JPS63215773A - Production of composition containing water-soluble high-molecular material - Google Patents

Abstract

PURPOSE:To produce the title compsn. in a short time with less energy, by stirring a mixture of a water-soluble high-molecular material, an org. solvent and water to obtain a slightly swelling dispersion of the water-soluble high- molecular material, adding water and other blend thereto and mixing them by stirring with an agitating blade at a specific peripheral speed. CONSTITUTION:A water-soluble high-molecular material, an org. solvent in which said high-molecular material is insoluble, and a small amount of water are fed to a container 1 equipped with an agitator and stirred to obtain a slightly swelling dispersion (A) of said water-soluble high-molecular material. Separately, water and other blend are fed to a container 2 equipped with an agitator to obtain a solution mixture (B). The components A and B are fed in a content ratio to a solid/liquid dispersion mixer 4 by means of constant delivery pumps 3 and 3 and mixed by stirring them with an agitating blade at a peripheral speed of 2m/sec to swell and dissolve said water-soluble high-molecular material, thus obtaining the title compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a composition in which a water-soluble polymeric substance is uniformly swollen and dissolved.

[Prior art] Water-soluble polymer substances have thickening properties, VC adhesion properties, emulsification and dispersion properties,
It has properties such as formability, water retention, protective colloidal, #acidic, #salt, and suspending properties.In recent years, these properties have been used to create products such as food, medicine, cosmetics, textiles, It is used in various industrial fields such as building materials, ceramics, civil engineering polling, paper manufacturing, and granulation, as well as in foam extinguishing agents, paints, adhesives, paints, etc.

However, in the preparation of a water-soluble polymer substance-containing composition, if an appropriate blending method is not taken, the water-soluble polymer substance may be mixed with other ingredients, such as salt, to be blended into the composition containing it. Electrolytes and metal salts such as calcium ions may adversely affect swelling and dissolution, or they may adsorb or react with other dispersion ingredients immediately upon addition, making it impossible to utilize the desired properties. In order to avoid such problems and from the viewpoint of nodling, a method is often adopted in which an aqueous solution is prepared in advance in which a water-soluble polymer substance with a concentration of 5% or less is completely swollen and dissolved. .

When preparing the above-mentioned pre-preparation liquid or directly adding a water-soluble polymeric substance to a blended system, the water-soluble polymeric substance first swells and then dissolves.
In many cases, the penetration of water into the inside of the mamako is significantly inhibited, and the swelling and dissolution time becomes extremely long, and in some cases, complete swelling and dissolution cannot be obtained. A dissolution method is used.

(a) Method of adding little by little while stirring.

A method in which water and other mixed raw materials are placed in a dissolution tank as necessary, and the water-soluble polymer substance is added in as small a quantity as possible while vigorously stirring near the water surface. (In many cases, good results can be obtained by passing the mixture through a coarse sieve.) (b) Pre-mixing method with powdered raw materials.

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

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

When used in combination with another organic solvent that does not dissolve the water-soluble polymer substance, a method of dispersing the water-soluble polymer substance in the organic solvent and then adding it to stirring water.

(d) A method of varying the temperature of dispersion, swelling, and dissolution.

Water-soluble polymer particles do not aggregate (do not form lumps)
A method where the polymer is dispersed in water at a certain temperature, and then the remaining water is added to bring the temperature to a level where the water-soluble polymer can dissolve.

However, these methods have the following problems.

(A) The amount of water in the target formulation is small.1. In case of ,
After preparing the dissolved wood sap, add the remaining ingredients to the aqueous solution, or add the above (a) to (a) to the formulation system.
The water-soluble polymeric substance must be added using method (d); however, in the former case, the pre-prepared liquid exhibits the viscous and "sticky" properties characteristic of aqueous solutions of water-soluble polymeric substances. ,
Mixing and dispersion properties are poor, and a large amount of energy and time is required using a powerful stirring device. Moreover, in this case, when trying to obtain the desired mixability and dispersibility, excessive mechanical force causes molecular destruction of the water-soluble polymer substance, making it impossible to achieve the required thickening and shaping properties. There is.

(B) Method for preparing a pre-prepared solution of water-soluble polymeric substance.

Or as a method of adding water-soluble polymeric substances to the main formulation system.
Methods (a) and (b) above have no particular problems when preparing a relatively low concentration, low viscosity polymer aqueous solution, but in many cases the resulting liquid is high viscosity, so In the latter half of the addition, entrainment becomes poor, and homogenization requires a great deal of time and energy, and furthermore, uniform dispersion and dissolution become difficult.

In particular, method (b) requires a great deal of effort to mix the powders together if the amount of powder is large.

