JP3274760B2 - Aqueous dispersion of esterified rosin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous dispersion of an esterified rosin material, which is suitable for use as a papermaking sizing agent, an aqueous paint, an aqueous ink and an aqueous adhesive, and has excellent stability. It relates to a low foaming oil-in-water dispersion.

[0002]

2. Description of the Prior Art Obtaining an aqueous dispersion in which an esterified rosin substance is stably dispersed in water in fine particles is generally extremely difficult compared to obtaining an aqueous dispersion of a non-esterified rosin substance. is there. Conventionally, when obtaining an aqueous dispersion of an esterified rosin substance, the esterified rosin substance is dissolved in an organic solvent such as benzene or toluene, and this solution is placed in water containing a surfactant, using a high-pressure emulsifier. A method of obtaining an aqueous dispersion by dispersing and emulsifying using an organic solvent and thereafter distilling off the organic solvent (hereinafter referred to as a solvent method);
A method of inverting and emulsifying a molten esterified rosin substance using a solution of casein in an alkaline substance as a protective colloid (hereinafter referred to as casein method) is mainly used.
However, in the former solvent method, in addition to using an expensive high-pressure emulsifying apparatus, the solvent distillation step after the emulsification step is complicated, and in addition, a small amount is contained in the product dispersion. Since the organic solvent remains, there is a problem in the health care of the handler and in fire prevention.

On the other hand, in the latter casein method, since casein is used as a protective colloid, the dispersion of the product is easily decomposed and decomposed by the action of microorganisms, and this tendency is particularly large in summer when the temperature is high and humid. As a drawback common to the aqueous dispersions obtained by the above two methods, it has been pointed out that foaming is remarkable during use because the dispersions contain a surfactant or casein. Recently, it has been proposed to disperse rosin or αβ unsaturated acid adduct of rosin or esterified product thereof in water as a special polymer as a protective colloid. Manufacturing itself is generally difficult. In addition, since the obtained dispersion liquid has a coarse particle diameter of 0.3 μm or more, good performance is not exhibited in various applications. Japanese Patent Publication No. Sho 57-5420, Japanese Patent Application Laid-Open No. 62-250297, and Japanese Patent Application Laid-Open No. 60-161472 propose a technique for emulsifying an esterified rosin substance.
There is a number.

[0004]

An object of the present invention is to provide an aqueous dispersion in which an esterified product of rosin or an esterified product of fortified rosin is stably dispersed in water with a fine particle size of 0.3 μm or less. To provide a liquid.

[0005]

The esterification according to the present invention
Aqueous dispersions of rosin material, a combination of a water-soluble salt of a water-dispersible polymer of anionic or amphoteric and alkyl-substituted or alkenyl-substituted succinic acids, esters of rosin and / or water esters of fortified rosin It is characterized by being dispersed. In the aqueous dispersion of the present invention, the dispersoid is composed of an ester of rosin and / or an ester of fortified rosin. Here, "rosin" includes gum rosin, tall rosin, wood rosin, hydrogenated rosin,
Various rosins such as polymerized rosin, (alkyl) phenol / formalin resin-modified rosin, xylene resin-modified rosin, aldehyde-modified rosin, and styrene-modified rosin are included, and the “reinforced rosin” includes the αβ unsaturated acid addition of the rosin described above. Things are included. Incidentally, although αβ unsaturated acid is allowed added to rosin by di <br/> Rusuaruda reaction, as the αβ-unsaturated acid in this case, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic Acids and itaconic anhydride can be exemplified.

[0006] The term "esterified rosin" and "esterified rosin" refer to products obtained by the esterification reaction of the above-mentioned rosin or fortified rosin with alcohols. Polyhydric alcohols, polyhydric amino alcohols, polyhydric epoxy compounds, polyhydric phenols and the like are frequently used in performance. Polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentyl glycol, hexanediol, glycerin, trimethylolpropane,
Trimethylolethane, sorbitol and the like can be used. Examples of polyvalent amino alcohols include diethanolamine,
Triethanolamine and the like can be used as polyhydric epoxy compounds, various epoxidized products of bisphenols, and as polyhydric phenols, bisphenol and the like can be used. It should be noted that the rosin esterified product and the fortified rosin esterified product (collectively referred to as esterified rosin substance) in the present invention do not necessarily mean a completely esterified product, but an esterification reaction. Due to economic factors such as time, the partial esterified product in which a part of the acid group remains is often occupied in large part.

