JPH0597500A - Production of fiber softening clay and fiber softening composition - Google Patents

Abstract

PURPOSE:To improve hand feeling by performing shearing treatment for specified suspension and blending the obtained fiber softening clay. CONSTITUTION:Suspension is obtained by incorporating water swelling three- layer clay (e.g. saponite) having >=10ml/2g swelling force which is obtained by a swelling force (volume method) measuring method (2.0g/100ml/24 hours) of bentonite adopted in Japanese pharmacopoeia. Then, this suspension is treated at 20-90 deg.C at the shearing velocity of >=50000sec<-1> for one minute to 5 hours and thereby fiber softening clay having <=5mum average particle diameter is produced. Pasty fiber softening composition is obtained by blending a nonionic surfactant with this clay.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a clay having an excellent effect of imparting softness to fibers, and a softening composition containing the clay.

[0002]

2. Description of the Related Art Improving the flexibility and texture of washed textile products is widely used in household laundry,
Fourth having usually at least one long chain alkyl group
Grade ammonium salts have been used. Generally, softening agents for these fibers have been sold as so-called "softening agents" in the form of liquid emulsions for use in rinse baths. However, although these cationic surfactants have an excellent softening effect, they are "sticky",
It has the disadvantage that it does not feel good to the touch because it has a "nullness" feeling.

On the other hand, a method using clay is known as another method for imparting softness to fibers. Clay is an excellent raw material that is cheap and safe, as well as having a different “feel” or good water absorption from cationic surfactants, but as it is, it gives a softening effect to cationic surfactants. It has the drawback of being significantly inferior to the comparison.

In order to make up for such drawbacks of clay minerals, attempts have been made to improve the softening effect by increasing the amount of clay adsorbed on the fiber surface. For example, a method of bridging a negative charge on the fiber surface and a negative charge on the clay surface by adding a polyvalent metal ion to increase the amount of clay adsorbed on the cloth (Japanese Patent Laid-Open No. 53-94695). A method of increasing the amount of clay adsorbed on the negatively charged fiber surface by adsorbing a cationic surfactant on the clay and positively charging the clay surface (JP-A-60-209069).
Alternatively, it may be used in combination with an anti-settling agent, and further in combination with a polymer flocculant (JP-A-2-103299).

However, in any of these methods, the softening effect is saturated when the adsorption amount is increased, and the saturated softening effect is still at an insufficient level, so that it cannot be used as a household softener. ..

In the above-mentioned Japanese Patent Laid-Open No. 2-103299, a mixed slurry of clay and an anti-settling agent is added to 1000
Shear rate higher than 0 sec ^-1 , specifically 1000
It is possible to improve the sedimentation stability of the liquid softening composition by shear mixing at a shear rate of ⁰ to 40,000 sec ⁻¹ to reduce the clay diameter to 1 μ or less and to sufficiently disperse and activate the anti-settling agent. Have been described. However, no improvement of the softening effect as in the present invention has been suggested, and in fact, the effect of the present invention cannot be obtained with the above-mentioned shearing force.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an inorganic softening agent having a different "touch feeling" made of clay mineral as an alternative to the conventional softening agent made of a cationic surfactant. is there.

[0008]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to solve the above problems, surprisingly, by treating a highly swelling three-layer clay under an ultrahigh shear rate, ,
We have found that we can achieve that purpose.

That is, the method for producing the softened clay of the present invention is a bentonite swelling force (volume method) measuring method (2.0 g / 100 ml / 24) adopted in the Japanese Pharmacopoeia.
A suspension containing a water-swellable three-layer viscosity swelling power is more than 10 ml / 2 g as determined by time), 50000sec ^-1
It is characterized in that it is processed under the above shear rate.

Further, the fiber softening composition of the present invention is characterized by being blended with the clay produced through the above treatment.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The water-swellable three-layer clay used in the present invention includes smectites such as montmorillonite, saponite, and hectorite, and swelling mica. An X-ray diffraction peak is shown at 6 Å. Further, all of these clays have the property of swelling remarkably when put into water. This is because these clays are SiO ₂ lattice / Al ₂ O
This is because a layered structure in which a ₃ or MgO lattice / SiO ₂ lattice and a three-layer lattice are overlapped with each other is formed, and moisture is introduced between the lattice units of the three layers and adjacent lattice units, that is, the layers expand. ..

