JPH07122025B2 - Method for producing composition containing water-soluble polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a composition in which a water-soluble polymer substance is uniformly swollen and dissolved.

[Prior Art] Water-soluble polymer substances have properties such as thickening, adhesiveness, emulsifying and dispersing properties, moldability, water retention, protective colloid properties, acid resistance, salt resistance, and suspension properties. Therefore, by utilizing these properties, in recent years, various industrial fields such as foods, pharmaceuticals, cosmetics, fibers, building materials, ceramics, civil engineering boring, paper industry, granulation, foam powder extinguishing agents, paints, adhesives, It is also used in paints.

However, in the preparation of a composition containing a water-soluble polymer substance, when an appropriate compounding method is not taken, the water-soluble polymer substance is used as another compounding ingredient to be compounded in the composition containing it, such as salt. Electrolysis cost and metal salts such as calcium ions may adversely affect swelling and dissolution, or may cause immediate adsorption or reaction with other dispersoid blending raw materials upon addition, so that the desired properties may not be utilized. Therefore, in order to avoid such problems and from the viewpoint of handling, a method of preliminarily preparing an aqueous solution in which a water-soluble polymer substance having a concentration of 5% or less is swollen and dissolved in advance is often employed.

Then, when preparing the above preparatory liquid or when directly adding the water-soluble polymer substance to the compounding system, the water-soluble polymer substance is first swelled and then dissolved.
In many cases, the permeation of water into the inside of the cod is significantly hindered, and the swelling and dissolution times become extremely long, or in some cases complete swelling and the dissolution cannot be obtained. A dissolution method is adopted.

(A) A method of adding little by little while stirring.

A method in which water and, if necessary, other ingredients are added to the dissolution tank, and the water-soluble polymer substance is added as little as possible while vigorously stirring near the water surface. (In many cases, good results are obtained by passing through a coarse sieve.) (B) Premixing method with powder raw material.

In order to prevent aggregation of water-soluble polymer particles, when used in combination with other powder raw materials such as sugar and inorganic powder raw materials, they are mixed well with those powder raw materials in advance and the method (a) is used.

(C) A method of dispersing in an organic solvent and charging.

When used in combination with another organic solvent that does not dissolve the water-soluble polymer, it is dispersed in the organic solvent and then added into stirred water.

(D) A method of changing the temperature of dispersion, swelling, and dissolution.

Water-soluble polymer particles do not aggregate (do not form lumps)
A method of once dispersing in water at a temperature and then adding the remaining water to a temperature at which a water-soluble polymer can be dissolved.

However, these methods have the following problems.

(A) When the amount of water to be mixed in the target compound is small, it becomes impossible to separately secure the water for the pre-prepared liquid of the swollen solution of the water-soluble polymer substance and the water for mixing the other raw materials. Therefore, after preparing an aqueous solution in which a water-soluble polymer substance is swollen and dissolved in advance, the remaining formulation is added to the aqueous solution, or the above-mentioned methods (a) to (d) are added to the formulation system. You have to add a water-soluble polymer in
In the former case, the preliminarily prepared liquid has a viscous and “dishing” property that is characteristic of an aqueous solution of a water-soluble polymer substance, so that the mixing and dispersibility is poor, and a large amount of energy and time are consumed by a powerful stirring device. You will need it. Moreover, in this case, the desired mixability,
When it is attempted to obtain dispersibility, the mechanical breakdown of the water-soluble polymer substance may occur due to excessive mechanical force, and the required thickening property and moldability may not be achieved.

(B) As a method of preparing a preliminarily prepared liquid of a water-soluble polymer substance or a method of adding a water-soluble polymer substance to a main compounding system, the above methods (a) and (b) are There is no particular problem when preparing a viscous polymer aqueous solution, but in many cases it becomes a high-viscosity liquid, so entrainment deteriorates in the latter half of the addition of the water-soluble polymer substance, and much time and energy are required for homogenization. It is necessary, and it becomes difficult to uniformly disperse and dissolve.

