JPH11106786A - Amorphous builder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amorphous builder having low water content, excellent cation exchange ability, high alkali buffering ability, excellent moisture absorption resistance, useful as a builder for detergents, and the amorphous builder. To provide a cleaning composition containing a quality builder. The general formula of the anhydride is xSiO ₂ · yM ₂ O · zMemOn (where M is an element of Group Ia of the periodic table, and Me is II of the periodic table.
a, IVa, IIb, IIIb, Vb or VIII group element;
x / y = 1.0-2.0, z / x = 0.001-1.
0, n / m = 1 to 2.5), and a detergent composition comprising the amorphous builder having a water content of 8% by weight or less and the amorphous builder. Stuff.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an amorphous builder which is excellent as a builder for detergents and has excellent cation exchange ability, high alkali buffering ability, and excellent storage stability. Agent composition.

[0002]

2. Description of the Related Art It has been known that amorphous silicates can be used as builders for detergents. Many of the amorphous silicates have a SiO ₂ / Na ₂ O (molar ratio) of 2
And water glass having a solids content of about 30 to 50% by weight. When the amorphous silicate is used as a detergent builder, it is made into a water slurry together with other detergent components, and is then made into a powder detergent by spray drying.

[0003] Powdered waterglass obtained by spray-drying the above waterglass is also used as a detergent formulation, but they have a water content of 15 to 25% by weight and have associated water.

However, the water glass or the powdered water glass has a water softening property, but has a low solid content and a high solubility in water as compared with other detergent builders. At this time, the captured Ca ions and Mg ions are liable to be eluted into water again, resulting in low water softening properties, and low alkali buffer capacity due to low solid content. In particular, when the powdered water glass is stored under high humidity, there is a disadvantage that the powdered water glass easily changes to a water glass-like highly viscous form because of high hygroscopicity.

A builder based on water glass is disclosed in Japanese Patent Application Laid-Open No. 4-275400.
The builder agent contains 30 silicon atoms in Q ₂ and Q ₃ forms.
By using water glass containing not less than 10% by weight, the cation exchange ability is improved. However, the solid content of the builder agent is as small as 10 to 60% by weight, and the amount of components effective for cation exchange is small. In addition, since water glass is sometimes adsorbed or absorbed by an inorganic carrier, the amount of the active ingredient is further reduced. Further, the builder disclosed in JP-A-6-184593 also has a disadvantage that the amount of the active ingredient is small because it contains water similarly to the above.

On the other hand, water-free amorphous silicates are disclosed in
It is disclosed in JP-A-8-26717. This is Si
O_Two/ Na_TwoCures having O (molar ratio) of 1.2 to 1.6
Crushed and used as a builder
You. However, the SiO _Two/ Na_TwoO (molar ratio)
When producing a cullet having a value of 1.2 to 1.6,
Because of the high alkalinity of the molten cullet,
Load is large, manufacturing is difficult and cullet S
iO_Two/ Na_TwoStorage under high humidity due to low O (molar ratio)
High moisture absorption, like water glass like dry water glass
Has the disadvantage of easily changing to a highly viscous form of
You. Therefore, as a method to improve such disadvantages, amorphous
Japanese Patent Laid-Open No. 8-2 discloses a method for bringing carbon dioxide gas into contact with porous silicate.
No. 25317, but neutralized with acid gas
The alkali buffering capacity of the amorphous silicate,
There is a disadvantage that the cation exchange capacity is reduced.

[0007]

SUMMARY OF THE INVENTION The inorganic builder of the present invention has been made in view of the above prior art, and has a low water content, an excellent cation exchange capacity, a high alkali buffer capacity, and a moisture absorption resistance. An object of the present invention is to provide an amorphous builder having excellent properties and useful as a builder for detergents, and a detergent composition containing the amorphous builder.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on the builder performance of amorphous silicate, and as a result,
We have found a completely new fact that a novel amorphous builder having a specific composition has excellent cation exchange ability, high alkali buffering ability, and excellent moisture absorption resistance. The present invention has been completed based on this fact.