As a dispersant for dispersing the above-mentioned esterified product of rosin and / or esterified product of fortified rosin in water as fine particles, the present invention relates to an anionic or amphoteric water-dispersible polymer and an alkyl- or alkenyl-substituted polymer. Use in combination with a water-soluble salt of succinic acid. The anionic or amphoteric water-dispersible polymer as the first dispersant includes styrene and / or (meth) acrylic acid esters and anions such as (meth) acrylic acid, maleic acid, itaconic acid and styrene sulfonic acid. Copolymerizable with a monomer or a salt thereof, or together with these monomers, a cation such as dialkylaminoalkyl (meth) acrylate, dialkylaminoalkylacrylamide, vinylpyridine or vinylimidazole. It can be obtained by copolymerizing a reactive monomer or a salt thereof. In this case, it is also possible to use another monomer copolymerizable with any of the above-mentioned monomers in combination, and examples of this type of monomer include acrylamide, N-substituted acrylamides, vinyl esters, and vinyl toluene. Can be.

Anionic or amphoteric water-dispersible polymers
Can be prepared by any known polymerization method such as emulsion polymerization, solution polymerization, etc., and when prepared by any method, when this is used as the dispersant of the present invention, its final form is It can be made into an aqueous dispersion. On the other hand, a water-soluble salt of an alkyl-substituted or alkenyl-substituted succinic acid, which is a second dispersant, is prepared by adding an alkenyl-substituted succinic acid obtained by an addition reaction of an olefin with maleic anhydride or a hydrogenated product thereof to caustic soda. Can be obtained by saponification with an alkali metal hydroxide exemplified by caustic potash, ammonia, amines, etc., but among them, having at least 12 carbon atoms and having a double bond at the 2-position or higher position A water-soluble salt obtained by saponifying a reaction product obtained by an addition reaction between an internal olefin and maleic anhydride or a hydrogenated product thereof with an alkali metal hydroxide, ammonia, amines, or the like is an esterified rosin substance. Is dispersed in water as fine particles, and the foaming property of the dispersion is preferably suppressed. Usually, the first dispersant and the second dispersant are separately prepared and mixed and used immediately before preparing an aqueous dispersion of an esterified rosin substance. In a dispersant aqueous solution, a monomer mixture as a raw material of the first dispersant may be emulsion-polymerized to prepare a mixture of both dispersants.

In preparing the aqueous dispersion of the present invention,
There is no particular limitation on the amount of both dispersants used for the esterified rosin material. However, in general, it is preferable to use 3 to 25 parts by weight of the first dispersant and 1 to 20 parts by weight of the second dispersant as solids with respect to 100 parts by weight of the esterified rosin substance. Then, as a specific means of preparing the aqueous dispersion, while stirring the heated melt of the esterified rosin substance, the first and second dispersants are added thereto to form a water-in-oil emulsion first, Thereafter, hot water is added to the mixture to invert the phase to obtain an oil-in-water dispersion, but as an alternative, the above-mentioned solvent method can be adopted, and a homogenizer is used under heat and pressure. It is, of course, possible to mechanically disperse them.

In the aqueous dispersion of the present invention, the esterified rosin substance as the dispersoid is fine particles having an average particle diameter of 0.3 μm or less, in other words, water having a very large surface area. Because of the stable dispersion of the sizing agent, the sizing agent for papermaking under neutral or alkaline conditions in the papermaking industry exhibits a remarkably excellent effect. In addition, the aqueous dispersion of the present invention can be used on any paper requiring water resistance,
Not only can it be applied internally or externally, it is also excellent as a waterproofing agent for building materials such as insulation boards, and can be applied to various base materials as a coating agent for the purpose of preventing moisture, slip and corrosion. Outside, moisture admixture for concrete admixture,
It can also be used as a binder for aqueous adhesives and aqueous ink paints. In addition, the aqueous dispersion of the present invention exhibits more excellent effects by adding a dispersant other than the above-described first and second dispersants to the aqueous dispersion. Examples of the dispersant include water-soluble salts of maleic anhydride-added petroleum resin (eg, alkali metal salts, ammonium salts, and organic amine salts), salts of modified naphthalenesulfonic acid formaldehyde, ligninsulfonic acid salts, starch, and derivatives thereof. , Water-soluble polysaccharides and the like. Particularly, a water-soluble salt of a petroleum resin maleate is very useful in combination with the first and second dispersants of the present invention. Demonstrates excellent performance when used for