The clay used in the present invention preferably has a higher swelling property, and the "swelling power" which is an index of the swelling property is 1
It is preferably 0 ml / 2 g or more, and particularly preferably 30 ml / 2 g or more. The swelling power referred to here is the swelling power (volumetric method) measuring method of bentonite adopted by the Japanese Pharmacopoeia (2.0 g /
100 ml / 24 hours). That is,
Add 2.0 g of the sample and 100 ml of pure water to a 100 ml graduated cylinder with a ground stopper in about 10 times. However, the amount of the previously added sample is adjusted so that the sample does not adhere to the inner wall and is smoothly deposited on the bottom of the cylinder. After most of the previously added sample is deposited, the next sample is added. After the addition is completed, the sample is left to stand for 24 hours, and the apparent volume of the sample deposited in the container is read. The unit of swelling power is (ml / 2g).

This swelling force is influenced by the kind of ion-exchangeable cations existing between the layers of clay. As the cation of the clay used in the present invention, a monovalent alkali metal,
Na, K, and Li are particularly preferable, but they may contain an alkaline earth metal or other polyvalent metal. In this case, at least 20 mol% of all exchangeable ions are preferably alkali metal ions. When the amount is 20 mol% or less, the swelling power of the clay is rapidly reduced, and the softening effect cannot be recognized.

The clay used in the present invention includes montmorillonite, which is manufactured by Kunimine Industry Co., Ltd.
Kunipia G and Kunipia F, Paulagel from American Colloid, Western Bond from Applied Industrial Materials, and Yellowstone from Dresser Minerals. Examples of those containing saponite include Veegum T, Veegum HV, Veegum F and Veegum K manufactured by Vanderbilt. Examples of those containing hectorite include Hectorite AW, Hectorite 200 and Benton EW manufactured by American Colloid, Macaloid manufactured by National Reed. Examples of the swelling mica include swelling synthetic mica ME series manufactured by Corp Chemical Co., Ltd., sodium tetrasilicon mica manufactured by Topy Industries, Ltd. (trade name, DP-
DM and DM clean).

In the present invention, clay containing swellable three-layer clay as a main component is suspended in a state of 50,000 sec ^-1 (5
0000 sec ^-1) or more, preferably it is necessary to process under 70000Sec ^-1 or more ultra-high shear rate, thereby a thin film-like clay particles are obtained, which exhibit excellent flexibility imparting effect. When the shear rate is less than 50,000 sec ^-1 , only the usual refining and dispersing actions are obtained, thin film clay particles are not obtained, and the softening effect is not exhibited.

In general, it is described in Torayo Sudo, "Clay Minerals," Iwanami Zensho p80, that clay minerals are strip-shaped or plate-shaped. Therefore, when there is a flow in the dispersion medium, the clay particles are oriented with their major axis oriented in the direction of flow.
When such a dispersion passes through a narrow gap,
It is considered that clay is subjected to a strong shearing force in the direction along the layers, and the layers of the clay are separated. It is presumed that such flat thin film-like particles have higher film-forming property than the agglomerate particles, can easily coat the fiber surface uniformly, and have a high softening effect. Therefore, in the present invention, it is preferable to treat the clay suspension by a method in which a shearing force is applied in a direction along the layers, and a homogenizer and a colloid mill which are usually subjected to shearing, breaking and dispersing when passing through a narrow gap. A jet crusher is effective. Preferably, it is processed through a gap having a clearance of 0.5 mm or less.

In order to effectively apply the shearing force, the viscosity of the clay suspension at 25 ° C. measured by a B-type viscometer is 500.
It is desirable that it is 00 cp or less, preferably 1000 cp or less. When the viscosity exceeds 50,000 cp, the shearing stress extremely increases and the shear rate decreases, and normally, a shear rate of 50,000 sec ^-1 or more cannot be obtained. Further, in some cases, the yield value of the suspension may be exceeded, idling of the stirring section may occur, the suspension may not flow, and an excellent softening effect cannot be obtained.

Further, the treatment time under a shear rate of 50000 sec ^-1 or more varies depending on the type of clay,
10 seconds to 24 hours are preferable, and more preferably 1 minute to 5 hours.
It's time. If it is less than 10 seconds, the treatment time is too short to obtain an effective shearing effect. On the other hand, when it exceeds 24 hours, the clay gradually becomes amorphous and the effect of imparting softness is lowered, which is not preferable.

The treatment of the present invention is carried out at a temperature of the clay dispersion liquid of 0.degree.
It can be carried out at 105 ° C, but 20 ° C to 90 ° C is particularly preferable. The clay after the treatment of the present invention has been refined to have an average particle size of 5 μm or less by a centrifugal sedimentation method, and most of the particles have a flaky shape by observation with an optical microscope and an electron microscope.