That is, the gist of the present invention is that (1) the general formula of an anhydride is: xSiO ₂ .yM ₂ O.zMemOn (where M is an element of Group Ia of the periodic table, and Me is II of the periodic table)
a, IVa, IIb, IIIb, Vb or VIII group element;
x / y = 1.0-2.0, z / x = 0.001-1.
0, n / m = 1 to 2.5) and an amorphous builder having a water content of 8% by weight or less. (2) Measurement using a Raman spectrophotometer (wavelength 1064 nm) , The shift peak of 970 ± 20 cm ⁻¹ / 1070 ±
The amorphous builder according to the above (1), wherein the area ratio of the shift peak at 30 cm ^-1 is 0.05 to 6, (3) M is N
a, the amorphous builder according to (1) or (2), wherein Me is Ca; (4) the amorphous builder according to (1) or (2), wherein M is Na and Me is Ca and / or P; Crystalline builder, (5) M′pCO _{3 with} respect to 100 parts by weight of the amorphous builder according to any one of the above (1) to (4).
And / or M'pSO ₄ (wherein, M 'is Na, K, Ca
Or an amorphous builder containing 1 to 75 parts by weight of Mg and p represents 1 or 2).
To (5) an amorphous builder further comprising 1 to 50 parts by weight of sodium metasilicate with respect to 100 parts by weight of the amorphous builder described in any of (1) to (5), (7) an oil absorption capacity of 20 to
The amorphous builder according to any one of the above (1) to (6), which is 300 mL / 100 g, and (8) the above (1).
A cleaning composition comprising the amorphous builder according to any one of (1) to (7).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The amorphous builder according to the present invention has a general formula of an anhydride of xSiO ₂ · yM ₂ O · zMemOn (where M is an element of Group Ia of the periodic table, and Me is an element of the periodic table). II
a, IVa, IIb, IIIb, Vb or VIII group element;
x / y = 1.0-2.0, z / x = 0.001-1.
0, n / m = 1 to 2.5) and has a water content of 8% by weight or less.

In the above general formula, M is Li, Na, K
And the like, selected from the group Ia elements of the periodic table, among which there is no particular limitation, but Na is preferred from the viewpoint of cation exchange capacity.
Group Ia elements of the periodic table such as Li, Na, and K are used alone or
More than one species may be mixed to form the M component. When stored under high humidity or when the amorphous builder of the present invention is added to water for use as a builder, the M component ion-exchanges with H ⁺ of a water molecule,
Some or all of the components may be H.

In the above general formula, Me is represented by II in the periodic table.
a, IVa, IIb, IIIb, Vb and VIII elements. Specifically, Mg, Ca, Ti, Zr, Zn,
Examples thereof include B, Al, N, P, and Fe, and are not particularly limited. Among them, Mg, Ca, and P are preferable from the viewpoint of cation exchange ability and storage stability. The elements can be used alone or in combination of two or more.

In the above general formula, x / y (molar ratio) is
It is desirably 1.0 or more, preferably 1.2 or more from the viewpoint of cation exchange ability and storage stability, and 2.0 or less, preferably 1.8 or less from the viewpoint of cation exchange ability and alkali buffering ability. It is desirable that

In the above general formula, z / x (molar ratio) is
From the viewpoint of preventing storage stability under high humidity from being significantly reduced, it is 0.001 or more, preferably 0.003 or more, and more preferably 0.01 or more. Z / x (molar ratio) is 1.0 or less, preferably 0.8 or less, and more preferably 0.5 or less from the viewpoint of preventing a decrease in solubility in water and a decrease in alkali buffering ability. More preferably, there is.

In the above general formula, n / m (molar ratio) is
It is determined by the combination of Me and O, and is in the range of 1 to 2.5.

Here, the cation exchange ability is exhibited by the ion exchange action between the alkali metal ions in the amorphous builder of the present invention and Ca or Mg ions in water. Therefore, when x / y (molar ratio) is smaller than 1.0, the Si silicate having a structure in which negatively charged silicate ions and positively charged alkali metal ions are electrically balanced. The strength of the -O-Si network structure is reduced,
Ca or Mg ions trapped by silicate ions are eluted into water again due to hydrolysis by water, and the cation exchange capacity is reduced. Further, the hygroscopic resistance is reduced due to the decrease in the network strength, and the storage stability is reduced. Decrease. When x / y (molar ratio) exceeds 2.0, exchangeable alkali metal ions decrease, so that the water softening ability decreases.

The storage stability is determined from a change in shape due to moisture absorption when stored under high humidity.
Even when stored under high humidity, those that hardly change to a viscous form like water glass are judged to have high storage stability.

In addition, when the amorphous builder of the present invention is dissolved in water, the alkali metal ions dissolve into water and the aqueous solution shows alkalinity. Expresses alkaline buffering capacity.
The amorphous builder in the range of x / y = 1.0 to 2.0 in the general formula of the present invention is suitable as a builder for detergents because a sufficient amount of alkali metal ions expressing alkali buffering capacity is present. A high alkaline buffering capacity.

The amorphous builder of the present invention has a halo peak at 2θ = 10 to 50 ° in X-ray diffraction. The X-ray diffraction was carried out using an X-ray diffractometer (Model RAD-200, manufactured by Rigaku Denki Co., Ltd.) under the conditions of Cuk α-ray, 40 kV, and 120 mA.
An amorphous builder may be used as long as it has a peak of cps or more.

[0020] The amorphous builder of the present invention may contain water. The water content of the amorphous builder is 8% by weight from the viewpoint of preventing a decrease in solid content, preventing a decrease in cation exchange capacity and alkali buffering ability, and further preventing a decrease in storage stability in high humidity storage. %, Preferably 4% by weight or less.

The amorphous builder of the present invention comprises Q ₂ and Q ₃
It preferably has a silicate ion network structure.

