JPS6034697A - Self-emulsifiable size composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION More specifically, the present invention relates to an internally added sizing agent composition that is suitable for neutral papermaking and has excellent self-emulsifying properties.

Conventionally, sizing agents for paper manufacturing have been widely used, such as sizing agents manufactured from natural rosin or modified rosin, especially so-called reinforced rosin sizing agents obtained by saponifying maleic acid adducts of rosin. However, the use of sulfuric acid, an essential component, lowers the pH of the papermaking system, which can lead to corrosion of papermaking equipment and decrease the strength of the resulting paper. Also, there is a drawback that durability is reduced. Furthermore, because it is difficult to use inexpensive alkaline fillers such as calcium carbonate, it has not been possible to expect a significant reduction in paper production costs.

In order to solve the drawbacks of the acidic sizing method, research has been conducted on neutral papermaking methods that do not use sulfate, and so-called neutral sizing agents have been proposed that provide excellent sizing effects to paper under papermaking conditions in the neutral range. 0 For example, the special public
A sizing agent containing a cyclic dicarboxylic acid anhydride described in Japanese Patent Publication No. 05, a sizing agent consisting of a maleic anhydride adduct of an internal olefin described in Japanese Patent Publication No. 55-28526,
Examples include a sizing agent consisting of a substituted dicarboxylic anhydride, an oxyalkylene compound, and water described in Japanese Patent Publication No. 53-36044.

However, Special Publication No. 39-2305 and Special Publication No. 5
All of the sizing agents described in Japanese Patent Publication No. 3-28526 have many restrictions in order to disperse the dicarboxylic acid anhydride in water, as is clear from the description in Japanese Patent Publication No. 53-36044. In other words, protective polymers, which are suspending agents such as cationized starch, gelatin, and polyvinyl alcohol, must be included as an essential ingredient, and in addition, special strengths such as high-speed shakers, mechanical homogenizers, and ultrasonic homogenizers must be Only by using a stirring device can it be dispersed in water.

On the other hand, Japanese Patent Publication No. 55-56044 describes that by using a polyoxyalkylene compound as a surfactant in the substituted dicarboxylic anhydride, the suspension step using a strong stirring device can be omitted. There is.

That is, when the dicarboxylic acid anhydride is suspended using the surfactant described in the same publication, such as polyoxyalkylene alkyl ether or polyoxyalkylene alkylaryl ether, the mixed pulp can be prepared without high-speed stirring. Simply pass it through an aspirator or orifice.

However, when a substituted dicarboxylic acid anhydride and the alkyl or aryl ether type surfactant are mixed and left to stand, the dispersibility of the mixture in water decreases over time, and the size effect tends to decrease accordingly. There is.

On the other hand, when the polyoxyalkylene alkyl diester described in the same publication is used, there is no decrease in the size effect over time due to neglect, which occurs when the alkyl or aryl ether type surfactant is used. Since the alkyl group originally has a large number of carbon atoms and is highly hydrophobic, it has the disadvantage that it is difficult to easily disperse in water by a simple mixing operation.

As mentioned above, none of the dispersants described in this publication can be suitably used.

As mentioned above, the conventionally known neutral sizing agents are not yet satisfactory in terms of various performances such as dispersibility in water, dispersion stability over time, and sizing effect, and even now, the above-mentioned reinforced Acidic papermaking methods using sizing agents are the mainstream.

In view of the current situation, the present inventors have conducted intensive studies to develop a neutral sizing agent that is comparable to reinforced rosin sizing agents and can be applied to actual equipment. It was discovered that a neutral sizing agent capable of simultaneously satisfying the above-mentioned properties could only be obtained by using the above-mentioned properties, and the present invention was completed based on this finding.