(C) Method (c) above is a relatively good preparation method, but if the organic solvent dispersion is not strongly stirred throughout the preparation, the polymer substance will settle in the organic solvent, so it must be continuously stirred. In this case, when the addition of the dispersion liquid is finished, the stirring χ may no longer come into contact with the dispersion liquid, and the dispersion liquid may not be stirred. Alternatively, the water-soluble polymer substance must be added while being washed away with the organic solvent, and this cannot be carried out unless the formulation system can secure that amount of organic solvent.

Furthermore, even if these problems do not exist, if an organic solvent dispersion is directly added to a blended system without preparing a pre-prepared solution, it may be affected by electrolytes, metal salts, and dispersions, resulting in high water solubility. The intended performance of the molecular substance may not be achieved. Particularly in the case of continuous mass production, the water-soluble polymeric substance in the organic solvent often settles or becomes impossible to pump.

(D) Preparing the pre-prepared liquid using the method described in (d) above also requires complicated operations, and when adding it directly to the blending system,
Other blended raw materials are limited to those that have little quality deterioration or alteration due to heat.

[Problems to be Solved by the Invention j The present invention provides a method for preparing a composition in which a water-soluble polymer substance is uniformly swollen and dissolved, without causing "stickiness", in a short time and with less energy. This is the problem we are trying to solve.

[Means for Solving the Problems] In order to solve the above problems, the present invention includes stirring a mixture of a water-soluble polymeric substance, an organic solvent in which the polymeric substance is substantially insoluble, and a small amount of water. The first step is to prepare a slightly swollen dispersion of a water-soluble polymeric substance.

The slightly swollen dispersion of the water-soluble polymer substance, water and other compounds are stirred and mixed using a stirring blade whose tip has a circumferential speed of 2 tn/sec or more to swell the water-soluble polymer substance. This method is characterized by comprising a second step of dissolving.

To explain in more detail, 1 In the present invention, after dispersing a water-soluble polymer substance in an organic solvent in which it is insoluble,
A uniform dispersion of a slightly swollen water-soluble polymer is prepared by adding water or adding a water-soluble polymer to an organic solvent containing a small amount of water and stirring. By adding to the rest of the formulation and stirring,
Prepare the desired formulation. In this case, the remaining mixed solution of the formulation may be prepared by dividing the mixture as necessary.

The above-mentioned water-soluble polymer substances include cellulose derivatives such as sodium carboxymethylcellulose, methylcellulose, and hydroxynitylcellulose, alkali metal alginates such as sodium alginate and cara dinan, xanthan gum, gum karaya, and gum arabic. There are synthetic binders such as polyvinyl alcohol, sodium polyacrylate, carboxyvinyl polymer, etc., and one or more of these can be used.

Also, as an organic solvent, methyl alcohol is used.

Ethyl alcohol, acetone, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, fats and oils, fatty acid esters, fatty acids (dissolved if solid at room temperature), and other fragrances with low viscosity when used. Any oil-soluble additive may be added to these solvents as long as they do not dissolve the polymeric substance.

Other compounds added to the slightly swollen dispersion of water-soluble polymeric substances include benzoic acid and sorbic acid.

Preservatives such as butyl P-oxybenzoate, antibacterial and antibacterial agents such as 2,4 thiazolylbenzimidazole, antioxidants such as nilinelupic acid and dibutylhydroxytoluene, and ultraviolet rays such as salicylic acid and benzphenone. There are absorbents, other pigments, dyes, colorants, etc.

Furthermore, inorganic or organic solid substances can also be added that do not impair the fluidity of the slightly swollen water-soluble polymer dispersion. In this case, the inorganic solid substance may be aluminum oxide zeolite, and the organic solid substance may be polyethylene or polypropylene powder, beads, or the like.

The ratio of water-soluble polymer substance to organic solvent is 1:1.1~
1:5, preferably 1:1.5 to 1:3, and the amount of water added to the organic solvent dispersion of the water-soluble polymer substance is:
It is preferably 5 to 70%, particularly 8 to 40%, of the water-soluble polymeric substance, and the viscosity of the slightly swollen dispersion is preferably 2 to 8 poise when mixed with other preparations.

When stirring and mixing a slightly swollen dispersion of a water-soluble polymeric substance and a mixture of other compounds, the circumferential speed of the tip of the stirring blade is at least 2 m/min in order to bring the slightly swollen polymeric substance into contact with water as much as possible. see, preferably 3 m 1 sec or more.

Also, the addition of water when preparing a slightly swollen dispersion of a water-soluble polymer substance.