The silicate ion network is represented by Qn
(N = 0 to 4), and the number n is the number of Si-
Shows the number of associations by O-Si bond. Specifically, when n = 3 in the above Qn, Q ₃ has three Si atoms associated by a Si—O—Si bond and the other one is a non-crosslinked Si—OM (M is an alkali). 2) having a metal) bond
Represents a silicate with a three-dimensional network structure. In the case of n = 2 in the Qn is, Q ₂ is two Si atoms are associated by Si-O-Si bond, but the remaining two represent a silicate of one-dimensional network structure having a non-cross-linked.

The silicate ion network is closely related to the strength of the structure of the polysilicate ion, and this has a great influence on the cation exchange capacity, alkali buffer capacity, and storage stability under high humidity.

In the above-mentioned Qn, when the number n is 3 or more, the silicate ion network has a high dimension and is strongly bonded. Thus Q ₃ or more silicates hardly hydrolyzed, but high storage stability. However, non-crosslinked Si—O—M bonded to alkali metal ions
(M is an alkali metal) Since the number of bonds decreases, water softening ability and alkali ability decrease.

In the case of Qn, when the number n is 2 or less, the silicate ion network structure becomes weak, so that the storage stability and the cation exchange ability are reduced.
Therefore, the structure of the amorphous builder of the present invention having the Q ₂ and Q ₃ forms at a predetermined ratio is excellent as a builder for detergents because it has excellent storage stability and water softening properties in a well-balanced manner.

The above Q_TwoAnd Q_ThreeForm ratio (Q_Two/ Q_Three)
Can be determined by Raman spectroscopy. Ingredient
Physically, Raman spectrophotometer (made by SPEX Co., Ltd., mold
Formula: Triplemate, Excitation light: Argon ion beam
Laser, wavelength 1064 nm, detector: CCD detector)
When the amorphous builder of the present invention was measured, it was 970 ±
20cm^-1Q near_TwoAnd a shift peak of 107 was obtained.
0 ± 30cm^-1Q near _ThreeIs obtained.
The Q_TwoShift peak and Q_ThreeArea ratio of the shift peak
By calculating, Q_Two/ Q_ThreeCan be measured
You.

Q ₂ / Q of the amorphous builder of the present invention
₃ is 0.1 from the viewpoint of cation exchange capacity and alkali buffer capacity.
It is desirably at least 05, preferably at least 0.2, and desirably at most 6, preferably at most 4, from the viewpoint of cation exchange capacity and storage stability.

The amorphous builder according to the present invention comprises M ′
pCO ₃ , M′pSO ₄ (where M ′ is Na, K, Ca
Or p represents 1 or 2), sodium metasilicate, or the like. As M '
Although not particularly limited, N is preferable in terms of storage stability.
a, Ca and Mg are preferred. These can be used alone or in combination of two or more to constitute the M ′ component.

The above-mentioned M'pC
When O ₃ and / or M′pSO ₄ is further contained, storage stability is further increased by adding 1 to 75 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the amorphous builder. Performance can be improved. That is, from the viewpoint of improving storage stability, M′pCO ₃ and / or M′pSO ₄ is preferably 1 part by weight or more based on 100 parts by weight of the amorphous builder.
From the viewpoint of cation exchange ability, the amount is preferably 75 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the amorphous builder.

Further, the amorphous builder according to the present invention or the aforementioned
M'pCO_ThreeAnd / or M'pSO _FourFurther contained
Amorphous builder further contains sodium metasilicate
When it is made to be 1 to 100 parts by weight of the amorphous builder,
50 parts by weight, preferably 1 to 40 parts by weight
With this, the alkali buffer capacity can be further improved.
Wear. That is, sodium metasilicate has an alkaline buffering capacity.
From the viewpoint of the improvement, 100 parts by weight of amorphous builder
Is preferably 1 part by weight or more, and storage stability
From the viewpoint of properties, based on 100 parts by weight of the amorphous builder
50 parts by weight or less, preferably 40 parts by weight or less
Is desirable. Note that M'pCO_ThreeAnd / or M'pSO
_FourAmorphous builder containing
In the case where soda is contained, "Amorphous builder 1
00 parts by weight "means M'pCO_ThreeAnd / or M'pSO
_FourBy weight of an amorphous builder containing no.

In order to prepare the amorphous builder of the present invention having such a constitution, for example, an M component and a Me component are added to water glass having a SiO ₂ / M ₂ O (molar ratio) of 2 to 4. , Mixing, preparing a mixture, and subjecting the mixture to a heat treatment.

The SiO ₂ / M ₂ O (molar ratio) is 2 to 4
As the water glass, a commercially available water glass may be used, and SiO ₂ / M ₂ O (molar ratio) is 2 to SiO ₂ components such as silica stone, silica sand, cristobalite stone, and kaolin.
Hydroxide, carbonate containing M component, so as to be 4,
An alkali source such as nitrate, sulfate, chloride, sulfide, silicate, etc. was added, heated to 1000 to 1500 ° C., melted, quenched at room temperature, and water glass was produced from the resulting cullet. You may. At that time, the cullet may be dissolved in water in a pressure reactor such as an autoclave (atmospheric temperature 80 to 200 ° C., atmospheric pressure 1 to 20 atm) or may be finely pulverized and dissolved in water or hot water. Good.

