JPS6258769B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a water-dispersible composition of substituted succinic anhydride (hereinafter simply referred to as "substituted succinic anhydride") consisting of an alkyl-substituted succinic anhydride, an alkenyl-substituted succinic anhydride, or a mixture of both. This composition contains a specific polyoxyalkylene derivative and a substituted succinic anhydride, and has extremely excellent water dispersibility. Simply mixing this in water produces fine particles. A substituted succinic anhydride that can be used as an aqueous dispersion that exhibits extremely excellent actions and effects as a sizing agent for paper manufacturing, a fiber treatment agent, etc. A water-dispersible composition is provided. It is known that an aqueous dispersion of substituted succinic anhydride can be used as a paper sizing agent or a fiber treatment agent, and substituted succinic anhydride can be used as a sizing agent for paper manufacturing or as a fiber treatment agent. Aqueous dispersions of anhydrides have been proposed (for example, Japanese Patent Publication No. 39-2305 and Japanese Patent Publication No. 36044-1982). However, when preparing an aqueous dispersion of substituted succinic anhydride using the cation-modified starch as a dispersant, it is necessary to boil the cation-modified starch in advance to make it water-solubilized, and in addition, a large-scale emulsification equipment is required. Since homogenization treatment is essential, the preparation process is complicated. Also,
On the other hand, as a method of using a dispersant using a specific nonionic surfactant, a method is known in which a premix of substituted succinic anhydride and the surfactant is instantaneously dispersed in water using a water pump. This method is extremely advantageous from an industrial perspective in that it can omit large-scale emulsification equipment and homogenization treatment, but it is possible to eliminate the need for a large-scale emulsification device or homogenization treatment. The dispersion ability is not necessarily sufficient, and it is difficult to obtain a fine particulate aqueous dispersion. In addition, the mixed composition of the substituted succinic anhydride and nonionic surfactant does not have sufficient dispersion ability when stored for a long time. There were defects such as decreased water dispersibility. On the other hand, in the water-dispersible composition of substituted succinic anhydride of the present invention, one or more polyoxyalkylene derivatives (a) selected from the following general formulas (a) and (b) are used as a dispersant. It is used as
It has extremely excellent water dispersibility, and its water dispersibility does not decrease even when stored for a long time, and it is an aqueous solution containing substituted succinic anhydride in the form of fine particles that can be immediately mixed with water. This provides a water-dispersible composition of substituted succinic anhydride which becomes a dispersion. The above-mentioned effects of the water-dispersible composition of substituted succinic anhydride of the present invention are such that the polyoxyalkylene derivative (a) having a half-ester residue of substituted succinic acid in the composition is This is due to the fact that it exhibits extremely excellent dispersibility in water for anhydride (b). [In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms. R′: represents a hydrophobic group. A: Represents a bond between a hydrophobic group and a polyoxyalkylene group. X: represents hydrogen or a methyl group. n, m: represents an integer of 21 or more. ] Polyoxyalkylene derivative utilized in the water-dispersible composition of substituted succinic anhydride of the present invention
(a) acts as a dispersant for dispersing substituted succinic anhydride in water, and is different from conventionally known polyoxyalkylene surfactants in that it has a substituted succinic acid residue as a hydrophobic group. have completely different chemical structures. The polyoxyalkylene derivative (a) is a polyoxyalkylene derivative in which both ends are composed of hydroxyl groups, or one end is composed of a hydroxyl group and the other end is composed of a non-reactive hydrophobic group, and a substituted succinic acid. by reacting the hydroxyl group in the polyoxyalkylene derivative with the anhydride in approximately equivalent amounts of the substituted succinic anhydride group in the substituted succinic anhydride, or in an excess equivalent amount of the substituted succinic anhydride group. A half-esterification reaction product of a polyoxyalkylene derivative and a substituted succinic anhydride, which (i) has a hydrophobic group at both ends, and (ii) at least one of the hydrophobic groups has a half-esterification reaction product of a substituted succinic acid anhydride. It must be an ester residue (iii) The polyoxyalkylene group moiety must simultaneously satisfy the three conditions of having 21 or more polyoxyalkylene units, and if any of these conditions is missing, However, it is impossible to achieve the object of the present invention. That is, when a polyoxyalkylene derivative that does not satisfy the condition (i) above is used, the dispersibility of the polyoxyalkylene derivative in water for substituted succinic anhydride is insufficient. In the case of a hydroxyl group like known nonionic surfactants, a composition comprising this and a substituted succinic anhydride has the defect that its water dispersibility decreases significantly over time. In addition, when a polyoxyalkylene derivative that does not satisfy the condition (ii) above is used, the polyoxyalkylene derivative has poor dispersibility in water for substituted succinic anhydride, resulting in a lack of easy dispersibility in water. Otherwise, it is not possible to obtain a composition that produces a finely divided aqueous dispersion. Furthermore, the condition (iii) above must be satisfied by the polyoxyalkylene derivative (a) used in the present invention. This is because this is a necessary condition for the substituted succinic anhydride to exhibit effective dispersibility in water.