Especially in the method (b), when the amount of the powder is large, a great amount of labor is required for mixing the powders with each other.

(C) The above method (c) is a relatively good preparation method, but during the preparation, unless the organic solvent dispersion liquid is vigorously stirred from beginning to end, the polymer substance precipitates in the organic solvent. Must be stirred. In this case, at the end of addition of the dispersion liquid, the stirring blade may not come into contact with the dispersion liquid, and stirring may not be added to the dispersion liquid. Alternatively, the water-soluble polymer substance must be added while being washed away with the organic solvent, and it cannot be carried out unless the compounding composition system can secure the amount of the organic solvent.

Furthermore, even if these problems do not occur, if the organic solvent dispersion is directly added to the blending system without preparing the pre-prepared liquid, it is affected by the electrolyte, metal salt, and dispersion, and the water-soluble polymer substance The desired performance of may not be achieved.
In particular, in the case of continuous production in large-scale production, the water-soluble polymer substance in the organic solvent often precipitates, or pumping becomes impossible.

(D) The procedure is also complicated when preparing the pre-prepared liquid by the method of (d) above, and when directly added to the compounding system, other compounding raw materials are less affected by deterioration of quality and deterioration due to heat. Limited to things.

[Problems to be Solved by the Invention] According to the present invention, a composition in which a water-soluble polymer substance is uniformly swollen and dissolved is prepared in a short time with a small amount of energy without causing “mamako”. That is the problem to be solved.

[Means for Solving Problems] In order to solve the above problems, the present invention comprises stirring a mixture of a water-soluble polymer substance, an organic solvent in which the polymer substance is substantially insoluble, and a small amount of water. Then, the first step of preparing a slightly swollen dispersion liquid of the water-soluble polymer substance, and the peripheral speed of the tip of the slightly swollen dispersion liquid of the water-soluble polymer substance, water and other compounds.
It is characterized by comprising a second step of swelling and dissolving the water-soluble polymer substance by stirring and mixing with a stirring blade of 2 m / sec or more.

More specifically, in the present invention, the water-soluble polymer substance is dispersed in an insoluble organic solvent and then a trace amount of water is added, or the water-soluble polymer substance is added to an organic solvent containing a trace amount of water. By adding and stirring, a uniform dispersion of the slightly swollen water-soluble polymer substance is prepared, and the slightly swollen dispersion is added to the remaining formulation and mixed by stirring,
Make the desired formulation. In this case, the liquid mixture of the remaining formulation may be prepared by dividing it if necessary.

Examples of the water-soluble polymer, sodium carboxymethyl cellulose, methyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, sodium alginate, alkali metal alginates such as carrageenan, xanthan gum, gum tragacanth, karaya gum, gum arabic, polyvinyl alcohol, polyacryl. There are synthetic binders such as sodium acidate and carboxyvinyl polymer, and one or more of these can be used.

Further, as the organic solvent, methyl alcohol, ethyl alcohol, acetone, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, fats and oils, fatty acid esters, fatty acids (dissolved when solid at room temperature), other fragrances As long as it is low-viscosity and does not dissolve the water-soluble polymer substance when used, any oil-soluble additive may be added to these solvents.

Other formulations added to the slightly swollen dispersion of water-soluble polymeric substances include preservatives such as benzoic acid, sorbic acid, butyl P-oxybenzoate, antibacterial agents such as 2,4 thiazolylbenzimidazole, Antifungal agent, erythorbic acid, antioxidants such as dibutylhydroxytoluene, salicylic acid type,
Examples include benzophenone-based ultraviolet absorbers, other pigments, dyes, colorants, and the like.

Furthermore, an inorganic or organic solid substance which does not impair the fluidity of the water-soluble polymer slightly swollen dispersion liquid can be added. In this case, aluminum oxide zeolite is used as the inorganic solid substance, and polyethylene, polypropylene powder, beads, etc. are used as the organic solid substance.