Further, the SiO ₂ component and the alkali source are placed in a pressure reactor (atmospheric temperature 80 to 200 ° C., atmospheric pressure 1 to 2).
Water glass obtained by directly reacting with water at 0 atm) may be used. When producing the water glass from the SiO ₂ component, a Me component can be added.

When the SiO ₂ / M ₂ O (molar ratio) is 2 to 4
The water content of the water glass is preferably 40 to 70% by weight in the mixture of the water glass, the M component and the Me component having SiO ₂ / M ₂ O (molar ratio) of 2 to 4.
From the viewpoint of viscosity, the content is desirably 40% by weight or more, preferably 50% by weight or more, and from the viewpoint of reducing the energy load for dehydration in the heat treatment step, 70% by weight or less, preferably 60% by weight or less. It is desirable that

Examples of the M component include hydroxides, carbonates, nitrates, sulfates, chlorides, sulfides, silicates, and the like containing a Group Ia element in the periodic table, and are not particularly limited. Of these, hydroxides are preferred. The state of the M component is not particularly limited, but is preferably an aqueous solution.

As the Me component, Me is represented by II in the periodic table.
In the case of a, IVa, IIb, and VIII group elements, hydroxides, carbonates, oxides, nitrates, sulfates, chlorides, silicates, and the like containing those elements are mentioned, and particularly limited. Among them, hydroxides, oxides, carbonates, silicates and the like are preferable. The state of the Me component is not particularly limited, but is preferably an aqueous solution or a water slurry.

In the case where Me is a Vb group element other than IIIb and N, examples of the Me component include nitrides, sodium salts, potassium salts, oxides and the like containing these elements. However, among them, a sodium salt is preferred. The state of the Me component is not particularly limited, but is preferably, for example, an aqueous solution.

As the Me component, when Me is N, compounds such as silicon nitride, urea, and amine can be mentioned, but there is no particular limitation. Among them, silicon nitride, urea and the like are preferable. The state of the Me component is not particularly limited, but is preferably an aqueous solution or an aqueous dispersion.

The amorphous builder according to the present invention comprises SiO ₂ /
Water glass having M ₂ O (molar ratio) of 2 to 4, M component and Me
The mixture of the components can be produced by heat treatment, but the temperature of the atmosphere during the heat treatment may be about 120 to 500 ° C. The heat treatment time at that time is not particularly limited, but may be about 1 minute to 5 hours.

The method of heat treatment is not particularly limited.
For example, heating equipment such as a blow dryer, a spray dryer, an electric furnace, and a gas furnace may be used. Further, these devices may be combined and heat-treated in multiple stages.

The amorphous builder according to the present invention has M'p
CO ₃ and / or M′pSO ₄ (where M ′ is Na,
K, Ca or Mg, and p represents 1 or 2), and a mixture of water glass having SiO ₂ / M ₂ O (molar ratio) of 2 to 4, M component and Me component After adding M′pCO ₃ and / or M′pSO ₄ , heat treatment is performed at 120 to 500 ° C. In this case, the form of M′pCO ₃ and M′pSO ₄ to be added is not particularly limited, but is preferably an aqueous solution or a water slurry. Also, M'p
When M ′ of CO ₃ is Na, a mixture of water glass, SiO ₂ / M ₂ O (molar ratio) in which a part or all of the M component is Na, and a mixture of the M component and the Me component is 2 to 4. In this case, heat treatment is performed in a carbon dioxide gas atmosphere so that Na of the M component is
And carbon dioxide to produce Na ₂ CO ₃ ,
a ₂ CO ₃ may be contained, and the heat-treated product may be exposed to a carbon dioxide gas atmosphere.

When the amorphous builder of the present invention further contains sodium metasilicate, SiO ₂ / M ₂ O
Sodium metasilicate is added to a mixture of water glass, M component and Me component having a (molar ratio) of 2 to 4, or to a mixture obtained by adding M′pCO ₃ and / or M′pSO ₄ to the mixture, The heat treatment can be performed at a temperature of up to 500 ° C. Alternatively, a raw material prepared so that x / y is in the range of 1.0 or more and less than 1.4 is prepared at 300 ° C.
By performing the heat treatment at 0 ° C., crystals of sodium metasilicate can be precipitated in the amorphous builder, whereby an amorphous builder containing sodium metasilicate can be obtained.

