JP5196096B2 - Washing soap - Google Patents

Description

  The present invention relates to a detergent comprising a composite clay composition containing a smectite clay mineral component.

Smectite clay represented by acid clay and bentonite has long been used as an inorganic detergent because it has a high affinity for water and also exhibits a surface-active effect on oil. For example, Patent Document 1 proposes an inorganic detergent composition containing composite magnesium phyllosilicate and smectite group clay.
JP 2000-319690 A

However, smectite group clay minerals are generally produced together with SiO ₂ crystals such as quartz, opal, cristobalite, and tridymite. In particular, opal and cristobalite that are intimately combined with smectite group clay minerals are considered to be extremely fine crystals of smectite. It is difficult to separate them together. Moreover, such a SiO ₂ crystal that is difficult to separate does not function as an active ingredient when the smectite clay is used for a cleaning agent or the like, and therefore, the smectite system containing a large amount of such SiO ₂ crystal. In order to obtain the desired cleaning effect, the clay has the disadvantage of having to use more than necessary.

  Furthermore, the inorganic cleaning composition of Patent Document 1 does not have a sufficient surface-active effect on oily substances (hereinafter sometimes simply referred to as “oil”), and further improvement in cleaning properties against oily soils is required.

Therefore, the object of the present invention is to contain smectite clay components in which SiO ₂ crystals of opal and cristobalite are contained as inevitable impurities in smectite clays from many production areas, and further improve the detergency against oily dirt. It is to provide a cleansing agent.

According to the present invention, there is provided a composite clay composition comprising (A) a smectite group clay mineral and (B) a synthetic talc, and in X-ray diffraction measurement, the [001] plane of smectite and the [001] plane of synthetic talc. Containing a composite clay composition in which the diffraction peak derived from
The composite clay composition has a BET specific surface area of 250 m ² / g or more, has a slurry or paste form, and further has a solid content concentration of the composite clay composition on a 105 ° C. dry basis. Is provided in the range of greater than 5% by weight and less than or equal to 50% by weight .

In the cleaning agent of the present invention,
(1) The composite clay composition is a weight ratio of (A) :( B) = 1: 2 to 1: 9 with (A) smectite group clay mineral and (B) synthetic talc on the basis of drying at 105 ° C. Containing in
(2) further containing an alkali metal bicarbonate or carbonate,
(3) In the X-ray diffraction measurement of the composite clay composition, the intensity of the X-ray diffraction peak due to the [111] plane of the opal or cristobalite SiO ₂ crystal is [020] plane of smectite and [020] of synthetic talc. Less than the intensity of the composite peak due to the surface,
(4) In the X-ray diffraction measurement, the composite clay composition is substantially free from the X-ray diffraction peak due to the [111] plane of the opal or cristobalite SiO ₂ crystal,
(5) (A) The smectite group clay mineral is a dioctahedral smectite. In X-ray diffraction measurement, the X-ray diffraction peak of the [060] plane of the dioctahedral clay mineral and the [060] plane of the trioctahedral clay mineral The X-ray diffraction peak produced by is synthesized and expressed ,
Is preferred.

The cleaning agent of the present invention is composed of a composite clay composition comprising (A) a smectite group clay mineral and (B) synthetic talc, and the synthetic talc (3MgO.4SiO ₂ ) in the composite clay composition. H ₂ O) has an important feature in that SiO ₂ crystals such as opal or cristobalite, which are included as inevitable impurities that are difficult to separate in many smectite clays produced in nature, are converted. Yes. That is, the SiO ₂ crystal that is difficult to separate from the smectite group clay mineral is a completely unnecessary component when the smectite group clay mineral is used for a cleaning agent. In the present invention, this unnecessary component is low crystalline. In addition, this synthetic talc is excellent in affinity for oil. Therefore, according to the present invention, the SiO ₂ crystal, which is an unnecessary impurity, is converted into synthetic talc having high lipophilicity, thereby providing a surfactant effect in combination with the hydrophilicity of the smectite clay mineral. In particular, the detergency against oil stains is enhanced.

In addition, in the present invention, as apparent from the fact that diffraction peaks derived from the [001] plane of smectite and the [001] plane of synthetic talc are substantially lost in X-ray diffraction measurement, (A) smectite A group clay mineral and (B) synthetic talc are combined and integrated. Further, the intensity of the diffraction peak due to the [111] plane of the opal or cristobalite SiO ₂ crystal is smaller than the intensity of the synthetic peak due to the [020] plane of smectite and the [020] plane of synthetic talc. In addition, most of the SiO ₂ crystals, which are unnecessary impurities, are converted to lipophilic synthetic talc. For these reasons, the detergent of the present invention has an enhanced surface activity, and as will be understood from the examples and comparative examples described later, it is simply a smectite clay (bentonite) that also contains SiO ₂ crystals of impurities. Etc.) Needless to say, it has a high detergency against oil stains as compared with a mixture of talc and a separately prepared synthetic talc.

(Manufacture of composite clay composition)
In the present invention, a natural smectite clay is used as a raw material for producing a composite clay composition used as a cleaning agent. As the smectite clay, dioctahedral smectites such as montmorillonite, beidellite and nontronite are mainly used. Typical examples include components (acid clay, bentonite) and components mainly composed of trioctahedral smectite such as saponite, hectorite, and saconite. Bentonite, which is mainly composed of montmorillonite and beidellite, is naturally alkali-rich and can be used for various purposes as it is depending on the production area, and some alkalis are leached with rainwater. There are so-called active bentonites that have been treated to return to alkali rich using soda ash, etc., and it goes without saying that any of them can be used as the raw material of the present invention as a natural smectite clay. . Further, montmorillonite and beidellite are dioctahedral smectite has a layered structure consisting of SiO ₄ tetrahedral layers -AlO ₆ octahedral layer -SiO ₄ tetrahedra layer, a part of Al of these octahedral layer is Mg Ya Fe (II) has a basic skeleton in which a part of Si in the tetrahedral layer is replaced with Al by the same type of dissimilar metal as the lower valence metal, and the crystal lattice generates a negative charge at the substituted portion. However, there are balanced amounts of cations and water between these laminated layers, and they are neutralized in terms of charge. That is, smectite exhibits a cation exchange capacity according to the type and amount of such a substituted metal or interlayer element. Derived from the organic affinity of the layer surface with such a layered structure of Si-O-Si bonds and the polarity of the metal substitution site, it exhibits hydrophilicity as well as lipophilicity, and exhibits a surface-active effect suitable as a cleaning agent it is conceivable that.

As already mentioned, natural smectite clay is often produced together with SiO ₂ crystals such as opal and cristobalite, and depending on the production area, such a SiO ₂ crystal is a fine crystal having the aforementioned layer structure of smectite. It is difficult to separate by physical means such as wind. In the present invention, a natural smectite clay containing such difficult-to-separate SiO ₂ crystals can be used. In particular, the content of SiO ₂ crystals such as opal and cristobalite is 5% by weight or more, particularly 10%. It is preferable to use about 35% by weight. That is, this low SiO ₂ crystal content has a small merit for converting the SiO ₂ crystal into talc by the means described below. Further, those having a SiO ₂ crystal content larger than the above range often have high SiO ₂ crystallinity and low reactivity, and have a low smectite content, so that as a raw material for obtaining the desired composite clay composition Has little merit.