The ratio of the water-soluble polymer substance to the organic solvent is 1: 1.1 to 1: 5, preferably 1: 1.5 to 1: 3, and the amount of water added to the organic solvent dispersion liquid of the water-soluble polymer substance is 5 to 70 of high molecular weight polymer
%, Particularly 8 to 40% is preferable, and the viscosity of the slightly swollen dispersion liquid is
It is preferable to adjust the porosity to 2 to 8 poise when mixed with other preparation liquid.

The stirring and mixing of the slightly swollen dispersion liquid of the water-soluble polymer substance and the mixed liquid of the other compound, in order to bring the slightly swollen polymer substance into contact with water as much as possible, the peripheral speed of the stirring blade tip is at least 2 m / sec, preferably 3 m / sec or more.

In addition, as for the addition of water in the preparation of the slightly swelling dispersion liquid of the water-soluble polymer substance, (a) the water-soluble polymer substance is dispersed in the organic solvent, and then a predetermined amount of water is added.

(B) After dispersing the water-soluble polymer substance in the organic solvent, a substance containing an organic solvent and / or water in which a predetermined amount of water is premixed is added.

(C) A water-soluble polymer substance is added while stirring a predetermined amount of water after adding it to the organic solvent.

(D) Add water to the combination of (c) and (a) or (b).

That is, any of (a) to (d) may be used.

FIG. 1 shows an outline of an example of an apparatus for carrying out the above method. In a stirring container 1, a water-soluble polymer substance, an organic solvent in which this is insoluble, and a small amount of water are agitated. A mixed solution of the compound of 1 is prepared, and these are sent to the solid-liquid disperser 4 at a constant ratio by the metering pumps 3, 3 and mixed with the solid-liquid disperser 4 for a short time to produce a desired compound. To be done. Further, the mixture mixed by stirring with the solid-liquid disperser 4 may be refluxed to the stirring container 2 through the reflux passage 5 shown by the dotted line, and the homogeneous dispersion liquid in which the water-soluble polymer substance is slightly swollen may be stirred and mixed again.

Furthermore, when the desired water-soluble polymer-containing composition has a relatively low viscosity (about 50 poise or less), the slightly swollen dispersion prepared in the stirring container 1 is directly stirred as shown by the dotted line 6. It may be added to the container 2.

Further, as shown in FIG. 2, a uniform dispersion liquid of the water-soluble polymer substance slightly swollen in the agitation container 7 is prepared, and this is prepared by a metering pump or a flow rate adjusting valve 8 to prepare a mixed liquid of other substances. It is also possible to supply the mixture directly into the container 9 and prepare a desired mixture by the mixer 10 provided in the container 9.

In the present invention, since the water-soluble polymer substance is only slightly swelling the water-soluble polymer substance with an insoluble organic solvent and a small amount of water, the preliminary dispersion liquid of the slightly swollen polymer substance,
Compared with the case of preparing a preliminary aqueous solution in which a water-soluble polymer substance is completely swollen and dissolved, the amount of the preliminary preparation liquid is 1/6 to 1
In addition, it can be set to 1 / 3-1 / 20 in the time from the start of preparation of the preparatory liquid to the end of blending of the entire composition. Moreover, unlike the above-mentioned dissolution methods (a) to (d), the high molecular weight substance is not blended as it is, but other compounded substances are blended after slightly swelling, so that the influence of the compound such as the electrolyte is almost eliminated. Never receive.

In addition, since the slightly swollen polymer substance is stirred and brought into immediate contact with a large amount of water, the water-soluble polymer substance swollen quickly,
Because of the dissolution, not only can the homogenization operation be omitted depending on the formulation, but continuous production of the entire formulation system can also be possible.