(a) After dispersing a water-soluble polymer substance in an organic solvent, a predetermined amount of water is added.

(b) After dispersing a water-soluble polymer substance in an organic solvent.

Adding an organic solvent and/or water-containing substance premixed with a predetermined amount of water.

(C) After adding a predetermined amount of water to an organic solvent and stirring, a water-soluble polymer substance is added.

(d) Add water to the combination of (C) and (a) or (b) above.

Any one 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 vessel 1, a water-soluble polymer substance, an organic solvent in which it is insoluble, and a small amount of water are stirred.

Separately, a mixed solution of other formulations is prepared in the stirring container 2, which is sent to the solid-liquid disperser 4 at a constant ratio by a metering pump 3.3, and stirred for a short time by the solid-liquid disperser 4. Mix to produce the desired formulation. In addition, the mixture mixed with stirring at a solid-liquid fraction of 94 was added to the reflux path 5 indicated by the dotted line.
The mixture may be refluxed into the stirring vessel 2 by stirring, and the uniform dispersion in which the water-soluble polymer substance is slightly swollen may be stirred and mixed again.

Furthermore, if the target water-soluble polymer-containing composition has a relatively low viscosity (approximately 50 voids or less), use the slightly swollen dispersion prepared in the stirring vessel 1.

It may also be added directly to the stirring vessel 2 as shown by the dotted line 6.

Further, as shown in FIG. 2, a uniform dispersion of a slightly swollen water-soluble polymer substance is prepared in a stirring vessel 7, and this is stirred using a metering pump or a flow rate adjustment valve 8 to create a mixed liquid of other substances. It is also possible to supply the mixture directly into the container 9 and form a desired mixture using a mixer IO provided in the container θ.

In the present invention, since the water-soluble polymeric substance is only tafv/wetted by the organic solvent in which the water-soluble polymeric substance is insoluble and a small amount of water, the preliminary dispersion of the slightly swollen polymeric substance is Compared to preparing a preliminary aqueous solution in which the molecular substance is completely swollen and dissolved, the amount of the preliminary solution is 176 to 1/40, and the time from the start of preparation of the preliminary solution to the end of blending the entire composition is 173%. ~l/20. Moreover, as in the above-mentioned dissolution methods (a) to (d), the polymeric substances are not blended as they are, but other blended substances are blended after slight swelling, so the influence of blended substances such as electrolytes is almost eliminated. I never receive it.

In addition, since the slightly swollen polymer material is stirred and instantly brought into contact with a large amount of water, the water-soluble polymer material quickly swells.
Since it dissolves, it is not only possible to omit a homogenization operation depending on the formulation, but also to enable continuous production of the entire formulation system.

[Example 1] Preparation composition of liquid cleanser Calcium carbonate 50.0% ethylene glycol 2.0 Coconut fatty acid diethalamide 2.0 Citric acid, trisodium,
Dihydrate 1.3 Citric acid monohydrate (30% aqueous solution)
0.45 fragrance $40.2 Sodium benzoate (20% aqueous solution) 1.5 water
To prepare a liquid cleanser with the remainder having the above composition, first add 0.25% water (2596 to carboxymethyl cellulose) to ethylene glycol based on the entire cleanser.
is added in advance, CMC is added and dispersed while stirring, and CM
A homogeneous dispersion in which C was slightly swollen was prepared.

Separately, add citric acid trisodium φ2 hydrate, coconut fatty acid jetanolamide solution, citric acid aqueous solution, calcium carbonate, sodium alkylbenzenesulfonate slurry, fragrance, An abrasive slurry was prepared by adding an aqueous sodium benzoate solution.

Next, the slightly swollen dispersion of CMC and the abrasive slurry were added,
Continuous solid-liquid dispersion at a predetermined ratio by each metering pump #! (Special mechanical industrial type, pipeline homomixer) with a processing speed of 500 kg/hr.

Then, the slurry was stirred at a circumferential speed of the stirring tip blade of the continuous disperser of 5 m/see, and the slurry was sent to the product tank by a product transfer pump.

The slurry taken out from the product tank was a stable liquid cleanser in which calcium carbonate was uniformly dispersed.

(Comparative Example 1) Using the same method as above, the circumferential speed of the stirring tip blade of the solid-liquid continuous disperser was
When stirred at 0.5 m/sec, the resulting liquid cleanser had a rough texture due to agglomeration of calcium carbonate.

(Comparative Example 2) When preparing a slurry in which calcium carbonate is dispersed in water, a fluid type slurry cannot be prepared unless the calcium carbonate DM is 65% or less.