The water content of the amorphous builder according to the present invention is such that the SiO ₂ / M ₂ O (molar ratio) is 2 to ₂ during the heat treatment.
Since water evaporates from the water glass obtained by adding the M component and the Me component to the water glass of No. 4, it is preferable to control the water glass to 8 wt% or less, more preferably 4 wt% or less. At that time, since a foaming phenomenon occurs due to the release of water vapor, the amorphous builder powder obtained by pulverization has a specific surface area of 0.3 to less than the specific surface area of powdered sodium silicate 1 which is a known builder. compared to 2.0m ² / g, 1.1~5.0m ² /
g of powdered sodium silicate 1
No. 20 to 30 compared to 5-20mL / 100g
It is as large as 0 mL / 100 g. For this reason, the amorphous builder of the present invention is suitable for a powder detergent using a liquid surfactant.

The specific surface area can be measured by a flow-type specific surface area automatic measuring device (Flowsorb 2 manufactured by Shimadzu Corporation).
(Type 300) after dehydration at 100 ° C. for 30 minutes, and using a nitrogen gas as an adsorbing gas to measure by the BET one-point method.

Further, the method for measuring the oil absorption capacity is described in JIS5.
According to the pigment test method (oil absorption capacity) of No. 101, the substance to be absorbed can be measured using a nonionic surfactant instead of oil.

The cation exchange capacity of the amorphous builder of the present invention was measured by the method described in Examples described later.
mg CaCO ₃ / g or more, more preferably 90 mg
CaCO ₃ / g or more, more preferably 130 mg C
aCO ₃ / g or more, which is excellent.

The alkaline buffering capacity of the amorphous builder of the present invention was 5 m when measured by the method described in Examples below.
L or more, more preferably 8 mL or more, which is excellent.

The obtained amorphous builder can be produced, for example, by crushing using a crusher. At this time, the average particle size of the amorphous builder is not particularly limited, but from the viewpoint of exhibiting effective water dispersibility and an excellent cation exchange rate, about 5 to 100 μm, preferably 5 to 100 μm. Desirably, it is 50 μm.

As a pulverizing method, for example, a mortar can be used when crushing into a small amount, but a mortar can be used when crushing into a large amount or finely.
Examples of the pulverizer include the pulverizers described on pages 826 to 838 (1988).

(1) Apparatus for crushing by pressure or impact force, mainly used for coarse crushing: jaw crusher, gyre crusher, roll crusher, roll mill, etc. (2) The impact plate is fixed around the rotor rotating at high speed,
Apparatus for pulverizing by a shear force or the like between the rotor and the impact plate: hammer mill, impact crusher, pin mill, screen mill, and the like. (3) A device in which a roll or ball is pressed and rotated on a ring, and is crushed and crushed between them.
Ring roller mill, ring ball mill, centrifugal roller mill, ball bearing mill, etc. (4) Apparatus for putting balls or rods as a grinding medium into a cylindrical grinding chamber and rotating or vibrating to grind them: ball mill, vibrating mill, planetary mill, etc. (5) A pulverizing medium such as a ball or a bead is put into a cylindrical pulverizing chamber, and a disk-type or annular-type stirring mechanism inserted into the medium pulverizes by shearing and frictional action: a tower mill, an attritor, a sand mill or the like. (6) Apparatus for engulfing the material to be crushed into the air or steam ejected from the nozzle at high pressure and crushing the material to be crushed or the material to be crushed by collision between the material and the impact plate: Jetmizer,
Jet mill etc.

As the pulverizer used in the present invention, among these, the devices described in (1), (2), (3) and (4) are particularly preferable. The pulverizers can be used alone or in combination of two or more.

The obtained amorphous builder is used, for example, as a detergent raw material, an abrasive, a wastewater treatment agent, an exhaust gas treatment agent, a moisture absorbent, a neutralizing agent for acidic substances, an ion exchange agent, an oil absorbing agent and the like. be able to.

When the amorphous builder of the present invention is used as a detergent raw material, the amorphous builder may be in the form of a powder or may be compacted and granulated.

By compacting and granulating the amorphous builder, the bulk density of the amorphous builder can be increased while maintaining the water dispersibility of the amorphous builder. Performance can be improved.

In the case where compaction granulation is used to heat-treat the raw material of the amorphous builder in multiple stages, the compact produced in the first stage is compacted and then heat-treated in the second and subsequent stages. be able to. In this case, there is an advantage that the throughput per unit time in the second and subsequent heat treatments is improved.

The average particle size of the compacted and granulated particles of the amorphous builder is not particularly limited, but is preferably 3 mm or less from the viewpoint of water dispersibility and handleability.

As a granulating apparatus used for compaction granulation,
Granulation Handbook (edited by Japan Powder Industry Association, pages 173 to 197 (19
An apparatus for granulating by a compression granulation mechanism described in 75)) is mentioned, and specifically, a roll compactor, a briquetting machine, a rotary tableting machine and the like are preferable.

The amorphous builder of the present invention produced by such a method has a low water content, excellent cation exchange ability,
In addition, it has a high alkaline buffering capacity and is excellent in moisture absorption resistance.

Next, the detergent composition containing the amorphous builder of the present invention will be described.