[Examples] <Example 1> Preparation of liquid cleanser Composition calcium carbonate 50.0% Alkylbenzene sodium sulfonate (40%) 5.0 Ethylene glycol 2.0 Coconut fatty acid diethyl amide 2.0 Citric acid / 3 sodium dihydrate 1.3 Citric acid / 1 Hydrochloride (30% aqueous solution) 0.45 Sodium carboxymethyl cellulose (CMC) 1.0 Perfume 0.2 Sodium benzoate (20% aqueous solution) 1.5 Water balance To prepare a liquid cleanser having the above composition, first add 0.25% of the cleanser to ethylene glycol. Water (25% with respect to carboxymethyl cellulose) was added in advance, and CMC was added and dispersed while stirring to prepare a uniform dispersion liquid in which CMC was slightly swollen.

Separately, citric acid / trisodium / dihydrate, coconut fatty acid diethanolamide solution, citric acid aqueous solution, calcium carbonate, sodium alkylbenzene sulfonate slurry, fragrance, and the like are added to the remaining water while stirring while suppressing foaming as much as possible. An aqueous solution of sodium benzoate was added to prepare an abrasive slurry.

Next, the slightly swelled dispersion of CMC and the abrasive slurry were supplied to the solid-liquid continuous disperser (manufactured by Tokushu Kika Kogyo Co., Ltd., pipeline homomixer) at a processing rate of 500 kg / hr at a predetermined ratio by a quantitative pump. Then, the peripheral speed of the stirring tip blade of the continuous disperser was stirred at 5 m / sec, and this slurry was sent to a product tank by a manufacturing transfer pump.

The slurry extracted from the product layer was a stable liquid cleanser in which calcium carbonate was uniformly dispersed.

<< Comparative Example 1 >> By the same method as above, the peripheral speed of the stirring tip blade of the solid-liquid continuous disperser was set to 0.
When stirred at 5 m / sec, the obtained liquid cleanser was rough with aggregates of calcium carbonate.

<< Comparative Example 2 >> When preparing a slurry in which calcium carbonate is dispersed in water, a fluidized slurry cannot be prepared unless the content of calcium carbonate DM is 65% or less.

In the case of the above example, 27% of the total cleanser water was required for the preparation of the calcium carbonate slurry and therefore the CMC
The amount of water available for pre-preparation was 9.55%.

An attempt was made to prepare a preliminary aqueous solution of CMC using this water, but it became very viscous and could not be prepared.

<< Comparative Example 3 >> A dispersion liquid of CMC in ethylene glycol was transferred by a metering pump without fine swelling, and CMC was settled and blocked, so that the transfer could not be carried out. However, when it was added from the top, the desired viscosity of the liquid cleanser was not obtained.

<< Comparative Example 4 >> The total amount of the ethylene glycol dispersion of CMC was added to water in the total amount of the liquid cleanser to swell and dissolve CMC, and it was about 10 poise at room temperature.

This was a pre-prepared and elastic liquid, and the liquid came up through the stirring rod due to the Weisenberg effect. Therefore, it was extremely difficult to mix the raw material of calcium carbonate or less into this.

<Example 2> Paint for indoor wall coating (water-based paint) Composition Titanium oxide 25.0% Carrageenan 1.5 Ethanol (for industrial use) 2.0 Benzalkonium chloride 0.1 TBZ (2,4 thiazolyl benzimidazole) 0.2 Water balance 1.8% of the total paint Add TBZ to ethanol and stir to TB
After confirming the dissolution of Z, water was added in an amount of 0.24% (16% based on carrageenan) of the whole paint, and the carrageenan was added while stirring. Further, 0.06% of water of the whole paint was mixed and dissolved in the remaining ethanol in advance and added while stirring.

This was a uniform dispersion in which carrageenan was slightly swollen.

Using the apparatus shown in FIG. 1, benzalkonium chloride and titanium oxide were added while stirring the remaining water to prepare a pigment slurry.