When the number of oxyalkylene units in the polyoxyalkylene group portion of a polyoxyalkylene derivative having hydrophobic groups at both ends is 20 or less, the new hydrophilic group portion becomes small (hydrophobic) due to the chemical structure of the polyoxyalkylene derivative. This is because the dispersibility of the substituted succinic anhydride in water decreases, making it impossible to obtain a water-dispersible composition suitable for the purpose of the present invention. The polyoxyalkylene derivative (a) used in the present invention is, for example, a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, or a polyoxyalkylene group based on a polyoxyethylene-polyoxypropylene-block copolymer. Those having a group are preferred. Examples of the hydrophobic groups constituting both ends of the polyoxyalkylene derivative (a) include alkyl groups, alkenyl groups, aryl groups, aralkyl groups,
Aralkenyl groups, various fatty acid or resin acid residues, substituted succinic acid residues, etc. are preferable, but at least one of the hydrophobic groups constituting both ends is preferably a half-ester residue of substituted succinic acid. This is necessary as described above. The substituted succinic acid half ester residue is a half ester residue based on an alkyl succinic anhydride or an alkenyl succinic anhydride having an alkyl or alkenyl group having 8 or more carbon atoms, preferably 12 or more carbon atoms, that is, a general formula R: represents an alkyl group or alkenyl group having 8 or more carbon atoms. A substituted succinic acid half ester residue represented by is preferred. The bond between the hydrophobic group (excluding the half ester residue of substituted succinic acid) and the polyoxyalkylene group in the polyoxyalkylene derivative (a) is an ester bond, ether bond, urethane bond, amide bond,
Alternatively, there is no particular problem if the bond is an imide bond or the like, which does not dissociate or decompose in water and is non-reactive with carboxyl groups. As explained in detail above, the polyoxyalkylene derivative (a) used in the present invention is composed of a hydroxyl group at both ends, or a hydroxyl group at one end and a non-reactive hydrophobic group at the other end. The polyoxyalkylene derivative and the substituted succinic anhydride are mixed in substantially equivalent amounts of the hydroxyl group in the polyoxyalkylene derivative and the substituted succinic anhydride group in the substituted succinic anhydride, or in a substituted succinic anhydride. It is a half-esterification reaction product of a polyoxyalkylene derivative and a substituted succinic anhydride obtained by reacting in an excess equivalent of anhydride groups, and the half-esterification reaction is generally
This is achieved by heating at ~120°C, preferably 85~100°C, but the reaction at this time needs to be completed sufficiently, and is usually heated at the above heating temperature for 5 hours or more. Reaction time is required. Incidentally, the reaction process of the half-esterification reaction product of the polyoxyalkylene derivative and substituted succinic anhydride is shown by the following reaction formula (1) and reaction formula (2). [In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms. R': represents a hydrophobic group. A: Represents a bond between a hydrophobic group and a polyoxyalkylene group. X: represents hydrogen or a methyl group. n, m: represents an integer of 21 or more. ] The substituted succinic anhydride (b) used in the water-dispersible substituted succinic anhydride composition of the present invention is, for example, a substituted succinic anhydride having an alkyl group or an alkenyl group having 5 or more carbon atoms, preferably 8 or more carbon atoms. An acid anhydride, alkenylsuccinic anhydride obtained by the addition reaction of α-olefin, internal olefin, or oligomers such as propylene or butene with maleic anhydride, and hydrogenating the alkenylsuccinic anhydride. The obtained alkylsuccinic anhydride, etc., specifically, octenylsuccinic anhydride, nonenylsuccinic anhydride, dodecylsuccinic anhydride, dodecenylsuccinic anhydride, pentadecenylsuccinic anhydride, pentadecylsuccinic acid Anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, (1-octel-2-decenyl)-succinic