In the case of the above example, 27% of the water of the total cleanser is required for preparing the calcium carbonate slurry, and therefore the C
The amount of water available for pre-rA production of MC was 9.55%.

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

(Comparative Example 3) When a dispersion of CMC in ethylene glycol was transferred using a metering pump without slight swelling, the CMC sedimented and blocked, making transfer impossible. However, when it was added from the top, the desired viscosity of the liquid cleanser could not be obtained.

(Comparative Example 4) Liquid Cleanser - When the entire amount of the ethylene glycol dispersion of CMC was added to the total amount of water to swell and dissolve CMC, it was about 10 poise at room temperature.

This was a jiggly, elastic bowl, and the Weisenberg effect caused the liquid to crawl up the stirring rod. Therefore, it has been extremely difficult to blend raw materials lower than calcium carbonate into this.

<Example 2> Indoor wall paint (water-based paint $4) set
Synthetic titanium oxide 25.0% carrageenan 1.5 Ethanol (industrial) 2.
0 Henzalkonium chloride 0.1 Water
Add TEZ to the remaining lq total 1.8% ethanol! After stirring and confirming the dissolution of TBZ, add water to 0.24% of the entire paint.
% (16% relative to carrageenan) plus J! l! Carrageenan was added while stirring. Furthermore, a premixed solution of 0.06% of the total paint water in the remaining ethanol was added with 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 to the remaining water while stirring to prepare a pigment slurry.

Next, while this pigment slurry was being recycled through a solid-liquid dispersion machine, the above-mentioned Larkinan slightly expanded pellet dispersion was supplied to the same solid-liquid dispersion machine as in Example 1 and instantly dispersed. The recycling amount at this time was 600 kg/hr, the circumferential speed of the stirring tip blade of the solid-liquid disperser 4 was 4 m/sec, and the circumferential speed of the stirring tip blade of the stirring container 2 was 1 m1sec. was a stable water-based paint in which titanium oxide was uniformly dispersed.

(Comparative Example 1) Using the same method as above, change the circumferential speed of the stirring tip blade of solid-liquid disperser 4.
When prepared at a rate of 0.5 mm/sac, the resulting slurry had a rough texture due to agglomeration of titanium oxide.

<Example 3> Method for preparing ice cream mix (ice cream mixture before freezing) Composition Cow Milk
37.1%/Heku (moisture 15%) 0.5 Cream (40%) 18.0 Skim milk powder 6.1 Sugar
14.5 Sodium alginate 03 Fatty acid monoglyceride
0.2 Water Remainder Place heating means around the stirring vessel 7 shown in Figure 2.

In an apparatus in which heating and cooling means are provided around the stirring vessel 9,! Add water, milk, and cream to mixing container 9.

Add sugar, powdered milk, and emulsifier in this order while stirring (only using a quick stirring method). Heat to 70°C for 20 minutes while stirring well, then cool to 40°C. Separately, sodium alginate is added to the stirred container 7 while the putter is melted and stirred to prepare a slightly swollen dispersion of sodium alginate having a final temperature of 40 to 50°C.

This slightly swollen dispersion liquid was added to the vicinity of the stirring χ of the homomixer 10 in the above-mentioned liquid, which was simultaneously performing the Ikari type stirring and homomixer stirring, and the peripheral speed of the Ikari type stirring station was set to 2 m1se.
c. The homomixer was stirred well for 5 minutes at a circumferential speed of 6 Ill/SeC.

The resulting ice cream mix had a very good viscosity.

(Comparative Example 1) Sodium alginate was thoroughly mixed with sugar and added as a powder into a stirring container s, but in order to obtain the same uniform and viscous liquid as above, it took 30 I understand.

<1m Example 4> Emollient lotion (softening emulsion or nutritional emulsion, O/W non-ionic emulsion type) Composition Oil-based component Sluriran 5.0% Vaseline 2.0 Beeswax
0.5 fragrance
0.5 paraoxyamin, 9. Butyl fragrant 0.01 Problen gelicol 5.0 Ethanol
5.0 Potassium hydroxide (10% aqueous solution) 1.0 Purified wood Remainder In the same apparatus as in Example 3, the oily components were mixed and heated in advance in the stirring vessel 7 to 70°C. Separately, paraoxyammobutyl was added to 0.6% of the entire lotion of pucopylene gellicol, and while stirring, 0.1% of the entire lotion of purified water and sodium carboxymethyl cellulose were sequentially added. , a slightly swollen dispersion of sodium carboxymethyl cellulose is prepared in advance. Add the remaining purified water and propylene glycol to the stirring container 9, heat mix, and then add ethanol.
'C. To this was added an oily component that had been mixed and heated to 70''C in advance for preliminary emulsification. At this time, the peripheral speed of the homomixer 10 was 7ffi/SeC tare.