The detergent composition of the present invention is not particularly limited. Examples thereof include a detergent for clothing, a softener, a detergent for dishes, a bath,
It is used for household detergents such as toilets and floors, toothpastes, body cleaners, metal cleaners, and the like. The content of the amorphous builder in the detergent composition at that time is not particularly limited, but is 0.1% by weight or more and 0.5% by weight or more from the viewpoint of exhibiting sufficient cleaning performance. And more preferably 1% by weight or more, and from the viewpoint of water dispersibility, 90% by weight or less, and 80% by weight or less.
Or less, more preferably 75% by weight or less.

The detergent composition of the present invention can usually contain a surfactant. The surfactant is not particularly limited as long as it is generally used in detergents, and examples thereof include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Is mentioned.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-
Olefin sulfonate, α-sulfo fatty acid salt or ester salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N acyl amino acid type surfactant and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyethylene glycol fatty acid alkyl ester, polyethylene Examples include polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkylglucoside, alkylglucoseamide, and alkylamine oxide.

The cationic surfactant includes, for example, alkyltrimethylammonium, alkyldimethylethylammonium chloride and bromide type surfactants.

The amphoteric surfactants include, for example, carboxy type and sulfobetaine type amphoteric surfactants.

The surfactants can be used alone or in combination of two or more. Further, the surfactant may be selected from the same type as in the case of selecting a plurality of anionic surfactants, or may be selected from anionic surfactants and non-ionic surfactants As such, a plurality of various types may be selected.

The amount of the surfactant is usually 0.1 to 90% by weight, preferably 0.5 to 90% by weight, and more preferably 1 to 80% by weight in the detergent composition. Is more preferable.

The detergent composition of the present invention can appropriately contain various additives which are usually contained in detergents.

The additive is not particularly limited as long as it is generally used in detergents. Examples of the additive include other inorganic chelates such as zeolite, crystalline silicate, sodium tripolyphosphate, and sodium metaphosphate. Agents, amino polyacetates, organic chelating agents such as polyacrylates, recontamination inhibitors such as carboxymethyl cellulose, amorphous aluminosilicates, amorphous silicates other than the present invention, sodium carbonate and potassium carbonate, etc. Alkaline agents, enzymes such as protease, lipase, cellulase, amylase, antioxidants,
Examples include clay minerals, bleaching agents such as sodium percarbonate and sodium pernitrate mono- or tetrahydrate, peroxide stabilizers such as magnesium silicate, bleaching activators, fluorescent dyes, bluing agents, and fragrances.

The method for producing the detergent composition of the present invention containing such surfactants, additives and the like is not particularly limited, and examples thereof include JP-A-61-69897 and JP-A-6-9897.
Known methods such as the methods described in 1-69899, JP-A-61-69900 and EP513824A can be used.

[0071]

EXAMPLES The present invention will be described in detail below with reference to examples, comparative examples, test examples and the like, but the present invention is not limited to these examples and the like.

The physical properties of the builders in this example and comparative examples were measured by the following methods.

(1) Measurement of Cation Exchange Capacity (CEC) 0.04 g of a sample was placed in an aqueous calcium chloride solution (concentration: Ca
In addition to 100 mg / L) 100 mL as CO _3, 20
Stirred at C for 10 minutes. Thereafter, the mixture was filtered through a 0.2 μm filter, and the amount of Ca contained in 10 mL of the filtrate was measured by EDTA titration, and the cation exchange capacity was determined based on the value.

(2) Alkaline buffer capacity 0.08 g of a sample was placed in an aqueous calcium chloride solution (concentration: Ca
(71.4 mg / L as CO ₃ ) in 500 mL,
Stir for 2 minutes at 20 ° C. Thereafter, 0.1 mol / L hydrochloric acid was added dropwise at a rate of 0.25 mL / 30 seconds, and the amount of hydrochloric acid added until the pH reached 10 was defined as the alkaline buffer capacity.

(3) Oil Absorption A 2 g sample was weighed into a beaker, and polyoxyethylene lauryl ether was added dropwise, followed by stirring with a glass rod. The oil absorption capacity was determined from the amount of polyoxyethylene lauryl ether required for the powder containing polyoxyethylene lauryl ether to clump and adhere to the glass rod.

(4) Storage stability 0.5 g of a sample was stored for 5 days in an environment of a temperature of 20 ° C. and a humidity of 65%, and the change in shape was observed with the naked eye. Was determined to be defective, and those in which the solid state was maintained or the shape did not change at all were regarded as good.

Example 1 No. 3 water glass (SiO ₂ 29.58% by weight, Na ₂ O
9.75 _{wt%, (SiO 2 / Na 2} O ( mole ratio) =
3.13), 60.67% by weight of H ₂ O)
32.5 g of 8% sodium hydroxide and 4.9 g of 15% calcium hydroxide slurry were mixed. The obtained solution was heat-treated at 400 ° C. for 2 hours using an electric furnace (manufactured by Motoyama Co., Ltd.), and then pulverized in a mortar to obtain amorphous builder powder 13.
0 g was obtained.