[0011]

In the aqueous dispersion of the present invention, the stable dispersion of the esterified rosin substance in water in the form of fine particles is due to the exceptional affinity of the second dispersant for the esterified rosin substance, This is considered to be because the esterified rosin substance is dispersed in water in fine particles due to excellent surface activity, and aggregation of the dispersed particles is prevented by the protective colloid property of the first dispersant.

[0012]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it goes without saying that the technical scope of the present invention is not limited by these Examples. In the following description, unless otherwise specified,% means% by weight and part means parts by weight. Production Example 1 A polyoxyethylene polyoxypropylene block polymer (trade name: Epan U-1) was used as an emulsifier in 288 parts of water.
03, manufactured by Daiichi Kogyo Chemical Co., Ltd.) and 30 parts of a 1.9% aqueous solution of sodium dodecylbenzenesulfonate were added.
A monomer mixture comprising 60 parts of styrene, 15 parts of butyl acrylate, 12.5 parts of acrylic acid, and 12.5 parts of methacrylic acid, and 5 parts of isopropyl alcohol and thioglycolic acid-2-yl as a chain transfer agent. Add 4.5 parts of ethylhexyl, stir, and then warm to an internal temperature of 30 ° C.
, 2 parts of ammonium persulfate and 2 parts of sodium hydrogen sulfite were added, and heating was continued. The temperature was raised to 80 ° C in 40 minutes, and polymerization was performed at 80 to 85 for 2 hours.

Next, 10.6 parts of a 24% aqueous solution of caustic soda was added to the mixture, and a neutralization reaction was carried out for 30 minutes. This is referred to as WP-1). Preparation Example 2 Preparation Example 1 except that the monomer mixture used in Preparation Example 1 was changed to a mixture consisting of 60 parts of methyl methacrylate, 15 parts of 2-ethylhexyl acrylate, 12.5 parts of acrylic acid, and 12.5 parts of methacrylic acid. Operate in the same manner as above to obtain a solid content of 25%
(Hereinafter referred to as WP-2).

Production Example 3 To 200 parts of the anionic emulsion obtained in Production Example 1, 3 parts of dimethylaminoethyl acrylate, 5 parts of styrene, 4 parts of butyl acrylate and 0.25 part of thioglycerin as a chain transfer agent were heated. Then, at 40 ° C., 0.13 part of ammonium persulfate and 0.13 part of sodium hydrogen sulfite were added and heating was continued, and the temperature was raised to 80 ° C. in 40 minutes.
Polymerization was carried out at ８５85 ° C. for 4 hours, pH was adjusted to 7.0 after cooling, and water was added to obtain an amphoteric polymer aqueous solution having a solid content of 25% (hereinafter referred to as WP-3).

Production Example 4 A mixed olefin containing 55% of an internal olefin having 16 carbon atoms and having a double bond within the 5-position,
Addition of maleic anhydride gave alkenyl succinic anhydride. A solution of 24 parts of caustic soda in 166 parts of water was added to 100 parts of the acid anhydride, and the mixture was heated to 80 to 90 ° C. to dissolve the acid anhydride in the solution. % Alkenyl succinic acid sodium salt aqueous solution (hereinafter referred to as AS-1).

Production Example 5 A solution of 65.5 parts of triethanolamine dissolved in 229 parts of water was added to 100 parts of the alkenyl succinic anhydride used in Production Example 4, and the mixture was heated to 80 to 90 ° C. After dissolving the product in the solution, the solution was cooled to obtain an aqueous solution of alkenyl succinic acid ethanolamine salt having a solid content of 40% (hereinafter referred to as AS-2).