The SiO ₂ crystal content of opal, cristobalite, etc. contained in the smectite clay was dissolved in the alkaline aqueous solution by dissolving the SiO ₂ crystal by, for example, alkali treatment using an alkaline aqueous solution such as sodium hydroxide. It can be calculated as soluble silicic acid (%) by measuring the amount of SiO ₂ .

  The naturally occurring smectite clay used as described above exhibits, for example, the X-ray diffraction peak shown in FIG. That is, FIG. 1A is an X-ray diffraction chart of natural smectite clay (bentonite containing dioctahedral smectite as a main component) used as a raw material in Example 1 described later. As can be understood from this, this smectite clay exhibits a diffraction peak derived from the [001] plane of smectite in the region of 2θ = 5.0 to 8.0 °, and 2θ = 19.0 to 20.5 °. Shows a diffraction peak derived from the [020] plane of smectite, and further shows a diffraction peak derived from the [060] plane of dioctahedral smectite in the region of 2θ = 61.0 to 62.5 degrees. A diffraction peak derived from the [111] plane of opal or cristobalite is shown in the region of 2θ = 21.0 to 22.5 degrees.

In the present invention, the natural smectite clay as described above is reacted with magnesium oxide or magnesium hydroxide. Specifically, both are mixed in the presence of water and then heat-treated with stirring. As a result, the aforementioned opal and cristobalite SiO ₂ crystals contained in the smectite group clay mineral are converted into talc having a non-laminated or low laminated structure.

This reaction is represented by the following formula as an example. In the following formulae, the smectite group clay mineral is represented by Smectite, and the opal and cristobalite SiO ₂ crystals compounded thereto are represented by OpalSiO ₂ .
[Smectite + OpalSiO ₂ ] + 4.5MgO + 4.5H ₂ O
→ Smectite + SiO ₂ + 4.5Mg (OH) ₂
→ Smectite + 0.25 [3MgO.4SiO ₂ .H ₂ O] +3.75 Mg (OH) ₂

  In the above formula, magnesium oxide (MgO) is used as a raw material. However, since magnesium oxide is easily hydrated and changed to magnesium hydroxide in the presence of water, water is used as a reaction raw material from the beginning. Even when magnesium oxide is used, the reaction is expressed by the same formula.

As understood from the above reaction formula, the magnesium oxide (or magnesium hydroxide) to be used is preferably used in an amount of 1.5 times mol or more of SiO ₂ crystals contained in the smectite, and more than necessary. Since it is not meaningful even if used in excess, it is generally preferable to use it in an amount of 1.5 to 10 moles. In addition, when using magnesium oxide, it is a matter of course that equimolar or more of the magnesium oxide used, which is the theoretical amount of hydration with MgO, is necessary, but from the standpoint of wet stirring (slurry) reaction, reaction slurry In view of the fact that the viscosity is sufficiently fluid and is a solid-liquid reaction, the solid content concentration should be high to some extent, and should be 85 to 95% by weight based on the total amount of the reaction slurry mother liquor. Is preferred.

  Moreover, it is desirable that the natural smectite clay used in the above reaction is preliminarily pulverized and adjusted to an appropriate particle size. In this case, the raw material clay may be wet pulverized in an aqueous medium as it is, or may be dried and then dry pulverized. Also,

  In the above reaction, the heat treatment temperature is 60 ° C. or more, particularly 70 to 100 ° C., and the heat treatment time is generally about 3 to 8 hours, although it varies depending on the amount of smectite clay used and the heat treatment temperature. .

  After producing talc as described above, silicon dioxide is further added and heat-treated at a temperature of 60 ° C. or higher, particularly 70 to 100 ° C. with stirring. As a result, excess magnesium hydroxide remaining in the above reaction is also converted into talc and becomes an active ingredient.

The silicon dioxide used for such heat treatment is not particularly limited, but is preferably amorphous so-called white carbon from the viewpoint of not adversely affecting the properties of the composite clay even when an excessive amount of silicon dioxide remains. Used for. Such amorphous silicon dioxide (hydrous silicic acid) usually has the following formula:
SiO ₂ · nH ₂ O
In the formula, n is a number from 0.1 to 0.3.
It is represented by

Such a conversion reaction of magnesium hydroxide is represented by the following formula as an example.
Smectite + 0.25 [3MgO · 4SiO ₂ · H ₂ O]
+ 3.75Mg (OH) ₂ + 5SiO ₂ .nH ₂ O
→ Smectite + 1.5 [3MgO · 4SiO ₂ · H ₂ O]
However, n is the same number as the above.

  As understood from the above formula, silicon dioxide used in this example is 1.2 mol times or more of magnesium hydroxide contained in the reaction system (in terms of stoichiometry, 5 ÷ 3.75). = 1.33 mole times), and in particular 1.2 to 1.5 mole times converts all or most of the produced magnesium hydroxide into talc and the remaining dioxide. This is suitable for significantly reducing the amount of silicon.

Such heat treatment for converting magnesium hydroxide into talc is usually performed for about 3 to 12 hours. At this time, a composite clay composition in which the total amount or most of the amorphous SiO ₂ used for the reaction between the SiO ₂ crystals contained in the smectite clay and the excess magnesium hydroxide in the subsequent stage is converted to talc is produced. A small amount of unreacted amorphous SiO ₂ and magnesium hydroxide may remain in the composition. Although it is difficult to accurately quantify the residual amount, the presence or absence can be qualitatively confirmed by X-ray diffraction measurement. The cleaning agent of the present invention may be any residual as long as it is practically usable in the cleaning performance due to the lipophilicity / oil absorption and surface active action described later.

Composite clay composition obtained as described above, and it is or concentrated, are subjected to use in the form of a slurry or paste.

(Composite clay composition)
The composite clay composition thus obtained is composed of (A) a smectite group clay mineral and (B) a synthetic talc [3MgO.4SiO ₂ .H ₂ O]. For example, as shown in FIG. It has an X-ray diffraction peak. FIG. 1B is an X-ray diffraction pattern of the composite clay composition produced in Example 1.

  That is, as understood from FIG. 1B, in such a composite clay composition, the smectite [020] plane and the synthetic talc [020] plane are in the range of 2θ = 19.0 to 20.5 degrees. The derived diffraction peak is synthesized and expressed (that is, the area is larger than the peak due to the [020] plane of smectite in FIG. 1A), and the presence of smectite and synthesized talc is confirmed. However, it should originally exist in the diffraction peak derived from the [001] plane of smectite that should exist in the region of 2θ = 5.0 to 8.0 degrees or in the region of 2θ = 9.0 to 10.0 degrees. The diffraction peak derived from the [001] plane of the synthetic talc is virtually eliminated or not observed. That is, in the composite clay composition used in the present invention, the smectite in the water-dispersed state and newly generated synthetic talc particles are mixed at the single-layer particle level by the semi-synthetic reaction under hydrothermal treatment performed in the two steps described above. Even when dried, smectite and talc do not stack in the C-axis direction, or even if they occur, it seems to be disordered stacking with irregular layer spacing, and diffraction peaks appear in these regions. The fact that the composite clay composition is different from a simple mixture of smectite group clay mineral laminated particles and talc laminated particles shows that both are randomly and uniformly compounded.