The water content of the obtained amorphous builder was determined by dividing the weight loss of 1 g of a sample heated at 700 ° C. for 1 hour by 1 g of the original sample, and found to be 4% by weight. Met.

The composition of the obtained amorphous builder was xS
It is represented by iO ₂ .yNa ₂ O.zCaO, and x / y = 1.
4, z / x = 0.02.

0.1 g of the obtained amorphous builder was
Ray diffractometer (Model RAD-20, manufactured by Rigaku Denki Co., Ltd.)
When X-ray diffraction was carried out under the conditions of Cukα ray, 40 kV, and 120 mA using 0), the maximum intensity of the obtained halo peak was 800 cps.

Further, a Raman spectrophotometer (SPEX Co., Ltd.)
(Model: Triplemate, excitation light: argon ion laser, wavelength: 1064 nm, detector: CCD detector), and 0.02 g of the obtained amorphous builder was measured. The obtained ^{value was} around 970 ± 20 cm ^−1. of was calculated shift peak area ratio of Q ₃ in the vicinity of the shift peak and 1070 ± 30 cm ^-1 in _{Q 2, Q 2 / Q 3} =
0.7.

The cation exchange capacity of the obtained amorphous builder powder was 160 mg CaCO ₃ / g.
Alkaline buffer capacity is 13.3 mL, oil absorption capacity is 260 mL /
The weight was 100 g, and the storage stability was good.

Example 2 No. 3 water glass (29.58% by weight of SiO ₂ , Na ₂ O
9.75 _{wt%, (SiO 2 / Na 2} O ( mole ratio) =
3.13), 60.67% by weight of H ₂ O)
187.4 g of 0% Na ₃ PO ₄ .12H ₂ O are added, followed by 29.9 g of 48% sodium hydroxide, 15%
4.9 g of the calcium hydroxide slurry was mixed. The obtained solution was heated at 400 ° C. using an electric furnace (manufactured by Motoyama Corporation).
, And then pulverized in a mortar to obtain 135 g of amorphous builder powder. The water content of the amorphous builder obtained in the same manner as in Example 1 was 5% by weight.

The composition of the obtained amorphous builder was xS
represented by iO ₂ .yNa ₂ O.z (CaO, PO ₄ )
x / y = 1.4 and z / x = 0.12.

X-ray diffraction was carried out in the same manner as in Example 1 using 0.1 g of the obtained amorphous builder.
The maximum intensity of the obtained halo peak was 800 cps. When the Raman spectrum was measured in the same manner as in Example 1, it was Q ₂ / Q ₃ = 0.5.

The cation exchange capacity of the obtained amorphous builder powder was 223 mg CaCO ₃ / g.
Alkaline buffer capacity is 12.7 mL, oil absorption capacity is 160 mL /
The weight was 100 g, and the storage stability was good.

Example 3 No. 3 water glass (29.58% by weight of SiO ₂ , Na ₂ O
9.75 _{wt%, (SiO 2 / Na 2} O ( mole ratio) =
3.13), 60.67% by weight of H ₂ O)
32.5 g of 8% sodium hydroxide and 4.9 g of 15% calcium hydroxide slurry were mixed. Next, 26.2 g of 20% sodium carbonate was added, and after stirring, an electric furnace (manufactured by
(Manufactured by Motoyama) at 400 ° C. for 2 hours, and then pulverized in a mortar to obtain 135 g of amorphous builder powder.
The water content of the amorphous builder obtained in the same manner as in Example 1 was 3% by weight.

The composition of the obtained amorphous builder was xS
iO ₂ .yNa ₂ O.zCaO further contained 10% by weight of sodium carbonate (based on the builder), and x / y = 1.4 and z / x = 0.02.

Using 0.1 g of the obtained amorphous builder, X-ray diffraction was carried out in the same manner as in Example 1.
The maximum intensity of the obtained halo peak was 850 cps. When the Raman spectrum was measured in the same manner as in Example 1, it was Q ₂ / Q ₃ = 0.8.

The cation exchange capacity of the obtained amorphous builder powder was 130 mg CaCO ₃ / g.
Alkali buffer capacity is 13.3 mL, oil absorption capacity is 150 mL /
100 g. Further, the storage stability was better than that of Example 1 in that the shape after storage maintained the shape before storage.

Example 4 No. 3 water glass (29.58% by weight of SiO ₂ , Na ₂ O
9.75 _{wt%, (SiO 2 / Na 2} O ( mole ratio) =
3.13), 60.67% by weight of H ₂ O)
42.3 g of 8% sodium hydroxide and 4.9 g of a 15% calcium hydroxide slurry were mixed. Next, 27.8 g of 20% sodium carbonate was added and mixed. The obtained solution was treated at 400 ° C. for 2 hours using an electric furnace (manufactured by Motoyama Corporation), and then pulverized in a mortar to obtain 140 g of amorphous builder powder. The water content of the amorphous builder obtained in the same manner as in Example 1 was 5% by weight.