anhydride, (1-hexyl-2-octenyl)-succinic anhydride , an addition reaction product between a butene oligomer and maleic anhydride, an addition reaction product between a propylene oligomer and maleic anhydride, an addition reaction product between a butadiene oligomer or its partially hydrogenated product and maleic anhydride, and the like. The ratio of the above-mentioned polyoxyalkylene derivative (a) and substituted succinic anhydride (b) in the water-dispersible composition of substituted succinic anhydride of the present invention can be determined arbitrarily depending on the use and purpose of the composition. Although it is of course possible to change the composition, when the composition is used as a paper-making size composition or a fiber treatment agent, the preferred range is 80 parts by weight of the substituted succinic anhydride for 3 to 20 parts by weight of the polyoxyalkylene derivative. ~97 parts by weight. In the water-dispersible composition of substituted succinic anhydride of the present invention having the above structure, the polyoxyalkylene derivative (a) having a special chemical structure is particularly superior to the substituted succinic anhydride (b). It has excellent compatibility and dispersibility in water, and since it does not have any reactive groups with the acid anhydride groups of substituted succinic anhydride, it not only has excellent stability over time, but also has excellent dispersibility in water. It is easy to use and has the characteristic that a stable and finely particulate aqueous dispersion of substituted succinic anhydride can be obtained simply by mixing the composition of the present invention with water without carrying out homogenization treatment using a large-scale emulsifying device or the like. It is something. Therefore, the water-dispersible composition of substituted succinic anhydride of the present invention is useful as a size composition for paper manufacturing, a composition for treating fibers, and a composition for water-repellent treatment of fiberboards, cement boards, etc. Not only that, but the resulting size effect and water repellency are also extremely excellent. Hereinafter, the specific structure of the water-dispersible composition of substituted succinic anhydride of the present invention will be explained based on Examples, and the actions and effects of the composition will be explained as well as the actions of the composition obtained in Comparative Examples. , compare and explain the effects. Example 1 [] Preparation of polyoxyalkylene derivative 0.1 mol of polyethylene glycol (oxyalkylene units 22 to 23) having an average molecular weight of 1000 and 0.25 mol of dodecenylsuccinic anhydride were charged into a 500 c.c. four-necked flask, and The reaction was heated at ~100℃ for 6 hours, and the formula A composition comprising 92% by weight of the compound represented by and 8% by weight of dodecenylsuccinic anhydride was obtained. [] Preparation of water-dispersible composition 12 g of the composition obtained in the above [] section and 88 g of dodecenylsuccinic anhydride were uniformly mixed to obtain a water-dispersible composition [A] of the present invention. Example 2 15 g of the composition obtained in section [] of Example 1 and 85 g of alkenylsuccinic anhydride, which is a maleic anhydride adduct of propylene oligomer mainly composed of propylene pentamer, were mixed uniformly. A water-dispersible composition [B] of the invention was obtained. Example 3 90 parts by weight of alkenylsuccinic anhydride obtained by adding maleic anhydride to a commercially available propylene oligomer (average molecular weight 225) having a carbon number distribution of 14 to 22 and polyethylene glycol (average molecular weight 1000, oxyethylene 10 parts by weight of units 22 to 23) are reacted at 90 to 100°C for 6 hours to obtain a compound of the present invention consisting of about 16.5 parts by weight of a polyoxyethylene derivative as a dispersant component and about 83.5 parts by weight of alkenylsuccinic anhydride. A water-dispersible composition [C] was obtained. Example 4 Instead of using polyethylene glycol (average molecular weight 1000) in Example 3, polyethylene glycol (average molecular weight 1500, oxyethylene unit) was used.