Moreover, in the composite clay composition used as a cleaning agent in the present invention, the opal and cristobalite SiO ₂ crystals contained as inevitable impurities in smectite clay from many localities are converted to talc. Therefore, as can be understood from the comparison of the X-ray diffraction peaks of FIG. 1A and FIG. 1B, the SiO ₂ crystal in the raw smectite in the region of 2θ = 21.0 to 22.5 degrees. The diffraction peak due to the [111] plane (see FIG. 1 (a)) is substantially lost or reduced in this composite clay composition (see FIG. 1 (b)). That is, loss or reduction of the diffraction peaks due to [111] plane of such SiO ₂ crystals, all or most of the SiO ₂ crystals such smectite clay minerals are telling that it is converted to talc.

As understood from FIG. 1 (a), in the present invention, the smectite clay used as a raw material has a diffraction peak (2θ = 21.0 to 22.5 degrees) on the [111] plane of the SiO ₂ crystal. Is larger than the diffraction peak (2θ = 19.0 to 20.5 degrees) of smectite [020] plane, but in the composite clay composition used in the present invention, the [111] plane of such SiO ₂ crystal The two-stage hydrothermal treatment described above is performed so that the diffraction peak becomes smaller than the synthetic peak (2θ = 19.0 to 20.5 degrees) of the smectite [020] plane and the synthetic talc [020] plane. If the synthetic talc is formed, desired effects such as improvement of the surface active effect can be ensured.

  In the present invention, when dioctahedral smectite such as bentonite or acid clay is used as the smectite clay, 2θ = 59.5 to 62.5 degrees as shown in FIG. 1 (b). In addition to the X-ray diffraction peak (2θ = 61.0 to 62.5 degrees) of the [060] plane of the dioctahedral clay mineral, the X-ray diffraction peak of the [060] plane of the trioctahedral clay mineral It is confirmed that (2θ = 59.5 to 61.5 degrees) is synthesized and expressed. That is, the expression of such a synthetic peak indicates that a low-layer synthetic talc, which is a trioctahedral three-layered clay mineral, is generated by the semi-synthetic reaction under the hydrothermal treatment in the two steps described above. Show.

  In the present invention, the above-described composite clay composition used as a cleaning agent generally comprises (A) smectite group clay mineral and (B) synthetic talc on the basis of drying at 105 ° C. (A) :( B) = 1: 2 to 1: 9, especially 1: 3 to 1: 7 in a weight ratio, and since it contains a smectite group clay mineral and a synthetic talc in such a balance, physical properties (interfaces) specific to smectite In addition to exhibiting an active action), combined with the lipophilicity and oil-absorbing properties of synthetic talc, the cleaning action by absorption, sorption and emulsification dispersion of oily substances is enhanced. Therefore, if the content ratio of the smectite group clay mineral is larger and the content ratio of the synthetic talc is smaller than the above content ratio, it can be said that the emulsification dispersibility is good, but the sorption amount of the oily substance is small and the cleaning performance is high. On the contrary, when the content ratio of smectite group clay mineral is small and the content ratio of synthetic talc is large, the sorption amount of the oily substance is increased, but the dispersibility of the oil absorption particles in the aqueous phase is deteriorated and the oil absorption particles are Since it adheres to the surface and becomes difficult to remove even by rinsing with water, it cannot be said that the cleaning property is good.

Further, such a composite clay composition is produced by converting an opal or cristobalite SiO ₂ crystal, which is intimately composited with a smectite ultrafine crystal, into a synthetic talc of an ultrafine crystal. And each fine crystal of synthetic talc is randomly dispersed, and even if it is concentrated or dried and solidified, each fine crystal does not cause further lamination, or even if it occurs, it becomes irregular and disordered laminated particles Therefore, for example, it has a considerably higher specific surface area than a simple mixture of raw smectite clay and natural talc. The BET specific surface area is 100 m ² / g or less for the mere mixture, whereas the composite clay composition used for the cleaning agent of the present invention is usually 250 m ² / g or more, particularly 250 to 500 m ^2. / G, which is extremely high, and therefore, the area of the contact interface with oil is large, and the oily substance is easily captured.

Furthermore, since this composite clay composition is converted to talc of SiO ₂ crystal by hydrothermal treatment to such an extent that the basic structure of the smectite group clay mineral is not impaired, the above-mentioned lipophilicity / oil absorption and surface activity are achieved. In addition to the above, it retains a cation exchange ability derived from smectite and properties as a solid acid, and also possesses a large amount of a solid acid having a relatively weak acid strength derived from a newly produced synthetic talc. For example, the composite clay composition has a cation exchange capacity of 5 meq / 100 g or more, particularly 10 to 50 meq / 100 g. Further, in the surface acidity distribution measured by the n-butylamine titration method, the acid strength function Ho is larger than −3.0 (indicator: dicinnamalacetone) and not more than +3.3 (indicator: p-dimethylaminoazobenzene). There are many acid points of moderate strength (-3.0 <Ho ≦ + 3.3) and relatively weak acid points in the acid strength region of +3.3 <Ho ≦ + 4.8 (indicator: methyl red). Existing. Since the acid amount (meq / g) of these solid acids varies depending on the type of smectite in the composite clay composition, the type of interlayer ions, the content ratio of smectite and synthetic talc, etc., it cannot be said unconditionally. The total acid amount is 0.5 meq / g or more, and in particular, some compositions have a large volume of solid acid of 1 meq / g or more.

(Washing soap)
The composite clay composition described above is usually used as a cleaning agent after adjusting the particle size to particles having an average particle size of about 1 to 10 μm. That is, the above-mentioned composite clay composition constituting such a detergent has a large specific surface area and pore volume, exhibits a cation exchange capacity peculiar to smectite, and is oily due to an increase in lipophilicity due to the formation of talc. It exhibits excellent detergency due to the substance absorption / adsorption action and the smectite interfacial activity (emulsification / dispersion action), and exhibits an extremely high detergency effect especially against oil stains.

  For example, FIG. 2 (a) shows that a water phase 1 and an oil phase 3 made of edible oil and fat are present in a container 10, and the water phase 1 contains the above-described composite clay composition. It is a schematic diagram which shows that the cleaning agent of invention is disperse | distributed. That is, in such an aqueous phase 1, the composite clay composition is synthesized by dispersing smectite into single-layer particles 5 (usually having a particle size of about 2 to 100 nm) due to swelling by absorbing water. Talc is divided into dispersed single-layer particles 7 (usually having a particle size of about 2 to 20 nm) and agglomerated secondary particles 9 (usually having a particle size of about 1 to 10 μm). In this state, when the container 10 is shaken to mix the aqueous phase 1 and the oil phase 3, the synthetic talc particles 7 and 9 have high affinity for oil, as schematically shown in FIG. The oil is taken in and dispersed in the oil droplet 15 (usually a particle size of about 10 to 100 μm), while the smectite particles surround the oil droplet 15 to form a hydrophilic film 17 and form one kind of protective colloid. Will be formed. The oil droplets 15 surrounded by such a hydrophilic film 17 are dispersed together with some smectite particles 5 and synthetic talc particles 7 and 9 in the aqueous phase 1 (continuous phase). In this way, the emulsion system in which the oil droplets absorbed and fixed to the composite clay composition particles are dispersed in the aqueous phase is washed away while being continuously diluted by pouring, for example, running water, and the oil phase components are removed. is there. Therefore, the cleaning agent of the present invention comprising such a composite clay composition exhibits excellent cleaning properties against oily soil.