The composition of the obtained amorphous builder was xS
iO ₂ .yNa ₂ O.zCaO further contained 10% by weight of sodium carbonate (based on the builder), and x / y = 1.2 and z / x = 0.02. According to the X-ray diffraction spectrum, 15% by weight (based on the builder) of sodium metasilicate crystals were precipitated in the amorphous builder, and the obtained amorphous builder was sodium metasilicate. And an amorphous builder containing sodium carbonate.

The maximum intensity of the halo peak is 800 c
ps. When the Raman spectrum was measured in the same manner as in Example 1, it was Q ₂ / Q ₃ = 1.2.

The cation exchange capacity of the obtained amorphous builder was 100 mg CaCO ₃ , the alkali buffer capacity was 16 mL, the oil absorption capacity was 140 mL / 100 g, and the storage stability was good.

Comparative Example The same builder performance evaluation as in Examples 1 to 4 was carried out using powdered sodium silicate No. 1 (manufactured by Nippon Chemical Industry Co., Ltd.) well known as a builder. As a result, the cation exchange capacity was 67 mg CaCO ₃ / g, and the alkaline buffer capacity was 4.1 m.
L, oil absorption capacity was 10 mL / 100 g. The water content of powdery sodium silicate No. 1 was 20% by weight. The storage stability also changed to a paste state, which was poor.

From the results of Examples 1 to 4 and Comparative Example, all of the amorphous builders obtained in Examples 1 to 4 had cation exchange ability and alkali It turns out that it is excellent in buffer capacity, oil absorption capacity and storage stability.

Test Example The detergency of the amorphous builder obtained in Examples 1 and 3 was compared with the powdered sodium silicate No. 1 described in Comparative Example by the method described below.

[0098] 850 m of ion-exchanged water is added to the tergotometer.
L, 100 mL of 1 g / L nonionic surfactant (polyoxyethylene lauryl ether) was added. To this, 0.2 g of the amorphous builder obtained in Example 1 or 3 or 0.2 g of powdered sodium silicate No. 1 was added, and sebum / carbon stained cloth (material: Tetron cotton, 5 cm)
× 5cm) 5 sheets, calcium chloride solution (concentration is CaCO
₍ 0.71 g / L as ₃ ) in the order of 50 mL and 2
Washing was performed at 0 ° C. for 10 minutes. Thereafter, the cells were rinsed with tap water and dried, and the cleaning rates were compared according to the following method.

<Calculation of cleaning rate> The reflectance of the original cloth of the contaminated cloth and the contaminated cloth at 550 nm before and after the cleaning were measured with a self-recording colorimeter (manufactured by Shimadzu Corporation). Was calculated.

D = (L ₂ −L ₁ ) / (L ₀ −L ₁ ) × 100 L ₀ : reflectance of original cloth L ₁ : reflectance of contaminated cloth before cleaning L ₂ : contaminant cloth after cleaning Reflectivity

As a result, the cleaning rates of the amorphous builders obtained in Examples 1 and 3 were 67% and 61%, respectively, which was much higher than that of the builder obtained in Comparative Example (35%). It can be seen that it has excellent cleaning properties.

[0102]

The amorphous builder of the present invention has a low water content, excellent cation exchange ability, high alkali buffering ability, and excellent moisture absorption resistance, and is useful as a detergent builder. It is something. Further, the detergent composition containing the amorphous builder has excellent detergency, a detergent for clothes, a softener, a detergent for dishes, a detergent for homes such as baths, toilets, floors, a toothpaste, It can be used as a body cleaner, metal cleaner and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mikio Sakaguchi 1334 Minato, Wakayama

Claims (8)

[Claims] 1. The general formula of an anhydride is xSiO ₂ .yM ₂ O.zMemOn (where M is an element of Group Ia of the periodic table, and Me is II of the periodic table)
a, IVa, IIb, IIIb, Vb or VIII group element;
x / y = 1.0-2.0, z / x = 0.001-1.
0, n / m = 1 to 2.5) and having a water content of 8% by weight or less. 2. Raman spectrophotometer (wavelength 1064 nm)
2. The amorphous builder according to claim 1, wherein an area ratio of a shift peak at 970 ± 20 cm ⁻¹ / shift peak at 1070 ± 30 cm ⁻¹ is 0.05 to 6. 3. The amorphous builder according to claim 1, wherein M is Na and Me is Ca. 4. The amorphous builder according to claim 1, wherein M is Na and Me is Ca and / or P. 5. An amount of M′pCO ₃ and / or M′pSO ₄ (wherein M ′ is Na, K, Ca) with respect to 100 parts by weight of the amorphous builder according to claim 1. Or an amorphous builder comprising 1 to 75 parts by weight of Mg and p represents 1 or 2. 6. An amorphous builder further comprising 1 to 50 parts by weight of sodium metasilicate based on 100 parts by weight of the amorphous builder according to claim 1. 7. The amorphous builder according to claim 1, which has an oil absorption capacity of 20 to 300 mL / 100 g. 8. A cleaning composition comprising the amorphous builder according to claim 1.