The method of Example 3 was repeated except that about 14.3 parts by weight of polyoxyethylene derivative and about alkenylsuccinic anhydride were used as dispersant components.
A water-dispersible composition of the present invention [D] consisting of 85.7 parts by weight was obtained. Example 5 Polyethylene glycol (average molecular weight 4000, oxyethylene unit) was used instead of polyethylene glycol (average molecular weight 1000) in Example 3.
The method of Example 3 was repeated except that about 11.6 parts by weight of polyoxyethylene derivative and about alkenylsuccinic anhydride were used as dispersant components.
A water-dispersible composition [E] of the present invention comprising 88.4 parts by weight was obtained. Example 6 The method of Example 3 was repeated except that polyoxyethylene-nonylphenol ether (21 oxyethylene units) was used instead of polyethylene glycol (average molecular weight 1000) in Example 3, and the dispersant was about 12.8 parts by weight of polyoxyethylene derivative and about alkenylsuccinic anhydride as
A water-dispersible composition [F] of the present invention consisting of 87.2 parts by weight was obtained. Example 7 Instead of using polyethylene glycol (average molecular weight 1000) in Example 3, polyoxyethylene-lanolin fatty acid ester (average molecular weight 1400,
The method of Example 3 was repeated except that the oxyethylene unit 23) was used, and the water dispersibility of the present invention was obtained by repeating the method of Example 3, except that the oxyethylene unit 23) was used, and the water dispersibility of the present invention was prepared by using about 12.3 parts by weight of a polyoxyethylene derivative as a dispersant and about 87.7 parts by weight of an alkenylsuccinic anhydride. Composition [G] was obtained. Example 8 Instead of using polyethylene glycol (average molecular weight 1000) in Example 3, polyoxyethylene-polyoxypropylene-block copolymer (average molecular weight 13000, molecular weight of polyoxypropylene group portion 2000, total oxyalkylene Repeating the method of Example 3 except using unit 285),
Polyoxyalkylene derivatives as dispersants approx.
A water-dispersible composition [H] of the present invention was obtained, consisting of 10.5 parts by weight and about 89.5 parts by weight of alkenylsuccinic anhydride. Comparative Example 1 Polyethylene glycol (average molecular weight 600, oxyalkylene unit) was used instead of polyethylene glycol (average molecular weight 1000) in Example 3.
14), except that the method of Example 3 was repeated, except that polyoxyethylene derivatives for comparison were used.
A composition [a] consisting of 20.8 parts by weight and about 79.2 parts by weight of alkenylsuccinic anhydride was obtained. Comparative Example 2 The method of Example 3 was repeated except that polyoxyethylene-nonylphenol ether (10 oxyethylene units) was used instead of polyethylene glycol (average molecular weight 1000) in Example 3, and the comparative example was Approximately 14.9 parts by weight of polyoxyethylene derivative and 85.1 parts by weight of alkenylsuccinic anhydride
A composition [b] consisting of parts by weight was obtained. Comparative Example 3 Alkenylsuccinic anhydride used in Example 3
90 parts by weight and 10 parts by weight of polyoxyethylene-nonylphenol ether (21 oxyethylene units) used in Example 6 were uniformly mixed at room temperature to obtain a composition [c] for comparison. Comparative Example 4 Polyoxyethylene-nonylphenol ether (10 oxyethylene units) was used instead of polyoxyethylene-nonylphenol ether (21 oxyethylene units) in Comparative Example 3, and mixed in the same manner as in Comparative Example 3. A composition [d] for comparison was obtained. Comparative Example 5 Polyethylene glycol (average molecular weight 800: oxyalkylene unit) was used instead of polyethylene glycol (average molecular weight 1000) in Example 3.
