JP2525318B2 - Synthetic inorganic builder - Google Patents

Description

Detailed Description of the Invention

[0001]

This invention relates to synthetic inorganic builders. More specifically, it relates to a synthetic inorganic builder having excellent ion exchange ability and water resistance.

[0002]

[Background Art] [Problems to be Solved by the Invention] To date, many chelating agents have been used as builders incorporated into detergents.
Builders, precipitants, dispersants, etc. have been reported. recent years,
The use of tripolyphosphate has decreased due to concern over eutrophication in closed water areas such as lakes and mars, and crystalline aluminosilicates represented by JP-A-50-12381 and JP-A-51-12805. Is often used.

Although sodium silicate has an ion exchange capacity higher than that of zeolite, its use is limited because it dissolves in water. As a means for solving this, a method of heating and dehydrating sodium silicate to pulverize it is disclosed in JP-A-60-239320, and in the same manner, a part of silicon of sodium silicate is replaced with aluminum in the same manner. The method is disclosed in Japanese Patent Laid-Open No. 3-93649,
Both have insufficient water resistance and low ion exchange capacity. Further, a crystalline calcium silicate alkali hydrate obtained by hydrothermal synthesis is disclosed in Japanese Patent Publication No. 61-59245, which has sufficient water resistance, but has a low ion exchange capacity and is substantially a detergent. Not suitable as a builder. Furthermore, since the particle shape is a coarse long fiber shape or a mica shape, the dispersibility in water is poor, and the substantial ion exchange capacity further decreases. Further, DD-279234A1 discloses a crystalline magnesium-containing silicate obtained by hydrothermal synthesis, but it has been pointed out that it has an extremely low ion exchange capacity and cannot be practically used as a builder for detergents. There is.

Based on their structure, these crystalline silicates can be classified according to their classification according to the form of the anion (Friedrich Liebau, "St.
realistic Chemistry of Sil
icates "p72, Springer-Verla
g, published in 1985). That is, for example, a 4A type zeolite having a composition of Na ₂ O.Al ₂ O ₃ .2SiO ₂ which is a typical inorganic builder has a tectosilicate structure in which a part of Si is replaced by A1 in the same type, and Na ₂ O / ₂ Si
The dimetasilicate (layered silicate) represented by the composition of O ₂ is classified into a phyllosilicate structure. Furthermore, Ca
Metasilicate (pyroxene, Diopside) and Na ₂ having a composition of O · MgO · 2SiO ₂ · nH ₂ O
The metasilicate (sodium metasilicate) represented by the composition of O.SiO ₂ is classified into the inosilicate (polysilicate) structure.

[0005] More specifically, it will bond to Si.
The oxygen can be classified by the number of cross-linking oxygen (Si-O-Si).
Corresponding to the number of cross-linking oxygen of 4, 3, 2, 1, 0,
Re Q _Four, Q₃, Q₂, Q₁, Q₀Classified into units
(Y. Tsunawaki, N. Iwamoto, T. et al.
Hattori and A. Mitsushi,
J. Non-Cryst. Solids, vol44,
p369 (1981)). In the case of tectosilicate structure
Q because the number of cross-linking oxygen is 4_FourFrom the unit only,
In the case of a rosilicate structure, the number of bridging oxygen is 3, so Q₃
From unit only, bridging oxygen for inosilicate structures
Q because the number is 2.0-2.5₂Only unit
Is Q₂Unit and Q₃Formed with a unit. here
So Q₂Silicate consisting of only units, Q₂Unit
To and Q₃Less like a silicate consisting of units
Tomo Q₂A silicate composed of units has a chain structure.
It is said to be. On the other hand, Q₃Unit only
The silicate consisting of is said to have a layered structure.
The persons are structurally distinct.

According to these classifications, looking at the above-mentioned silicate compounds, which are inorganic builders used in detergents,
The 4A type zeolite having a tectosilicate structure formed from Q ₄ units has theoretically high cation exchange ability, but its dispersibility in water is poor and the compounding amount in a detergent is limited. Further, as the layered silicate having a phyllosilicate structure formed from Q ₃ units, there are the above-mentioned JP-A-60-239320 and JP-A-3-936.
Examples of those described in Japanese Patent Publication No. 49 are those having excellent dispersibility in water as described above because of their hydration properties, but on the contrary, the amount of dissolution in water is large and the cation exchange ability is 4A type. It is smaller than zeolite and insufficient as a builder for detergents.