The fiber softening composition of the present invention may be composed of only the above-mentioned treated clay, and a small amount of a water-soluble electrolyte, a nonionic surfactant, an anionic surfactant and the like as a component other than clay. May be included. The softening composition can be used in an appropriate form such as an aqueous dispersion, a paste, a flake or a powder.

The fiber softening composition of the present invention can be used by adding it to a rinsing liquid for washing, but it can also be incorporated into a detergent and used in a washing liquid.

[0022]

According to the present invention, the swelling power is 10 ml / 2.
g of water swellable tri-layer clay suspension for 50000 sec
^-By treating under an ultra high shearing force of ^-1 or more, clay which imparts excellent flexibility to fibers such as cotton can be obtained.
Moreover, the softness of the fibers after the softening treatment is light, and a feeling different from that of conventional cationic surfactants can be obtained.

[0023]

EXAMPLES The softening effect in the following examples and comparative examples was performed as follows.

[0024]Evaluation method of softening effect  Household mini-mini washing machine with 5 liters of tap water (pine
Specified as an electric washing machine NA-33 type manufactured by Shimodenki Sangyo Co., Ltd.
Add a quantity of clay or clay treatment solution with stirring, and
Stir for 5 minutes to disperse the clay. Preprocessed here
Put two cotton towels (about 170g) and stir for 5 minutes
Rinsed. The treated cotton towel was dehydrated for 2 minutes
After that, air-dry, and then a constant temperature and humidity room at 25 ° C and 60% RH
The humidity was controlled for 1 day. The evaluation is sensual, and an untreated cotton towel is used.
0 point, standard amount of commercially available softener (Lion Co., Ltd.
Cotton towel treated with soft & dry) is 4 points and 5 points method
I did it in.

The pretreatment of the used cotton towel was performed as follows. That is, 25 g of detergent (Lion Co., Ltd., high top) was used in a household two-tub type washing machine,
30 liters of tap water at 50 ℃, unbleached cotton towel 12
The pieces (about 1 kg) were washed for 15 minutes. After dehydration for 5 minutes, washing, dehydration and rinsing were performed under the same conditions. For rinsing, tap water was used as it was, and the operation of rinsing for 15 minutes and dehydration for 5 minutes was repeated 6 times and then air-dried.

Examples 1 to 3 and Comparative Examples 1 to 2 23.5 g of saponite (brand name: Veegum T, water content: 14.7%) manufactured by Vanderbilt with a swelling power of 45 ml / 2 g
Was added to 1976.5 g of water in a 3 liter beaker with stirring, and the mixture was allowed to swell sufficiently by stirring for 4 days (stirring blade: flat paddle, rotation speed: 200 rp).
m). The viscosity of this suspension was 20 cp. afterwards,
Kinematica homogenizer (Polytron PT35
Mold, clearance: 0.2 mm, stirring section radius: 10 m
m) was treated at a predetermined rotation speed for 20 minutes to obtain a clay treatment liquid, and the softening effect was evaluated.

Further, the same evaluation was carried out using a clay treatment liquid treated by changing the rotation speed. In the evaluation of the softening effect in each of the above examples, 75 g of the clay treatment liquid was used. In addition, the shear rate was calculated by the following equation 1 from the rotation speed of the pomogenizer.

[0028]

[Equation 1]

Furthermore, the case where 75 g of the clay dispersion liquid not treated with a homogenizer was used (Comparative Example 2), and 0.88 g of Veegum T powder was added directly to tap water instead of the clay treatment liquid (Comparative Example 1) Was similarly evaluated. The above results are shown in Table 1.

Examples 1 to 3 exhibited an excellent effect of imparting softness, had a soft feel to the touch, and had a feel different from that of conventional cationic surfactants.

[0031]

[Table 1]Table 1: Clay processing conditions and softening effect Comparative Example Comparative Example Comparative Example Example Example Example 1 2 3 1 2 3 Homogenizer No No No Yes Yes Yes Yes Number of revolutions (rpm) − − 5,000 10,000 15,000 20,000 Shear rate (sec^-1) − − 2.6 × 10^Four5.2 x 10^Four7.9 x 10^Four10.5 x 10 ^Four Softening effect 2 2 2 3 4 4

Comparative Example 4 Ca-type montmorillonite (water content: 8 ml / 2 g)
%) 21.8 g of water in a 3 liter beaker 19
78.2 g was added with stirring, and the mixture was stirred as it was for 4 days to be sufficiently swollen (stirring blade: flat paddle, rotation speed 2
00 rpm). The viscosity of this suspension was 15 cp.
Then, the homogenizer treatment is performed in the same manner as in Example 3,
A clay treatment liquid was obtained. Next, when 75 g of this clay treatment liquid was used to evaluate the softening effect, the results were 2 points equivalent to those of an untreated towel, and the touch was a stiff feel.
There was almost no softening effect.