The method of Example 3 was repeated except that 18) was used, and the polyoxyethylene derivative for comparison
A composition [e] consisting of 15.6 parts by weight and about 84.4 parts by weight of alkenylsuccinic anhydride was obtained. Comparative Example 6 The method of Example 3 was repeated except that polyoxyethylene-nonylphenol ether (18 oxyethylene units) was used instead of polyethylene glycol (average molecular weight 1000) in Example 3, and a comparative example was prepared. Approximately 12.2 parts by weight of polyoxyethylene derivative and approximately alkenylsuccinic anhydride
A composition [f] consisting of 87.8 parts by weight was obtained. Test Example 1 Regarding the water-dispersible compositions [A] to [H] of the present invention obtained in Examples 1 to 8 and each composition [a] to [f] obtained in Comparative Examples 1 to 6, The stability of each composition, ease of emulsification, emulsion particle size (μ) in the emulsion, and stability of the emulsion were tested. The results are shown in Table 1 (Part 1) and (Part 2). The stability of the compositions was evaluated as good if no particular change was observed in the appearance of each composition after it was left at room temperature for one week. Ease of emulsification (immediately) was determined by stirring a mixture of 1 g of each composition and 99 g of water within 24 hours after preparation with a glass rod, and determining the emulsification suitability of the composition. In addition, emulsification ease (40°C, after 1 week) was determined by allowing each prepared composition to release at 40°C for 1 week, and then treating it in the same manner as above to determine its emulsification ease. Judgment; ◎Easy to emulsify, 〇Emulsifiable, ×Not emulsifiable. The emulsion particle size (μ) is the emulsion particle size of each emulsion used in the above emulsification test (immediately). As for the stability of the emulsion, each emulsion used in the above emulsification ease (immediately) was allowed to stand for 1 hour. Those with no separation of oily substances were considered good, and those with oily substances separated were considered poor. And so.

【table】

[Table] Test Example 2 Water-dispersible compositions [D] and [G] of the present invention obtained in Example 4 and Example 7 and compositions [d] to [f] obtained in Comparative Examples 4 to 6 ]For every,
The performance as a paper sizing agent was compared according to the hand papermaking conditions described below. The results are shown in Table 2. As a reference example, a similar hand-paper test was conducted on a commercially available reinforced rosin sizing agent, and the results are also listed in Table 2. [Hand papermaking conditions] Paper making machine: TAPPI standard sheet machine Pulp used: L-BKP CSF400c.c. Paper basis weight: 80g/m ²

【table】

【table】

Claims (1)

[Claims] 1 1 selected from the following general formulas (a) and (b)
Contains at least one polyoxyalkylene derivative (a) and a substituted succinic anhydride (b) consisting of an alkyl-substituted succinic anhydride, an alkenyl-substituted succinic anhydride, or a mixture of both. A water-dispersible composition of a substituted succinic anhydride. [In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms. R′: represents a hydrophobic group. A: Represents a bond between a hydrophobic group and a polyoxyalkylene group. X: represents hydrogen or a methyl group. n, m: represents an integer of 21 or more. 2. The water-dispersible composition of substituted succinic anhydride according to claim 1, wherein the polyoxyalkylene derivative (a) is a polyoxyethylene derivative. 3. The water-dispersible composition of substituted succinic anhydride according to claim 1 or 2, wherein the substituted succinic anhydride (b) is an alkenyl succinic anhydride having an alkenyl group having 8 or more carbon atoms. thing.