Production Example 6 Alkenyl succinic anhydride produced by adding maleic anhydride to a mixed olefin containing 75% of an internal olefin having 16 carbon atoms and having a double bond at the 2-position to 4-position is obtained. Was. A solution prepared by dissolving 24 parts of caustic soda in 166 parts of water was added to 100 parts of the acid anhydride, and the mixture was heated to 80 to 90 ° C. and cooled, and an aqueous solution of sodium alkenyl succinate having a solid content of 40% (hereinafter referred to as “this solution”). As AS-3).

Production Example 7 Alkenyl succinic anhydride was obtained by adding maleic anhydride to a pentamer of propylene. A solution obtained by dissolving 80 parts of triethanolamine and 268 parts of water was added to 100 parts of the above acid anhydride, heated to 80 to 90 ° C., cooled, and cooled to an aqueous solution of alkenyl succinic acid ethanolamine salt having a solid content of 40% ( Hereinafter, this is referred to as AS-4).

Production Example 8 A solution prepared by dissolving 27 parts of caustic soda in 175 parts of water was added to 100 parts of the same alkenyl succinic anhydride as used in Production Example 7, heated to 80 to 90 ° C., and cooled. And solid content 40
% Alkenyl succinic acid sodium salt aqueous solution (hereinafter referred to as AS-5).

Production Example 9 100 parts of a petroleum resin ("Hi-Resin" manufactured by Toho Chemical Co., Ltd.) was heated and melted, and 20 parts of maleic anhydride was added thereto to obtain 2 parts.
By reacting at 00 ° C. for 8 hours, a maleated petroleum resin was obtained. A solution prepared by dissolving 50 parts of triethanolamine in 200 parts of water was added to 100 parts of the maleated petroleum resin, and the mixture was stirred at 80 to 90 ° C. for 7 hours. This is referred to as MP-1).

Production Example 10: Preparation of esterified rosin substance (1) To 100 parts of rosin, 9.3 parts of glycerin and 0.25 part of zinc resinate as an esterification catalyst were added, and heated.
The esterification reaction was carried out at 0 ° C. for 16 hours, and the JIS method acid value 1
3.4 An esterified rosin substance having a softening point of 85 ° C. according to the JIS method (hereinafter referred to as ER-1) was obtained.

Production Example 11 Preparation of Esterified Rosin Material Part 2 100 parts of rosin was heated and melted, heated to 190 ° C., 6 parts of maleic anhydride was added with stirring, and reacted at 200 ° C. for 4 hours. , 12.6 parts of cyclohexanedimethanol, 1.8 parts of glycerin and 0.25 part of zinc resinate as an esterification catalyst were added thereto, and the mixture was subjected to an esterification reaction at 250 ° C. for 16 hours. Esterified rosin substance having a softening point of 9.0 ° C. (hereinafter referred to as ER-
2).

Production Example 12 Preparation of Esterified Rosin Material Part 3 100 parts of rosin was heated and melted, and the temperature was raised to 190 ° C. After that, 8 parts of itaconic acid were added with stirring and reacted at 200 ° C. for 5 hours. 7 parts of glycerin and 0.25 part of zinc resinate as an esterification catalyst were added, and an esterification reaction was carried out at 250 ° C. for 16 hours to obtain an esterified rosin substance having an acid value of 59.1 according to JIS and a softening point of 95 ° C. according to JIS. (Hereafter this is called E
R-3).

Example 1 100 parts of an esterified rosin substance (ER-1) was heated and melted, and the temperature was raised to 150 ° C.
And a mixture of 20 parts of dispersant (AS-1) and 20 parts of water are added with vigorous stirring to form a water-in-oil dispersion, and then hot water is added thereto to form an oil-in-water dispersion. After phase inversion, the mixture was diluted to obtain an aqueous dispersion of the esterified rosin substance of the present invention having a solid content of 35%.

Examples 2 to 8 and Comparative Examples 1 to 5 In the same manner as in Example 1 except that the esterified rosin substance and the dispersant used were changed as shown in Table 1, esters having a solid content of 35% were used. An aqueous dispersion of the activated rosin material was obtained.