Example 4 A dispersion (1 wt%) of clay (Vegum T) treated under the same conditions as in Example 3 was centrifuged (8000 rpm, 1
The resulting cake was spread thinly on a polyester film and dried at 50 ° C. for 5 hours. The dried clay was weakly crushed into flakes (solid content: 92
%). When the softening effect was evaluated using 0.8 g of this treated clay flake, the softening effect was 4 points, which is equivalent to that of a commercially available softening agent (soft & dry). Further, the feel was light and the feel was different from that of conventional cationic surfactants.

Example 5 Hectorite (trade name: macaloid, water content 16.6%) manufactured by National Lead Co. having a swelling power of 45 ml / 2 g 48.0
g was added to 1952 g of water in a 3 liter beaker while stirring, and the mixture was stirred as it was for 5 days to prepare an aqueous suspension of 2% clay (stirring blade: propeller, rotation speed 800).
rpm). The viscosity of this suspension was 80 cp. Then, Kinematica homogenizer (Polytron PT3
Type 5, clearance: 0.2 mm, stirring section radius: 30 m
m), 20,000 rpm, that is, a shear rate of 15.7 × 1
Clay treatment liquid was obtained by treatment at 0 ⁴ sec ⁻¹ for 10 minutes.

When 38.0 g of this clay treatment liquid was used to evaluate the softening effect, the results were 4 points, which are equivalent to those of a commercially available softening agent (soft & dry). Further, the feel was light and the feel was different from that of conventional cationic surfactants.

Example 6 Hectorite (trade name: Hectabrite AW, water content 16.6, manufactured by American Colloid Co., Ltd.) having a swelling power of 70 ml / 2 g
%) 430.0 g was added to 4570 g of water with stirring, and the mixture was stirred as it was for 5 days to prepare an aqueous suspension of clay 7.2% (stirring blade: flat paddle, rotation speed 300 rp).
m). The viscosity of this suspension was 980 cp. After that, using an emulsifying machine (disper mill, clearance: 0.2 mm, stirring section radius: 100 mm) manufactured by Hosokawa Micron Co., Ltd., a rotation speed of 6000 rpm, that is, a shear rate of 3.2 ×.
A clay treatment solution was obtained by treating at 10 ⁵ sec ^-1 for 20 minutes.

When 20.8 g of this clay treatment liquid was used to evaluate the softening effect, the results were 4 points, which are equivalent to those of a commercially available softening agent (soft & dry). Further, the feel was light and the feel was different from that of conventional cationic surfactants.

Example 7 Hectorite (trade name: Hectabrite AW, water content 16.6, manufactured by American Colloid Co., Ltd.) having a swelling power of 40 ml / 2 g.
%) 48.0 g of water in a 3 liter beaker 1
Added to 952 g with stirring. The viscosity of the obtained suspension was 50 cp. Then, using a homomixer HV-M type (clearance: 0.5 mm, stirring section radius: 20 mm) manufactured by Tokushu Kika Kogyo Co., Ltd., the clay was treated for 60 minutes at 12000 rpm, that is, a shear rate of 50,000 sec ^−1. A treatment liquid was obtained.

The softening effect was evaluated using 75 g of this clay treatment liquid, and a commercially available softening agent (soft & dry) was used.
It was 3 points equivalent to. Further, the feel was light and the feel was different from that of conventional cationic surfactants.

Comparative Example 5 167.9 g of the same hectorite as that used in Example 7
Was added to 1832 g of water in a 3 liter beaker with stirring. The viscosity was 52,000 cp. When this clay suspension was treated with the same homomixer as in Example 5, the shear stress was high and the maximum output was 1,000 rpm.
Was obtained. The shear rate at this time is 4,100 s
It was ec ^-1 . The clay treatment liquid was obtained by performing the treatment at the shear rate for 10 minutes.

When the softening effect was evaluated using 21.5 g of this clay treatment liquid, the softening effect was almost the same as that of the untreated towel, and the softening effect was almost nonexistent.

Claims (2)

[Claims] 1. A method for measuring the swelling force (volumetric method) of bentonite adopted by the Japanese Pharmacopoeia (2.0 g / 100 ml).
/ 24 hours) swelling power is 10ml / 2g
The suspension containing the above water-swellable three-layer clay is added to 50,000 se
A method for producing a fiber-softened clay, which comprises treating at a shear rate of c ^-1 or more. 2. A fiber softening composition comprising the fiber softening clay obtained by the production method according to claim 1.