On the other hand, pyroxene having an inosilicate structure composed of Q ₂ units shows almost no cation exchange ability and is insufficient as an inorganic builder. In addition, with inosilicate, a composition with a high cation exchange capacity (Na ₂ O
Although SiO ₂ ) exists as a crystalline metasilicate, its solubility in water is remarkable and its structure is destroyed, so that the actual cation exchange capacity is extremely low, and it is not suitable as an inorganic builder. As described above, it is difficult to obtain an inorganic builder that is excellent in both water resistance and ion exchange ability, and development of an inorganic builder that improves these is demanded.

An object of the present invention is to provide a synthetic inorganic builder having excellent ion exchange ability and water resistance, and its hydrate.

[0009]

That is, the gist of the present invention is as follows.
The anhydride is represented by the general formula: xM ₂ O · ySiO ₂ · zM ′ O (where M represents Na and / or K, M ′ represents Ca and / or Mg, and y / x = 0.5 to 2. 0, z / x = 0.
It is 005 to 1.0. ) A synthetic inorganic builder having a composition represented by the formula: 900 cm ^{-1 to} 1200 cm ^-1
In a Raman scattering spectrum for the range of at least 970 ± 20 cm ⁻¹ for a synthetic inorganic builder.

The synthetic inorganic builder of the present invention is xM ₂ O.
It has a composition represented by ySiO ₂ · zM′O, and is classified into an inosilicate structure according to the classification according to the form of anion, and has only a Q ₂ unit or a Q ₂ unit and a Q ₂ unit.
It is a crystalline silicate compound formed from ₃ units. In other words, the synthetic inorganic builder of the present invention has at least Q ₂ units and has a chain structure.

Specifically, the presence of Q ₃ and Q ₂ units can be identified by Raman spectroscopy. In Figure 1, FT-
Raman spectroscopy (manufactured by JEOL, format: JRS-FT650
0, excitation light: YAG laser, wavelength = 1064 nm, detector: InGaAs), an example of Raman spectrum is shown.

Since the synthetic inorganic builder of the present invention is a crystalline inosilicate compound having the above composition (see Example 61, FIG. 1 (a)), it is a layered silicate having a phyllosilicate structure (comparative). Example 1, see FIG. 1 (b)), showing a scattering peak pattern that is clearly different from that of 970 ± 20
At least a main shift peak derived from the Q ₂ unit is present at cm ^-1 . Here, the main shift peak refers to a clear shift peak that can be substantially identified in the Raman scattering spectrum in the range of 900 to 1200 cm ⁻¹ . On the other hand, the shift peak derived from the Q ₃ unit is observed at 1070 ± 30 cm ⁻¹ . Therefore, builder silicate compound is according to the present invention, which is constituted by the only or Q ₂ units and Q ₃ units Q ₂ units, in the range of 900～1200Cm ^-1, only 970 ± 20 cm ^-1, Or 970 ± 2
0 cm ^-1 and a shift peak at 1070 ± 30 cm ^-1, The shift peak derived from Q _0, Q ₁ unit for a crystalline substantially absent. When it is composed of Q ₂ unit and Q ₃ unit, as shown by the scattering peak pattern obtained by Raman spectroscopic measurement in Examples described later, the shift peak derived from Q ₂ unit and the peak derived from Q ₃ The shift peak intensity ratio is 0.1 to 1
It becomes 00. Here, the intensity ratio of the shift peak is 1070.
97 against the height of the shift peak appearing at ± 30 cm ^-1
It is calculated from the ratio of the heights of peaks appearing at 0 ± 20 cm ⁻¹ .

Further, despite having a Q ₂ unit structure, it exhibits high structural stability in water because Ca and / or Mg ions are contained in an appropriate amount in the silica network. This is clear from the measurement results of cation exchange capacity and Si elution amount in Examples described later.

The synthetic inorganic builder of the present invention having such a chain-like structural feature has an anhydrous composition represented by the general formula, xM ₂ O.ySiO ₂ .zM'O. Here, M represents Na and / or K, which may be a single component or both components of Na and K, and is not particularly limited, but from the viewpoint of cation exchange capacity, both Na and K are preferable. This is the case when it consists of components. In this case, the K / Na molar ratio is preferably 0.01 to 10.0.

M'represents Ca and / or Mg, which may be either alone or as both Ca and Mg components, and is not particularly limited. When it consists of both Ca and Mg components, the Mg / Ca molar ratio is preferably 0.01 to 10.0.