That is, the present invention relates to the general formula (1): (wherein, R1 has 9 to 23 carbon atoms, preferably 13 to 19 carbon atoms)
linear or branched substituted cono-monolyric acid anhydride represented by the alkyl group or alkenyl group) and the general formula (n): A chain alkyl group, R3 represents a straight chain or branched alkyl group or alkenyl group having 2 to 28 carbon atoms, and R2
and R3 have a total number of carbon atoms of 9 to 29, preferably 13 to 2.
At least one substituted succinic anhydride selected from the group consisting of branched chain substituted succinic anhydrides represented by linear or branched alkyl group, n is 5 to
30, preferably an integer from 8 to 26 and X is -803M
1 (1 to 3 alkyl groups)) and a polyoxyethylene type represented by the general formula (piece; (wherein, R', n, and/or are the same as those in general formula (1)) The present invention relates to a self-emulsifying sizing agent composition containing as a main component a dispersant selected from the group consisting of compounds.

In the present invention, the substituted succinic anhydride represented by the general formula (1) is obtained by an addition reaction between an α-olefin having a double bond at the terminal or an oligomer thereof and maleic anhydride.

Specific examples of the substituted succinic anhydride include isooctadecenylsuccinic anhydride, n-hexadecenylsuccinic anhydride, dodecenylsuccinic anhydride, triisobutenylsuccinic anhydride, and the like. In addition, these unsaturated substituted succinic anhydrides can be subjected to a hydrogenation reaction to obtain the corresponding saturated substituted succinic anhydrides.

The branched substituted succinic acid hydrothermal hydrate represented by the general formula (II) can be obtained by an addition reaction between an internal olefin and maleic anhydride.

Specific examples of the substituted succinic anhydride include adducts of internal olefins such as decene-5, dodecene-6, tetradecene-7, hexadecene-7, octadecene-9, and eicosene-11 and hydrothermal maleic acid. In addition, these unsaturated substituted succinic anhydrides can be subjected to a hydrogenation reaction to obtain the corresponding saturated substituted succinic anhydrides.

The reaction between the α-olefin or internal olefin and maleic anhydride is carried out in the presence or absence of a catalyst, preferably under an inert atmosphere, at normal pressure or under increased pressure. The reaction temperature is 180-2500 ()1 preferably 190-2
20°C, and reaction time is 1 to 50 hours, preferably 1
The molar ratio of olefins to maleic anhydride is not particularly limited, but is usually 0.4 to 2 mol of maleic anhydride, preferably 0.8 to 1 mol of maleic anhydride to 1 mol of olefins. A suitable amount is .3 mol.

After the reaction is completed, substituted succinic anhydride can be obtained by removing unreacted olefins and maleic anhydride by distillation.

In addition, a specific dispersant essential to the present invention is represented by the general formula (1).
and (limited to polyoxyethylene type compounds represented by pieces).

Examples of the monovalent cation represented by M in general formulas (1) and (g) include lithium, sodium,
Examples include alkali metal ions such as potassium, ammonia, and ammonium groups derived from various amines such as trimethylamine, dimethylamine, diethylamine, and triethanolamine.

The dispersant must not contain hydroxyl groups and must have appropriate hydrophilicity. That is, even if the substituted succinic anhydride of the general formula (I) and/or (II) and the dispersant are mixed and left for a long time, the anhydride ring of the substituted succinic acid does not open and is chemically stable. Therefore, the dispersibility of the mixture in water does not change orally. In addition, the dispersant has moderate hydrophilicity and therefore has excellent self-emulsifying properties, and requires a smaller amount of use than conventionally known dispersants such as polyoxyalkylene alkyl ether or polyoxyalkylene alkylaryl ether. It is possible to improve defects such as foaming, which was a problem when applied to.

The paper making method for the self-emulsifying sizing agent of the present invention obtained as described above is usually carried out by dispersing the sizing agent in water in advance or by proportionally injecting the sizing agent and water at the time of use. In addition, various cationic compounds such as polyethyleneimine resin, cationic polyacrylamide resin, cationic polyamide polyamine resin, cationic compound can be added to the pulp slurry in a predetermined amount to further improve the fixing properties to the pulp. Starch derivatives and the like can be used.