  Further, the composite clay composition used in the present invention has the above-described cation exchange capacity and solid acid in addition to the lipophilicity / oil absorption property, and also has a high specific surface area. In addition to adsorbing basic pigments well, it also adsorbs other basic, neutral to acidic water-soluble pigments and oil-soluble pigments, and resists stains caused by pigments (colored substances) contained in dyes and foods. Even high detergency.

  Furthermore, for the same reason, the composite clay composition adsorbs basic odors such as trimethylamine and ammonia well, and neutrals such as unsaturated aliphatic compounds, aldehydes, sulfides and lower fatty acids. It also adsorbs acidic odor substances well and adheres to cooking utensils such as manita and frying pan with odorous ingredients such as fish internal organs, fish meat, livestock meat, onion and garlic. Malodorous components such as raw odor are adsorbed at the same time as oily stains, and show high cleaning power.

  Furthermore, since the cleaning agent of the present invention contains microparticles made of synthetic talc of moderate hardness that is not too hard, the function of scraping various stains without damaging the container or equipment by a soft polishing action It also has.

  Thus, the cleaning agent of the present invention comprising the above composite clay composition exhibits a high detergency against various types of dirt, and particularly has a high detergency against oily dirt. Cleaners, such as kitchen cleaners, burners around kitchen ranges, kitchen ventilation fans, etc., oil stain cleaners on kitchen floors and machine floors, cleaning agents for hands dirty with machine oil, etc. Degreasing cleaner for pre-painting equipment, degreased cleaner for various pre-dyeing fibers (fabric), hair cleaner, toothpaste, pet shampoo, outdoor oil stain cleaner, laundry detergent, automatic dishwasher detergent, food It can be suitably used as a fat / oil refining / cleaning agent, various decolorizing / cleaning agents, various deodorizing / cleaning agents, and the like. In addition, as a special use as a cleaning agent, it is possible to use the lipophilic, oil-absorbing, emulsifying and dispersing action for silver tableware and silver accessories polishing agents and resin-based oils using the soft polishing action described above. There is pitch control in the papermaking process. Furthermore, it can be used for oil absorption, fixation, and separation treatment of oils that have leaked to the sea and floated in wastewater pits of automobile repair shops and food processing plants.

The cleaning agent of the present invention, to use and dispersed in water to form a slurry or paste. When used in such form, rapidly dispersed in water in the form as shown in FIG. 2 (a), Ru der from exhibits faster cleaning effect.

  In addition, the detergent comprising the composite clay composition of the present invention can be used alone. For example, detergents for automatic dishwashers, detergents for removing scorch from cooking utensils, oils around gas ranges and range hoods It can be used in combination with alkaline carbonate detergents such as sodium bicarbonate (sodium bicarbonate) and sesquicarbonate soda that are used in detergents for removing dirt. In this case, the decolorization / deodorization effect combined with the particularly high oily soil removal effect of the composite clay composition of the present invention is due to the partial decomposition action of proteins and oils by alkali in alkaline carbonate detergents and the promotion of dissolution in starches. Deodorization (neutralization of acidic odor components) effect combined with the removal effect such as etc. is added, and it exhibits a better cleaning effect against various types of dirt.

  Therefore, the combined use of the detergent comprising the composite clay composition of the present invention and the alkali carbonate detergent such as baking soda can be used at the same time, or can be used at different times. It is extremely useful in that it is possible to provide a cleaning agent having excellent characteristics of both of the above by preparing them in advance as a homogeneous identical composition and using it as the cleaning agent of the present invention.

In the mixed cleaning agent of the present invention, in the detergent in the form of slurries or paste, depending on the mixing ratio and the water content, the alkali carbonate compounds such as premixed baking soda, the total amount Alternatively, most of them are dissolved in the aqueous phase, or partially undissolved soot or reprecipitate to form a solid phase together with the composite clay composition. The mixing ratio of the composite clay composition and the alkali carbonate-based compound may be any ratio at which the characteristics of the cleaning action can be expressed appropriately depending on the purpose of cleaning, but on the basis of 105 ° C drying of the composite clay composition. Is expressed as X, and the weight of alkali metal bicarbonate or carbonate in terms of anhydrous carbonate is expressed as Y, where X: Y = 1: 10 to 10: 1. It is preferable.

  Furthermore, the cleaning agent of the present invention includes other inorganic detergents or auxiliaries commonly used in detergents (such as synthetic aluminosilicate builders represented by Na-A zeolite), enzyme auxiliaries, bleaching. It can be used in combination with or mixed with agents, brighteners, fragrances and the like. Of course, other organic detergents (soap, synthetic organic anion / nonionic surfactants, natural saponin-containing plants, etc.) may be used in combination or mixed.

  Thus, according to the present invention, the whole is made of an inorganic substance, does not contain any harmful components to living organisms in the human body and the natural environment, has decoloring / deodorizing properties as well as lipophilic, oil-absorbing and emulsifying properties, and has high performance and high safety. We have been able to provide cleaners that are extremely gentle to the sex environment.

The superior effect of the present invention is illustrated in the following examples.
Application Example 6 is a reference example.
Various tests in the examples were performed by the following methods.
(1) Preparation of X-ray diffraction sample:
The powder sample is left as it is, and for the slurry or paste sample, the wet cake obtained by suction filtration is dried at 110 ° C. and then crushed in a mortar to form a powder. To do.
X-ray diffractometer: Rigaku Co., Ltd., MultiFlex
Measurement conditions: X-ray = Cu-Kα ray, tube voltage = 40 kV, tube current = 30 mA, divergence slit: 0.15 mm, scattering slit: 1 °, light receiving slit = 0.15 mm
Scanning range: diffraction angle (2θ) = 3 ° to 70 °

(2) Soluble Silicic Acid A clay sample (150 g) dried at 110 ° C. is dispersed in 450 g of pure water, 53.3 g of sodium hydroxide (NaOH) is added, and the mixture is heated and stirred at 100 ° C. for 5 hours. Allow to cool and measure the total weight of the dissolved reaction solution. The dissolved mother liquor is allowed to stand for 1 day or longer to allow the solid content to settle, and a transparent supernatant is collected to quantify the SiO ₂ concentration in the solution portion. The amount of SiO ₂ eluted from 100 g of the sample is obtained by calculation and used as the soluble silicic acid (%) in the sample.

(3) BET specific surface area It was measured by a so-called BET method by adsorption of nitrogen gas. In this example, measurement was performed using an automatic specific surface area measuring device (TriStar 3000, measurement method: gas adsorption method by a constant volume method) manufactured by Micromeritec.
For details on BET theory, refer to the following document.
S. Brunauer, PH Emmett, E. Teller, J. Am. Chem. Soc., Vol. 60, 309 (1938)

(4) Preparation of oily soil cleaning sample:
In any of a slurry, paste, wet cake or powder sample, water was added to adjust the solid content concentration to 5.0% by weight to obtain a fluid and homogeneous suspension. A sample is used. In addition, in the case of a powdery sample, after adding water, if necessary, it is put on a shaker or the like to form a homogeneous suspension, and further left for 1 hour or more to make a test sample.