Next, while the pigment slurry was being recycled through a solid-liquid disperser, the above-mentioned color genin micro-swelled product dispersion was supplied to the same solid-liquid disperser as in Example 1 and dispersed instantly. The recycling rate at this time was 600 kg / hr, the peripheral speed of the stirring tip blade of the solid-liquid disperser 4 was 4 m / sec, and the peripheral speed of the stirring tip blade of the stirring container 2 was 1 m / sec.

The obtained slurry was a stable aqueous paint in which titanium oxide was uniformly dispersed.

<< Comparative Example 1 >> By the same method as above, the stirring tip impeller peripheral speed of the solid-liquid disperser 4 was set to 0.
When the slurry was prepared at 5 m / sec, the obtained slurry was rough with aggregated titanium oxide.

<Example 3> Preparation method of ice cream mix (mixture of ice cream before freezing) Composition Milk 37.1% Butter (water content 15%) 0.5 Cream (40%) 18.0 Skim milk powder 6.1 Sugar 14.5 Sodium alginate 0.3 Fatty acid monoglyceride 0.2 Water Remaining part In a device provided with heating means around the stirring container 7 and heating and cooling means around the stirring container 9 shown in FIG. 2, water, milk, cream, sugar, powdered milk, emulsifier in the stirring container 9 Add in this order with stirring (squid type stirring only). Warm to 70 ° C for 20 minutes with good stirring and then cool to 40 ° C.
Separately, while stirring the butter while melting it in the stirring vessel 7, sodium hair alginate was added and the final temperature was 40%.
Prepare a slightly swollen dispersion of sodium alginate at ~ 50 ° C.

This slightly swollen dispersion is added to the vicinity of the stirring blade of the homomixer 10 in the above liquid which is simultaneously performing squid type stirring and homomixer stirring, and the peripheral speed of the squid type stirring blade is 2 m / sec, the peripheral speed of the homomixer. The speed was set to 6 m / sec and well stirred for 5 minutes.

The obtained ice cream mix had a remarkable viscosity and was extremely good.

Comparative Example 1 Sodium alginate was well mixed with sugar, and a method of adding powder to the stirring container 9 was performed. To obtain the same uniform and viscous liquid as above, 6 times 30 It took a minute.

<Example 4> Emollient lotion (soft emulsion or nutrient emulsion, O / W nonionic emulsion type) Composition Oily component Squalane 5.0% Vaseline 2.0 Beeswax 0.5 Sorbitan sesquioleate ester 0.8 Polyoxyethylene oleyl ether (20E.O.) 1.2 Fragrance 0.5 Butyl paraoxybenzoate 0.01 Propylene glycol 5.0 Ethanol 5.0 Potassium hydroxide (10% aqueous solution) 1.0 Sodium carboxymethyl cellulose 0.2 Purified water balance In the same apparatus as in Example 3, the oily components were mixed and heated in advance in the stirring container 7. To 70 ℃. Separately, butyl paraoxybenzoate was added to 0.6% propylene glycol of the whole lotion, and 0.1% of purified water and sodium carboxymethylcellulose of the whole lotion were sequentially added under stirring to slightly swell the sodium carboxymethylcellulose. Prepare the dispersion. The remaining purified water and propylene glycol are added to the stirring container 9 and mixed by heating, and then ethanol is added and the temperature is brought to 70 ° C. Preliminary emulsification was performed by adding an oily component which had been mixed and heated to 70 ° C. in advance. The peripheral speed of the homomixer 10 at this time was 7 m / sec.

To this preliminary emulsion, a slightly swelled dispersion of sodium carboxymethyl cellulose was added from the stirring container 7 in the same manner as the oily component, and mixed uniformly, and then an aqueous potassium hydroxide solution was added from the stirring container 7 to neutralize the mixture. After uniformly emulsifying with a mixer, stop the homomixer, cool the stirring container 9 while slowly rotating the squid-type stirring blade, and cool to 30 ° C.
The lotion was prepared by cooling to.