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples, but the present invention is not limited to such Reference Examples, Examples, and Comparative Examples.

Reference Example 1 Alkenylsuccinic anhydride was obtained by addition-reacting maleic anhydride to a branched α-olefin oligomer having 14 carbon atoms.

Reference Example 2 Realkenylsuccinic anhydride was obtained by addition-reacting maleic anhydride to a branched α-olefin oligomer having 20 carbon atoms.

Reference Example 3 Alkenylsuccinic anhydride was obtained by addition reaction of maleic anhydride to tetradecene-7.

Reference Example 4 Alkenylsuccinic anhydride was obtained by subjecting eicosene-11 to an addition reaction with maleic anhydride.

Reference Example 5 Alkenylsuccinic anhydride was obtained by subjecting octadecene-9 to an addition reaction with maleic anhydride.

Example 1 Alkenylsuccinic anhydride obtained in Reference Example 1 109klj
1 g of polyoxyethylene dispersant shown in Table 1 of Shitsugi
After adding and mixing well, 1 g of the mixture was added to 100 m
A sample was taken into a sample bottle, 86 g of water was added thereto, and the mixture was shaken gently by hand to form an emulsion to obtain a sizing agent.

Examples 2 to 20 Various sizing agents were obtained by emulsifying scallops in the same manner as in Example 1 except that the substituted succinic anhydride and dispersant used were changed to those shown in Table 1.

The self-emulsifying properties of the sizing agents obtained in Examples 1 to 2o above were tested immediately after production and 7 days later, and the results are shown in Table 1.

The size effect of the obtained sizing agent was also measured using the test method described above, and the results are shown in Table 1.

(Size Performance Test) Pulp (It-BICP) was beaten to 450 ml of Canadian Standard 7 consistency to form a 1% aqueous slurry. Arafix 1oo made of polyamide polyamine resin (Hikariyo Kagaku Kogyo@) was added to the slurry as a fixing agent.
) was added at 0.3% (solid content equivalent) to the pulp, and the sizing agent obtained in this example was added at 0.2% to the pulp.
Or add 0.5% (in terms of solid content) and disperse it uniformly◇ The resulting slurry was processed using a Tappi Standard Sheet Machine with a basis weight of 609±19/! The paper was made to be II2. The resulting wet paper was then compressed and dehydrated to 100°0
After drying for 1 minute, the humidity was controlled at a relative temperature of 65% for 24 hours, and the size degree (seconds) of each sample was measured by the Stekicht method.

Comparative Examples 1 to 4 Emulsification was attempted in the same manner as in Example 1 except that the substituted succinic anhydride and dispersant used were changed to those shown in Table 1, but emulsification did not occur in any case. Ta.

Claims (1)

[Scope of Claims] 1 General formula (I): 1 1 (In the formula, R1 represents an alkyl group or an alkenyl group having 9 to 23 carbon atoms.) Straight chain or branched substituted succinic anhydride and general formula (■): 1 (wherein, R2 is a straight or branched alkyl group having 1 to 27 carbon atoms, and R3 is a straight or branched alkyl group or alkenyl having 2 to 28 carbon atoms. represents a group, and R2
and R3 have a total number of carbon atoms of 9 to 29), and at least one substituted succinic anhydride selected from the group consisting of branched substituted succinic anhydrides represented by the general formula (
I): R' -o -(-0H20H20-)-X (B)(
In the formula, R4 is a linear or branched alkyl group having 6 to 20 carbon atoms, n is an integer of 5 to 30, and or -803M
(M is a monovalent cation) 11) and general formula (Pl): (wherein, R
4. A self-emulsifying type characterized by containing as a main component a dispersant selected from the group consisting of polyoxyethylene type compounds represented by (4) n and X are the same as those in general formula (II). Sizing agent composition 0