Method for measuring oil absorption and sorption:
10.0 g of the test suspension was taken in each of the six polypropylene centrifuge tubes with screw caps (internal volume: 15 ml), and each variable (0 ml [blank], 0.05 ml, 0 ml) was added as an oily substance. .25 ml, 0.50 ml, 0.75 ml, 1.00 ml) of edible rapeseed oil (Nisshin Oilio Group Co., Ltd.) was added using a borosilicate hard glass syringe (for 2 mL), respectively. Set the centrifuge tubes (6) with lids on a constant temperature shaker (shaking incubator SI-300 manufactured by AS ONE Co., Ltd.) for 1 minute under the prescribed conditions (shaking speed: 1750 rpm, set temperature: 25 ° C.) Shake and place on a test tube stand. A small amount of each emulsified suspension is collected with a clean Komagome pipette (for 1 ml) after a predetermined time, and two drops are added to the periphery of the qualitative filter paper (No. 2). Get (6). When air-dried in the room for 6 to 24 hours and the almost circular suspension produced by dripping is solidified, a round thin flat trapezoidal mass (dry spot) made of the solid content of the suspension ) Around the filter paper, the presence or absence of translucent halo (ring) and / or exudation on the back side of the dry-spot due to the exudation of oil that could not be absorbed was confirmed by visual observation, and the saturation point (1 ) And / or saturation point (2), and the oil absorption / sorption amount is determined as a range value as in the example of the determination method shown below. Normally, it is a range value with the saturation point (1) as the upper limit, but when it is difficult to determine whether the saturation point (1) is [-] or [±], the range value with the saturation point (2) as the upper limit is set. Become. However, the state of oil absorption and sorption is not only determined as [−] in the above determination method, but also visually observe the remaining 5% suspension after being left on the test tube stand for 24 hours. It is also a necessary condition that the oil phase is clearly not separated and floated on the upper liquid surface. For example, the oil oozing halo is not clearly observed and determined as [-] in the above determination method, and the oil phase is clearly separated on the upper liquid surface by visual observation of a 5% suspension after standing for 24 hours. If it floats, it is determined that the oil / sorption saturation point has been exceeded.

Comprehensive evaluation of oily dirt cleaning performance:
The degree of oil absorption / sorption (ml / g) with respect to the oily substance obtained by the above oil absorption / sorption amount measurement and the dispersibility of the oil-absorbed particles in the water phase (water in the test tube contents after the test) It is also related to the rinsability by

Example 1
As a natural smectite clay, activated bentonite (hereinafter simply referred to as bentonite) produced by activating sub-bentonite from the A district of Shibata City, Niigata Prefecture by sodium carbonate treatment by a conventional method, drying and grinding, is used as a raw material. It was. Impurity silica in the raw clay is mostly low-crystalline silica composed of opal A to opal CT according to XRD measurement, and about 30% is contained as soluble silicic acid according to the alkali dissolution method.

<First stage reaction>
The raw material bentonite powder (adhesion moisture: 6.8%, dry matter standard ⇒ Smectite: 70%, OpalSiO ₂ : 30%) 215g (Smectite: 140g, OpalSiO ₂ : 60g) made of stainless steel with about 6kg of water 273 g (MgO: MgO: commercially available magnesium hydroxide powder (adhesion moisture: 1.6%, dry matter basis => MgO: 67%) commercially available as a first stage reaction raw material under stirring while being added to a tank (internal volume: 11 liters) 180g) was added to form a mixed slurry, and the temperature was raised while stirring, and the reaction was continued for 8 hours at 95 ° C (during the course of the reaction, the viscosity of the slurry increased due to water evaporation due to the progress of the reaction or heating) Therefore, an appropriate amount of additional water was added twice.). At this time, the crystal opal-like silica almost disappeared by XRD measurement, and a large amount of unreacted magnesium hydroxide was confirmed.

<Second stage reaction>
Next, commercially available white carbon (as a raw material for the conversion reaction (second stage reaction) of unreacted magnesium hydroxide (MgO conversion: 150 g) remaining after being added in large excess (six times the theoretical reaction amount) to talc ( = amorphous silica, water attached: 6.7%, dry basis _{⇒SiO 2: 95%) 338g (} SiO 2: 300g = theoretical reaction volume) was added, similarly to the first stage reaction, 10 at 95 ° C. The reaction was continued for a time and ended.
According to the XRD measurement, it was confirmed that unreacted magnesium hydroxide was not substantially present and that the conditions of claims 1, 4, 5, and 6 were satisfied.
Moreover, as a result of measuring the BET specific surface area, it had a specific surface area of 370 m ² / g. The specific surface area of the starting bentonite powder was 104 m ² / g.
Thus, a cleaning agent comprising a paste-like composite clay composition containing a smectite group clay mineral and synthetic talc in a weight ratio of 1: 4 was obtained. Table 3 shows the results of the oily soil detergency test for the pasty composition (solid content concentration: 11.9%, pH: 8.7).

Measurement of oil absorption and sorption on other oily substances:
The pasty composite clay composition obtained in Example 1 was measured using “liquid paraffin” or “silicone oil” instead of “edible rapeseed oil” as an oily substance in the method for measuring oil absorption and sorption amount. The results are shown in Table 2 below.

Compared with the amount of oil absorption / sorption (1.0 to 1.5 ml / g) for “edible rapeseed oil”, the amount of oil absorption / sorption for “liquid paraffin” and “silicone oil” is 0.5- It was measured as 1.0 ml / g.
From this, the composite clay composition according to Example 1 of the present invention is slightly polar even in the presence of water, which is mostly fatty acid tri-glyceride and contains a small amount of fatty acid and mono- or di-glyceride. It shows an extremely high oil absorption and sorption amount of 1.0 to 1.5 ml / g for ordinary edible oils and fats, which are oily substances, and is almost non-polar oily substances and petroleum and synthetic silicone oils. However, it has an oil absorption / sorption amount of 0.5 to 1.0 ml / g, has a high lipophilicity / absorbency for a wide range of oily substances, and also has a surface-active effect due to smectite, a composite component. Therefore, it is evaluated that it exhibits excellent detergency against various oily soils.
In addition, the 5% suspension after standing for 24 hours used for the measurement of the oil absorption and sorption amount in this example is because the smectite component particles and the synthetic talc component particles are not simply mixed but combined. In addition, it was found that the two types of components did not segregate and settled and the dispersion stability was maintained high even when the viscosity was lowered by dilution, and the paste was suitable for use.

(Example 2)
In Example 1, the conditions of the first stage reaction and the second stage reaction were changed as follows.

<First stage reaction>
18.3 g (Smectite: 12.0 g, OpalSiO ₂ : 5.1 g) of raw material bentonite powder (adhered moisture: 6.8%, dry matter basis => Smectite: 70%, OpalSiO ₂ : 30%), about 260 g of water In a hard glass beaker (inner volume: 500 mL), and commercially available magnesium hydroxide powder as a first-stage reaction raw material with stirring (adhesion moisture: 1.6%, dry matter standard⇒MgO: 67% ) 11.7 g (MgO: 7.7 g) was added to form a mixed slurry. The temperature was raised while stirring and the reaction was continued at 95 ° C. for 8 hours.

<Second stage reaction>
Next, commercially available white carbon (= amorphous silica) is used as a raw material for the conversion reaction (second stage reaction) of unreacted magnesium hydroxide that has been added in large excess (about three times the theoretical reaction amount) to the remaining unreacted magnesium hydroxide. , Adhesion moisture: 6.7%, dry matter basis => SiO ₂ : 95%) 11.6 g (SiO ₂ : 10.3 g = theoretical reaction amount) was added, and at 95 ° C. for 8 hours as in the first stage reaction. (10 hours in Example 1) The reaction was continued and finished.