<< Comparative Example 1 >> Similar to Example 4, in order to obtain a uniform and stable lotion,
When an aqueous solution of sodium caboxymethyl cellulose was prepared, it was necessary to dilute it to a 1% aqueous solution, which required a volume ratio of 20 times or more, and an aqueous solution preparation time of 5 times or more.

<Example 5> Method of preparing slurry in manufacturing soft ferrite (magnetic head core) In recent years, a method of using granulated powder (granule) by a spray dryer is used for molding precision shaped parts such as magnetic head cores as functional ceramics. Came to be. This is because the granules obtained by the same method have excellent fluidity, the filling into the mold during molding is stable, and a molded product having a high density is easily obtained.

Here, a method for preparing a slurry before granulation will be described. Incidentally, in the following composition, polyvinyl alcohol (PVA) is for tackiness for stabilizing the spherical particles and for maintaining the strength of the molded body, and glycerin is for imparting rheological properties, plasticity and flexibility. It was added to make the PVA solidify and to make soft granules.

Slurry composition Ferrite calcined pulverized product (water dispersion having a slurry concentration of 60%) 96.0% Polyvinyl alcohol 1.0 Glycerin 2.0 Purified water 1.0 Purified water was added to glycerin in advance in a stirring vessel 7 in the same apparatus as in Example 3, Under stirring, polyvinyl alcohol is added to prepare a slightly swollen dispersion of polyvinyl alcohol.

The ferrite slurry is put in the stirring container 9 and heated to about 60 to 65 ° C. At this time, the peripheral speed is
It is 1 m / sec. After reaching the above temperature, homomixer 10
Also, stirring was started at a peripheral speed of 6 m / sec, a slightly swollen dispersion of polyvinyl alcohol was added near the stirring blade, and the mixture was stirred well for about 5 minutes.

In this slurry, polyvinyl alcohol is completely swollen,
It was melted and ferrite was uniformly dispersed.

After adding a small amount of antifoaming agent to this product, granules were made by a spray dryer, zinc stearate was added in an appropriate amount, and press molding (sintering) was carried out to obtain a high density and dimensional stable ceramics. .

<< Comparative Example 1 >> As a general addition method of polyvinyl alcohol, a method of preparing a 10% aqueous solution and adding it to a ferrite slurry was performed, but the slurry concentration was lowered, and a granule having an intended bulk density was obtained by a spray dryer. There wasn't.

In the ceramic industry, a water-soluble polymer substance was added for the same purpose as in the same example, but the raw material slurry itself was already 30
In terms of the density of the molded product and the cost of drying,
The question is how to add a water-soluble polymer without increasing the water content. Therefore, in the same industry, the manufacturing method of the present invention sufficiently answers it.

EFFECTS OF THE INVENTION According to the present invention, a water-soluble polymer substance is slightly swollen with an insoluble organic solvent and a small amount of water. Not only can it be prepared by stirring the dispersion with a stirring blade with a peripheral speed of 2 m / sec or more at the tip and contacting it with a large amount of water in a short time, the water-soluble polymer substance swells and dissolves quickly. Therefore, the composition containing the water-soluble polymer substance can be produced in a short time with a small amount of energy.

[Brief description of drawings]

1 and 2 are schematic explanatory views of an apparatus used for carrying out the present invention. 1,2,7,9 …… Stirring container, 4 …… Solid-liquid dispersion machine.

Claims (1)

[Claims] 1. A mixture of a water-soluble polymer substance, an organic solvent in which the polymer substance is substantially insoluble, and a small amount of water is stirred to obtain a mixture.
First step of preparing a slightly swelling dispersion of a water-soluble polymer substance, stirring the slightly swelling dispersion liquid of a water-soluble polymer substance, water and other compounds at a peripheral speed of the tip of 2 m / sec or more A method for producing a composition containing a water-soluble polymer substance, which comprises a second step of swelling and dissolving the water-soluble polymer substance by stirring and mixing with a blade.