[0026]

[Table 1]

Comparative Example 6 100 parts of the esterified rosin substance (ER-1) was
Of polyoxyethylene distyryl phenyl ether ammonium sulfate 5 as a dispersant.
After adding 300 parts of dissolved water and emulsifying with stirring,
300 kg / cm ² using a high pressure discharge type homogenizer
Then, the toluene was distilled off under reduced pressure and the concentration was adjusted to obtain an aqueous dispersion of an esterified rosin substance having a solid content of 35%.

Comparative Example 7 100 parts of the esterified rosin substance (ER-2) was heated and melted and heated to 150 ° C. A solution obtained by adding 10 parts of casein to 50 parts of warm water in which 3.7 parts of boric acid soda was dissolved was added to the above-mentioned molten esterified rosin substance with vigorous stirring. An aqueous dispersion of 35% of the esterified rosin material was obtained. Evaluation of Performance of Dispersion The properties of the aqueous dispersions obtained in the above Examples and Comparative Examples and the size effect when these were used as paper sizing agents were evaluated in the following manner.

1) Average particle diameter: The state of the dispersed particles in the dispersion was observed under a microscope, and the average particle diameter was measured. 2) Dispersion stability: Take the dispersion into a test tube, stopper tightly,
It was allowed to stand in a thermostat at 0 ° C. for one week, and the stability (presence or absence of separation) was observed. 3) Size effect: 1% pulp slurry (L-BKP, C
SF450ml) calcium carbonate (20% precipitated calcium carbonate), cationic starch (Pas - Rugamu HMS) 1.0%, aluminum sulfate _{(Al 2 (SO 4) 3} · 13
~14H ₂ O) 1.0%, esterified rosin material aqueous dispersion 0.6% (addition rate are both Taikiinui pulp,
Solid content% by weight), and TAPP is added according to a conventional method.
Paper was made with an I-standard sheet machine. 90 ° C for wet paper
Dry with a rotary drier for 1 minute, and weigh 60 g
/ M ² . This was conditioned at 20 ° C. and a humidity of 65% for 24 hours, and then the size effect was measured by the JIS Steicht method. 4) Foamability test: 0.75% pulp slurry (L-BK
P, CSF450ml) 800cc with stopper 100c
Take in a graduated cylinder of c volume, add 0.5 cc of 1% aqueous solution of aluminum sulfate, add 2.5 cc of 1% aqueous dispersion of esterified rosin substance, shake up and down 20 times, and let it stand.
After 10 minutes, the capacity of the lower transparent aqueous layer was measured. As the foaming property increases, the pulp floats and the capacity of the lower transparent water layer increases. Table 2 shows the evaluation results.

[0030]

[Table 2]

As is evident from Table 2, the aqueous dispersion of the esterified rosin substance of the present invention has fine and stable dispersed particles, has a low foaming property, and has an excellent effect when used as a sizing agent for papermaking. Show.

[0032]

The aqueous dispersion of the esterified rosin substance according to the present invention is more stable than conventional aqueous dispersions of the same kind, and is therefore suitable for various uses such as paper sizing agents. Very useful to use.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-140891 (JP, A) JP-A-7-189174 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 11/00-27/42

Claims (4)

(57) [Claims] 1. An anionic or amphoteric water-dispersible polymer.
And a water-soluble salt of an alkyl-substituted or alkenyl-substituted succinic acid, wherein an esterified product of rosin and / or an esterified product of fortified rosin is dispersed in water. . 2. The aqueous dispersion according to claim 1, wherein the rosin esterified product and / or the fortified rosin esterified product is a partially esterified product of rosin or fortified rosin and a polyhydric alcohol. . 3. A water-soluble salt of an alkyl-substituted or alkenyl-substituted succinic acid obtained by an addition reaction between an internal olefin having 12 or more carbon atoms and having a double bond at a 2-position or more and maleic anhydride. The aqueous dispersion according to claim 1, which is an alkali metal salt, an ammonium salt or an amine salt of the obtained reaction product or a hydrogenated product thereof. 4. An anionic or amphoteric water-dispersible polymer.
Is a polymer of a monomer mixture containing styrene and / or (meth) acrylates.