According to the XRD measurement, there is substantially no unreacted magnesium hydroxide, the diffraction peaks derived from the [001] plane of smectite and the [001] plane of synthetic talc disappear, and the SiO2 of opal or cristobalite. The intensity of the X-ray diffraction peak due to the [111] plane of the _two crystals is smaller than the intensity of the synthetic peak due to the [020] plane of smectite and the [020] plane of synthetic talc, and [060] of the dioctahedral clay mineral. It was confirmed that the X-ray diffraction peak due to the plane and the X-ray diffraction peak due to the [060] plane of the trioctahedral clay mineral were synthesized and expressed .

(Example 3)
In Example 1, the conditions of the first stage reaction and the second stage reaction were changed as follows.

<First stage reaction>
The raw material bentonite powder (adhesion moisture: 6.8%, dry matter standard => Smectite: 70%, OpalSiO ₂ : 30%) 5.5g (Smectite: 3.6g, OpalSiO ₂ : 1.54g), about 260g of water In addition to a hard glass beaker (internal volume: 1 L), a commercially available magnesium hydroxide powder as a first stage reaction raw material under stirring (adhesion moisture: 1.6%, dry matter standard ⇒ MgO: 67%) 15.6 g (MgO: 10.3 g) was added to form a mixed slurry. The mixture was heated with heating while stirring, and the reaction was continued at 95 ° C. for 8 hours.

<Second stage reaction>
Next, commercially available white carbon (= amorphous silica) is used as a raw material for the conversion reaction (second stage reaction) of unreacted magnesium hydroxide remaining after adding a large excess (approximately 134 times the theoretical reaction amount) to talc. , Adhesion moisture: 6.7%, dry matter basis => SiO ₂ : 95%) 338 g (SiO ₂ : 19.1 g = theoretical reaction amount) was added, and at 95 ° C. for 8 hours (implementation as in the first stage reaction) In Example 1, the reaction was continued for 10 hours.

According to the XRD measurement, unreacted amorphous silica and magnesium hydroxide remain, but it was confirmed that the conditions of claims 1, 4 and 6 were satisfied.
As a result of measuring the BET specific surface area, it had a specific surface area of 250 m ² / g.
It should be noted that although a large amount of synthetic talc (SA = 550 to 650 m ² / g) component having a large specific surface area is contained, it is not so much that the unreacted component remains. It is thought that there is.
Thus, a detergent comprising a paste-like composite clay composition containing smectite group clay mineral and synthetic talc (including unreacted components) in a weight ratio of about 1: 9 was obtained. Table 1 shows the results of the oily soil detergency test for the pasty composition (solid content concentration: 13.0%, pH: 8.8).

(Comparative Example 1)
21.5 g of bentonite powder (Smectite: 14 g, opalSiO ₂ : 6 g) used as a raw material in Example 1 was added to a stainless steel beaker filled with 550 g of water, and the raw material of the first stage reaction of Example 1 was stirred. Commercially available industrial magnesium hydroxide powder 27.3 g (MgO: 18 g) used as a starting material and 33.8 g of commercially available white carbon (SiO ₂ : 30 g) used as a raw material for the second stage reaction of Example 1, A composition obtained in Example 1 by stirring for 1 hour without heating so as not to substantially convert the silica component and the magnesia component into a synthetic talc, and by adding the smectite group clay mineral component and the silica / magnesia component. The slurry-like mixed composition containing the same weight ratio (1: 4) was obtained. Table 3 shows the results of the oily soil detergency test on the slurry composition (solid content concentration: 13.5%, pH: 9.7).

(Comparative Example 2)
Add 21.5 g of bentonite powder (Smectite: 14 g, opalSiO ₂ : 6 g) used as a raw material in Examples 1 to 3 to a stainless steel beaker filled with 245 g of water, and stir and disperse over 1 hour. A clay slurry was obtained. Table 3 shows the results of the oily soil detergency test for the clay slurry (solid content concentration: 7.4%, pH: 9.7).

(Comparative Example 3)
10.7 g (Smectite: 7 g, opalSiO ₂ : 3 g) of bentonite powder (adhesive moisture: 6.8%, dry matter basis => Smectite: 70%, opalSiO ₂ : 30%) used as a raw material in Example 1 275 g of water In addition to a glass wide-mouthed bottle (with screw lid), tightly close the lid, shake well, leave it for 2 hours to swell, and then synthesize synthetic talc powder (adhesion moisture: (10.0%) 31.1 g was added and stirred for 1 hour to obtain a paste-like mixed clay composition containing smectite group clay mineral and synthetic talc in a weight ratio of 1: 4. Table 1 shows the results of the oily soil detergency test for the pasty composition (solid content concentration: 11.9%, pH: 8.6). However, in the oil absorption / sorption amount test of this example, no oil oozes out to the surrounding filter paper and no halo was clearly observed. Although the cause is unknown, on the other hand, when the 5% suspension after standing for 24 hours was visually observed, Run No. In 4 and later, since it was observed that the oil phase separated from the suspended aqueous phase and floated at the top of the liquid, the oil absorption / sorption amount of this example was determined to be 0.5 to 1.0 ml / g. . In addition, the 5% suspension after standing for 24 hours used for the measurement of oil absorption and sorption amount in this example has components that seem to be synthetic talc particles segregated and settled and separated in the lower part. It was found to be a paste with reduced stability.

Separate preparation of synthetic talc powder:
Commercially available white carbon (water attached: 6.7%, dry basis _{⇒SiO 2: 95%) 406g (} SiO 2: 360g) stainless steel tank filled with water to about 6 kg (internal volume: 11L) was added purse While stirring, add 273 g (MgO: 180 g) of commercially available magnesium hydroxide powder for commercial use (adhesion moisture: 1.6%, dry matter standard => MgO: 67%) to make a mixed slurry. Then, the reaction was continued at 95 ° C. for 8 hours (when the viscosity of the slurry increased due to the progress of the reaction or transpiration of water due to heating, which hindered stirring), an appropriate amount of additional water was added). After completion of the reaction, the mother liquor slurry was separated into solid and liquid by suction filtration, and the filter cake was put in a box-type electric dryer and dried at 110 ° C. The dried cake was pulverized with a small impact pulverizer (a sample mill manufactured by Fuji Electric Industry Co., Ltd.) to obtain the desired synthetic talc powder. As a result of measuring the BET specific surface area, this product had a specific surface area of 598 m ² / g.

(Application Example 1)
The pasty composite clay composition obtained in Example 1 was subjected to a practical test as a dishwashing detergent.
A ceramic dish (diameter: 20cm) that was simmered with pork and stir-fried after meals, and after the uneaten food was thrown away, a large amount of oil stains were washed away with running water. About 20 g of a product (paste-like composition) was placed. From there, apply a dishwashing sponge (unused product) that has been squeezed out with water after it has been soaked in water, and the oil and paste are mixed well while applying the paste evenly to the entire surface of the dish. I did it. Immediately to several minutes later, when rinsed with running water, it was observed that the entire surface of the dish was completely wet with water and almost no oil remained. Dirt was hardly observed on the surface of the dish after drying, showing excellent performance as a dishwashing detergent.