A slightly swollen dispersion of sodium carboxymethylcellulose was added to this pre-emulsion from the stirring vessel 7 in the same manner as the oily component, and after uniformly mixing, an aqueous potassium hydroxide solution was further added from the stirring vessel 7 to neutralize and homogenize. After uniformly emulsifying with the mixer, the homomixer was stopped, and the stirring container 9 was cooled while slowly rotating the Ikari type stirring bowl.
The lotion was prepared by cooling to °C.

(Comparative Example 1) Similar to Example 4, to obtain a uniform and stable lotion,
When an aqueous solution of carboxymethyl cellulose sodium was prepared, it was necessary to dilute it to a 1% aqueous solution, which required more than 20 times the volume ratio, and more than 5 times as much time to prepare the aqueous solution.

(Example 5) Preparation of slurry in the production of soft ferrite (magnetic head core) In recent years, granulated powder (!D grains) using a spray dryer has been used in the molding of precision-shaped parts such as magnetic head cores as functional ceramics. This method has come to be used because the granules obtained by this method have excellent fluidity, can be stably filled into a mold during molding, and can easily produce a molded product with high density.

Here, the slurry preparation method before granulation will be described. In addition, in the following composition, polyvinyl alcohol CPVA)
Glycerin is used to provide adhesiveness to make the spherical particles stable and to maintain the strength of the molded product, and glycerin is used to provide rheology, plasticity, and flexibility.PV
Prevents solidification of A and makes it soft! Added to create σ grains.

Slurry composition Polyvinyl alcohol 1.0 Glycerin 2.0 Purified water
1.0 In the same apparatus as in Example 3, purified water is added to glycerin in advance in a stirring vessel 7, and polyvinyl alcohol is added under stirring to prepare a slightly swollen dispersion of polyvinyl alcohol.

Put the ferrite slurry into the stirring container 8 and make it about 60-65
Heat to °C. At this time, by stirring only with the Ikari type stirring purchase,
The circumferential speed is lIl/SeC. After reaching the above temperature,
The homomixer 10 also started stirring at a circumferential speed of 6 ffl/sea, and the slightly swollen dispersion of polyvinyl alcohol was added to the vicinity of the stirring blade, followed by thorough stirring for about 5 minutes.

This slurry is completely swollen with polyvinyl alcohol.
It was dissolved and the ferrite was uniformly dispersed.

After adding some antifoaming agent to this material, granules were made using a spray dryer, an appropriate amount of zinc stearate was added, and press (sintering) molding was performed to obtain ceramics with high density and good dimensional stability. .

(Comparative Example 1) As a general method of adding polyvinyl alcohol, 10%
An aqueous solution was prepared and added to the ferrite slurry, but the slurry concentration decreased and granules with the desired bulk density could not be obtained using a spray dryer.

In addition, in the ceramic industry, a water-soluble polymer substance is added for the same purpose as in the same example, but the raw material slurry itself is already
It contains 0% water, and from the viewpoint of the density of the molded product and the cost of drying, the question is how to incorporate water-soluble polymer substances without increasing the water content. Therefore, in the same industry, the manufacturing method of the present invention satisfies this need.

[Effects of the Invention] According to the present invention, a water-soluble polymer substance is slightly wetted with an organic solvent in which it is insoluble and a small amount of water, so that a slightly swollen dispersion of a water-soluble polymer substance is formed in a small amount and in a short period of time. Not only can the dispersion be prepared in an hour, but the dispersion can be prepared at a peripheral speed of 2 mlse at the tip.
By stirring with a stirring blade of c or more and bringing it into contact with a large amount of water in a short period of time, the water-soluble polymer substance quickly swells and dissolves.

Compositions containing water-soluble polymeric substances can be produced in a short time and with less energy.

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic explanatory diagrams of an apparatus used to carry out the present invention. 1.2,7.9 Stirring vessel, 4 fists...Solid-liquid dispersion machine.

Claims (1)

[Claims] 1. A slightly swollen dispersion of a water-soluble polymer is prepared by stirring a mixture of a water-soluble polymer, an organic solvent in which the polymer is substantially insoluble, and a small amount of water. The first step is to stir and mix the slightly swollen dispersion of the water-soluble polymer substance with water and other compounds using a stirring blade whose tip has a circumferential speed of 2 m/sec or more to form the water-soluble polymer substance. A method for producing a water-soluble polymer substance-containing composition, comprising: a second step of swelling and dissolving the water-soluble polymer substance.