and the (D) component is usually the (A) m min/(B) component (however, the weight of the active ingredient amount of the (B) component). ratio) is 20 to 4
, preferably 8 to 15, ((A) + (B) )
/(D) (weight ratio) is 0.01-10, preferably 0.1-1.0.

A common propeller stirrer is sufficient for mixing the three components, and conventional expensive emulsifying equipment such as a high-speed mixer and a high-speed homogenizer is not required. Further, there is no need to apply a phase inversion method or the like.

The size emulsion obtained by the method of this invention is 1 to 5I
It is an emulsion of about L size.

This size emulsion is mixed with a filler such as calcium carbonate, a fixing agent (cationic starch, etc.), a retention aid (cationic polyacrylamide, etc.), etc. to prepare a pulp suspension, and paper is made. As a result, the desired paper can be obtained.

[Advantageous Effects of the Invention 1] According to the present invention, a size emulsion with a good emulsified state can be obtained within a short time simply by mixing an aqueous emulsifier solution of a specific concentration, a sizing agent, and water in a specific order. Moreover, the emulsion for size obtained by the method of the present invention can efficiently produce paper having excellent sizing effects.

[Examples] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention.

(Example of synthesis of sizing agent) 1 mole of butene oligomer having 16 to 24 carbon atoms and containing inbutylene as a main component and 1 mole of maleic anhydride at 220°C.
After reacting in an autoclave for 5 hours at
Vacuum distillation was performed at mm Hg to obtain an alkenyl anhydride with a boiling point of 160-230°C.

(Emulsification Example 1) Add 300 mJL of water in a bead with a volume of 500 mJ1,
While stirring this at a rotation speed of 600 revolutions per minute,
5 g of sizing agent and 1.43 g of 35% by weight aqueous solution of emulsifier
(active ingredient o, 5 g) was added at once and stirring was continued for 2 minutes to prepare a size emulsion.

(Emulsification Example 2) 5 g of sizing agent and 0.0 g of emulsifier. ! While stirring the mixture with i g (active ingredient amount) using a stirring blade, water was gradually added to the mixture to prepare a size emulsion.

(Emulsification Example 3) While stirring 300 m of water in a bead with a volume of 500 mm with a high-speed mixer at a rotation speed of 12,000 revolutions per minute, 1.5 g of a sizing agent and 0.15 g of an emulsifier (active ingredient amount) were added to it. After adding 1.85 g of the mixture, stirring was continued for 5 minutes to prepare a size emulsifier.

(Examples 1 to 5 and Comparative Examples 1 to 9) Using the alkenyl succinic anhydride obtained in the above synthesis example as a sizing agent and the compounds of the types shown in Table 1 as an emulsifier, the emulsification examples shown in Table 1 were prepared. An emulsion for size was prepared by the method.

Next, the pH was adjusted to 7.5 with sodium hydrogen carbonate.
% pulp suspension, the emulsion for the size shown in Table 1,
0.8% by weight of cationic starch, 20% by weight of ground calcium carbonate and 0.0% by weight of cationic polyacrylamide
3% by weight (each amount added is based on the solid content of PAMEP) was added, and paper was made using a hand-sheet machine (JISP8209) to produce paper sheets. The size degree (JISP8122, Stekicht method) of the obtained paper sheets was measured. The results are shown in Table 1.

(Hereinafter, blank spaces) Procedural amendment 1 Indication of the case 1985 Patent Application No. 117345 2 Name of the invention Method for manufacturing size emulsion 3 Person making the amendment Relationship to the case Patent applicant address Maruno, Chiyoda-ku, Tokyo 1-1 Shiratama-chome Name Idemitsu Petrochemical Co., Ltd. Representative Takeshi Yamato 4 Agent address 2nd floor 8, Karakawa Building, 6-3-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contents of amendment (1) Second page of the statement In line 15, "and the emulsifying aid and water are corrected according to q", and J is corrected to "water and, optionally, the emulsifying aid."

(2) "Emulsifier for products" written on page 2, line 16 of the specification is corrected to "emulsifier for products".

(3) "Method for phase inversion emulsification" described in the first line of page 3 of the specification is "method for phase inversion emulsification by gradually adding water"
Correct to.

(4) "The phase inversion emulsification method" written in the fourth line of page 3 of the specification is amended to "this phase inversion emulsification method".

(5) ro stated in the first line of page 12 of the specification,
01~IOJ is corrected to rO, 01~1.0''.

(6) ro stated in the second line of page 12 of the specification,
oi~1.0'' is corrected to ro, 01~0.10J.

Claims (3)

[Claims] (1) A method for producing an emulsion for size, which comprises mixing a sizing agent and an aqueous emulsifier solution containing 20 to 70% by weight of an emulsifier, and mixing the resulting mixture with water. (2) The method for producing a size emulsion according to claim 1, wherein the sizing agent is a substituted cyclic dicarboxylic acid anhydride represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the above formula, R^1 represents a dimethylene group or trimethylene group, and R^2 represents an alkyl group, alkenyl group, aralkyl group, or aralkenyl group.) (3) Claims 1 or 2, wherein the emulsifier is one or a mixture of two or more selected from the group consisting of anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers. Method for producing emulsions for the sizes described.