(Application Example 2)
The pasty composite clay composition obtained in Example 1 was subjected to a practical test as a detergent for cooking utensils.
After cooking cooked pork-fried vegetables on a cooking plate, a frying pan that was wiped with a lot of oil that had adhered to it was defatted completely, including the oil and fat that had been stuck in the past. About 50 g of this product (paste-like composition) was placed on the center of the frying pan. After that, soaked in water and applied a dishwashing sponge that was squeezed out by hand, and spread the paste evenly over the entire surface of the bread so that the oil and paste were mixed well. Immediately to several minutes later, it was observed that almost no oil remained when rinsed with running water. Dirt was hardly observed on the surface of the bread after drying, and it showed excellent performance as a detergent for cooking utensils.

(Application Example 3)
The paste-like composite clay composition obtained in Example 1 was subjected to a practical test as a manita and a hand cleaner.
On top of that, it was carried out for the purpose of washing the resin manaita after craving 5 sardines (raw fish). About 50 g of this product (paste-like composition) was placed on the center portion of the same manita. From there, apply a dishwashing sponge that has been squeezed out of water by hand, and apply oil to the entire surface of the manita so that the paste is evenly swirled. Things and paste were mixed well. A few minutes later, when rinsed with running water, it was observed that almost no oil remained. The unique sardine of the sardine was also deodorized, and even if the nose was brought close to the surface of Manita, it almost did not smell. If you have a fish body in cooking and leave it unpleasant with oily dirt, apply this paste (approx. 20 g) evenly with both hands and rinse it with running water and rinse it with running water. Oil stains were also removed. Further, when the paste (about 10 g) was evenly applied to the entire surface of the blade and handle portion of the blade knife used for cooking and rinsed with running water several minutes later, the raw odor almost disappeared. Thus, this product showed excellent performance as a cleaning agent for manitas and fingers.

(Application Example 4)
About the paste-like composite clay composition obtained in Example 1, 84 g of sodium bicarbonate (sodium bicarbonate, reagent grade, purity: 99.5 to 100.3%) was added to a practical test as a cleanser for cleaning the kitchen around the range. I did it.
The purpose was to remove oily dirt (cured oil film) on the cooking table floor around the range where the fats and oils scattered during cooking of conventional fried foods and fried foods were oxidized and polymerized to form a film. This product has a sticky feeling when boiled with a finger and is in the center of a circular area with a diameter of about 10 cm, which is close to the range of a stainless steel cooker covered with a light grayish brown hardened oil film. About 20 g was placed. On top of that, we put a commercially available cooking paper (kitchen towel, 210mm x 220mm / 2 layers) into four folds, and applied the paste to the circular area so that the paste was evenly swirled. . Immediately or a few minutes later, wipe off the oily soil paste several times with a towel cloth that has been squeezed and lightly squeezed once. Finally, wash it with water several times to clean it. Wipe clean with a clean bedcloth. After that, in the circular area, the light brown oily dirt almost disappears, compared to the area stained with the surrounding hardened oil film, a clean stainless steel background appears, and even when touched with a finger, there is a feeling of stickiness due to oil I couldn't. In addition, there were no scratches on the metal surface of the ground that were thought to have been newly made other than the conventional fine scratches. As described above, this product showed excellent performance as a cleanser for cleaning a cooking table around a range to which a polymerized oil adhered with high viscosity.

(Application Example 5)
The paste-like composite clay composition obtained in Example 1 was added with 10 g of sodium bicarbonate (sodium bicarbonate, reagent grade, purity: 99.5 to 100.3%) and subjected to a practical test as a detergent for a bedcloth.
After spilling the spilled Chinese dish (maki tofu) with a lot of oil on the table, wipe it with a white towel cloth that has been wrung out and then wrung out. I squeezed it tightly. When I spread the bedcloth by hand, there was no solid stain, but there was a strong odor mainly consisting of oil stains containing a slightly red pigment from the ingredients and garlic odor, and it was also sticky in my hands The unpleasant feel that remained. Put about 20 g of this product (baking soda-containing paste-like composition) on the center of the spread cloth, and swab the entire cloth with both hands so that the paste or slurry-like product enters the gaps between the fabric fibers. Rubbed together. Once the water was rinsed and wrung out, the same operation was repeated once more. Finally, after rinsing with water and squeezing it tightly, no oil stains were felt even when touching the cloth, and no unpleasant touch that was sticky on the hands remained. Moreover, neither the cloth width nor the hand had a strong odor before washing, and the food odor mixed with the garlic odor was slightly felt. As described above, this product showed practically sufficient performance even when used for cleaning the bedcloth width.

(Application Example 6)
The pasty composite clay composition obtained in Example 1 was subjected to a practical test for cooking paper (kitchen paper).
A commercially available sheet of cooking paper (cooking paper, 275 × 240 mm) is placed on a glass plate, and the paste-like composite clay composition of Example 1 is diluted with water to form a fluid slurry (solid content concentration: 9. 7%) and coated on the sheet using a coating rod (wire bar). After air-drying indoors, the coated surface was cut as homogeneously as possible to obtain four composite clay composition coating sheets (60 × 60 mm, coating amount: about 50 g / m ² ). At this time, on the coated surface, the composite clay component was not only applied in a slightly thicker layer on the upper surface of the sheet, but also penetrated into the entire interior reaching the back surface of the sheet. Two sheets of the pre-coating cooking paper for comparison with the one (A set, double sheet) where one sheet of the pre-coating (cooking paper) is placed on top of the other side of the coated sheet turned upside down. Two sets of stacked (B set, double sheet) were prepared.

<Test for fried dishes>
When edible rapeseed oil (slight yellow) was dropped from the 1 mL Komagome pipette on each double sheet of both sets, the oil absorption area in the A set spread in a large circle in the horizontal two-dimensional direction as it was dropped. It was difficult to reach the second lower sheet, and a small oil absorption point finally appeared on the back of the lower sheet when 10 drops (0.25 ml) were dropped. On the other hand, in the case of set B, 1 drop (0.025 ml) was dropped, and when seen from above, it became a small circular spot that did not spread much in the horizontal direction but spread in the 3D direction. The oil absorption point appeared to the back of the lower sheet and the penetration of the oil reached the back of the double sheet. In addition, the other uncoated sheet (cooking paper) is placed on each double set of both sets, and each of them is the same as A ′ set / triple sheet and B ′ set / triple sheet. As a result of the test, even if 10 drops (0.25 ml) were dropped on the A ′ set, the oil did not penetrate to the back of the bottom third sheet, and 1 drop (0.025 ml) on the B ′ set. ) Reached the surface layer of the lowermost third sheet, and it was found that the oil penetrated to the back of the sheet when 2 drops (0.05 ml) were dropped.

<Test for thawing ingredients for laying paper>
Frozen tuna fillets (red meat, 3 pieces, 50 x 50 x 10 mm) are placed in three dishes (φ90 mm) one by one as drip (liquid juice) that exudes from the thawed food and left at room temperature for about 6 hours The drips that had oozed out were collected (about 1 ml) and diluted 3 times with water to prepare about 3 ml of a test drip solution.
When the drip liquid (light reddish brown) is dropped from the Komagome pipette (for 1 ml) onto the double sheets of both sets, the liquid absorption area in A set becomes larger and circular in the horizontal two-dimensional direction as it is dropped. Since it spreads and is absorbed and absorbed by the coating layer, it is difficult to reach the second sheet below. When 5 drops (0.1 ml) are dropped, a small liquid absorption point finally appears on the back of the lower sheet. It was. On the other hand, in the case of set B, when one drop (0.02 ml) was dropped, it became a small circular spot when viewed from above, and it did not spread much in the horizontal direction but spread in the same way in the three-dimensional direction. It was also found that the drip solution penetrated to the back of the sheet by dropping 2 drops (0.04 ml).
From the two test results, the cooking paper of this application example was evaluated as highly practical as a fried food laying paper or a thawing food laying paper.

(Application Example 7)
The pasty composite clay composition obtained in Example 1 was subjected to a practical test as a hair shampoo.
Three days after normal shampooing with a commercially available shampoo, about 30 g of this product (paste-like composition) was spread over the entire hair, and then thoroughly rinsed by hand in the same way as normal shampooing. After pouring water once, wash with the same paste using about 30 g of this paste-like composition, rinse well with watering by shower, wipe well with a dry towel, and then use a hair dryer. I dried my hair. After washing the hair according to this example, even if the hair is sandwiched with tissue paper, for example, translucency of the paper contact part due to the transfer of sebum is not seen, and it is understood that the scalp and hair are well-greased However, the moisturizing effect of the smectite component did not cause the hair to feel dry. Finally, when the hair was toned using a hair tonic, the result was the same as usual. Thus, this product not only has practically sufficient performance as a hair shampoo, but also contains no organic compound components (such as organic surfactants) that have a large environmental load. It was highly evaluated as a hair shampoo and body shampoo for outdoor activities such as camping.

(Application Example 8)
The pasty composite clay composition obtained in Example 1 was subjected to a practical test as a pet body shampoo.
About 150g of this product (paste-like composition) for small indoor breeding dogs (dog type: Shih Tzu, sex: male, age: 10 years old) 7 days after normal shampooing with commercially available shampoo for pets Was applied over the entire body and the four legs behind the shoulders, and then thoroughly washed by hand (about 2 minutes) in the same manner as normal shampoo. Then, it rinsed well with the watering by the shower, and after wiping off well with the dry towel, the hair was dried with the hair dryer. After washing according to this example, the body hair on the back of the body and legs (washed part) has no stickiness due to sebum, compared to the area around the head and neck (unwashed part) that was not intentionally washed for comparison. When touched by hand, it was finished with a plump feel. By the way, even when rubbing strongly with tissue paper on the body hair at the washing site, translucency of the paper contact part due to transfer of sebum was not seen, and it was found that the hair was greasy well, but smectite component Because of the moisturizing effect by the hair, there was no feeling of looseness of the hair and the gloss of the hair was also good. In addition, the body odor peculiar to dog breeds that remained strongly in the non-cleaning part was deodorized in the non-cleaning part and diluted to a slight odor. Thus, this product not only has practically sufficient performance as a pet shampoo, but also does not contain any organic compound components (such as organic surfactants) that may cause an allergic reaction to the pet's skin. Therefore, it was evaluated as extremely useful as a highly safe shampoo for pets.

(Application Example 9)
The paste-like composite clay composition obtained in Example 1 was subjected to a practical test as a toothpaste cleaning agent.
In this example, this paste-like composition is used for the purpose of removing fats and fine starchy plaque remaining in the mouth and teeth and gums even if the mouth is sprinkled with water after eating tonkatsu rice in a meal. About 5 g was taken on a toothbrush and brushed for 2 minutes in the usual way. Once you rub your mouth with water, use about 5 g of this paste to polish it for 1 minute in the same way, and rub your mouth cleanly with about 180 ml of water, leaving it in your mouth compared to before eating after eating. There was no greasy feeling and a refreshing feel. Further, when the surface of the tooth was touched with an index finger, it was wet with moisture, and no residual fat or debris was found even when enlarged with a concave mirror.

(Application Example 10)
The pasty composite clay composition obtained in Example 1 was subjected to a practical test as a cleaning agent for removing machine oil stains.
Simulate oil stains on fingers after work such as machine repairs, drop about 0.5 ml of machine oil (mineral oil-based lubricant) from the Komagome pipette to the palm of your left hand and slide the palms of both hands together. After spreading over the whole, about 20 g of this paste-like composite clay composition was placed on the palm of one hand, and then rubbed so that both fingers were evenly entangled with each other, so that the oil and paste were well mixed. Rinse once with running water, repeat the same operation using about 20 g of this paste again, rinse with a large amount of running water, and the entire surface of both palms and back will be wet without showing water repellency It was observed that almost no oil remained. In addition, from the touch of the fingers, there was no stickiness due to oil stains, and the fingers were washed clean and returned to their original clean state. Thus, this product showed practically sufficient performance even when used as a cleaning agent for removing machine oil stains.

(Application Example 11)
The pasty composite clay composition obtained in Example 1 was subjected to a practical test as a cleaning agent for experimental instruments.
About 10 g of this product (paste-like composition) is put in a borosilicate glass test tube (φ21 x 200 mm) with a large amount of oil on the inner wall used in experiments using edible oil (soybean oil), and a test tube brush The operation of rubbing the inner wall and the outer wall of the tube evenly using was repeated to mix the oil and paste well. When rinsing the inside and outside of the tube with a large amount of running water, it was observed that the entire surface of the tube was completely wetted with water and no oil remained. Dirt was hardly observed on the inner and outer surfaces of the test tube after drying, and it showed excellent performance as a cleaning agent for laboratory instruments.

It is a figure which shows the X-ray-diffraction pattern of the bentonite (a) of the natural smectite type clay used as a raw material in Example 1, and the obtained composite clay composition (b). It is a figure for demonstrating the cleaning power with respect to the oil stain of the cleaning agent of this invention.

Claims (6)

(A) A composite clay composition comprising a smectite group clay mineral and (B) a synthetic talc, and in X-ray diffraction measurement, diffraction peaks derived from the [001] plane of smectite and the [001] plane of synthetic talc Containing a composite clay composition that has substantially disappeared,
The composite clay composition has a BET specific surface area of 250 m ² / g or more, has a slurry or paste form, and further has a solid content concentration of the composite clay composition on a 105 ° C. dry basis. In the range of more than 5% by weight and not more than 50% by weight .   The composite clay composition contains (A) smectite group clay mineral and (B) synthetic talc in a weight ratio of (A) :( B) = 1: 2 to 1: 9 on a 105 ° C. dry basis. The cleaning agent according to claim 1.   The cleaning agent according to claim 1 or 2, further comprising an alkali metal bicarbonate or carbonate. In the X-ray diffraction measurement of the composite clay composition, the intensity of the X-ray diffraction peak due to the [111] plane of the SiO ₂ crystal of opal or cristobalite is synthesized from the [020] plane of smectite and the [020] plane of synthetic talc. The cleaning agent according to any one of claims 1 to 3, wherein the cleaning agent is smaller than the peak intensity. The cleaning according to any one of claims 1 to 4, wherein in the composite clay composition, the X-ray diffraction peak due to the [111] plane of the SiO ₂ crystal of opal or cristobalite is substantially lost in X-ray diffraction measurement. Agent.   (A) The smectite group clay mineral is dioctahedral smectite, and in X-ray diffraction measurement, the X-ray diffraction peak of the [060] plane of the dioctahedral clay mineral and the X-ray of the [060] plane of the trioctahedral clay mineral The cleaning agent according to any one of claims 1 to 5, wherein the diffraction peak is synthesized and expressed.

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