In the general formula, y / x is 0.5 to
It is 2.0, preferably 1.0 to 1.85. y
If / x is less than 0.5, the water resistance is insufficient and 2.0
If it exceeds, the ion exchange capacity will be low, and it will be insufficient as an inorganic builder. z / x is 0.005 to 1.0, preferably 0.01 to 0.8, and more preferably 0.1.
It is 02-0.6. If z / x is less than 0.005, the water resistance is insufficient, and if it exceeds 1.0, the ion exchange capacity is low and the inorganic builder is insufficient. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. When xM ₂ O is, for example, x′Na ₂ O · x ″ K ₂ O as described above, x is x ′ + x ″, which is the same for z, and zM′O is, for example, z When ′ CaO · z ″ MgO, z becomes z ′ + z ″. The inorganic builder of the present invention may be a hydrate, and the hydration amount in this case is usually 0 to 20 in terms of H ₂ O molar amount.

The synthetic inorganic builder of the present invention is obtained by synthesis and, as shown in the above general formula, M
_It consists of three components, ₂ O, SiO ₂ , and M'O. Therefore, in order to produce the synthetic inorganic builder of the present invention, a substance corresponding to each component is required as a raw material thereof, but known compounds are appropriately used in the present invention without any particular limitation. For example, as the M ₂ O component and M ′ O component, single or complex oxides, hydroxides, salts of the respective relevant elements, and the element-containing minerals are used. Specifically, for example, as the raw material of the M ₂ O component, NaOH, KO
H, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO _4, etc. are M '
As the raw material of the O component, CaCO ₃ , Ca (O
H) ₂ , MgCO ₃ , Mg (OH) ₂ , MgO, dolomite and the like. As the SiO ₂ component, silica stone, silica sand, cristobalite stone, kaolin, talc, fused silica, sodium silicate and the like are used.

In the present invention, these raw material components are mixed in a predetermined quantitative ratio so that the intended synthetic inorganic builder is x, y, z, and are usually 300 to 1300 ° C., preferably 500 to 1000 ° C. More preferably 600-90
Examples include a method of firing in the range of 0 ° C. to crystallize, a method of similarly mixing, then once melting at 1100 ° C. to 1600 ° C. to obtain a vitrified product, and then firing, and a method of further melting and water-vitalizing and firing. To be done. In this case, the heating temperature is 300 ℃
If it is less than 1, the crystallization is insufficient and the water resistance is poor, and the temperature is 1300 ° C.
If it exceeds, coarse particles are formed and the ion exchange capacity is reduced. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.
Further, after firing, the powder is crushed as necessary to have a predetermined particle size. As the crusher, for example, a ball mill, a roller mill or the like is used. By such a production method, the synthetic inorganic builder of the present invention having the above-mentioned structural features can be obtained.

The hydrate of the synthetic inorganic builder of the present invention can be easily prepared by a known method and is not particularly limited. For example, a method may be mentioned in which the anhydride of the synthetic inorganic builder obtained as described above is suspended in ion-exchanged water to be hydrated, and dried to be powdered.

The thus obtained synthetic inorganic builder of the present invention or a hydrate thereof has an ion exchange capacity of at least 100 mg CaCO ₃ / g or more, preferably 2 or more.
It has from 100 to 600 mg CaCO ₃ / g.
In the present invention, the ion exchange capacity refers to the value of cation exchange capacity obtained by the measuring method described later in the examples.
However, in the case of 500 mg CaCO ₃ or more, it is a value measured with the amount of the calcium chloride solution being 200 ml. In the present invention, water resistance means the stability of an inorganic builder in water. Therefore, poor water resistance means that the stability of the inorganic builder in water is poor and the amount of Si eluted in water increases. On the other hand, having excellent water resistance means that the inorganic builder has high stability in water and the amount of Si eluted in water is very small. In the synthetic inorganic builder of the present invention, the amount of Si eluted into water is usually 1 in terms of SiO _2.
It is 20 mg / g or less, preferably 90 mg / g or less, more preferably 60 mg / g or less, and most of them are substantially insoluble in water. In the present invention, “substantially insoluble in water” means that 2 g of a sample is treated with 10
S when added to 0 g and stirred at 25 ° C. for 30 minutes
i means that the elution amount is usually less than 100 mg / g in terms of SiO ₂ .

The synthetic inorganic builders of the present invention exhibit excellent alkaline ability. Here, the alkalinity means the ability to show a buffering action against an acid, and in the synthetic inorganic builder of the present invention, 15 ml of 0.25 N hydrochloric acid was added to 1000 ml of 0.1 wt% ion-exchanged water dispersion. Even 9 to 12 p
H is shown. In addition, the alkaline buffering effect is also particularly excellent, and the alkaline buffering effect is also excellent as compared with sodium carbonate and ordinary amorphous sodium silicate. Since the synthetic inorganic builder of the present invention has the excellent ion-trapping ability as described above, the detergent composition containing the same has excellent cleaning performance.

Since the synthetic inorganic builder of the present invention has an excellent ion-trapping ability as described above, the detergent composition containing the same has excellent cleaning performance. Such a detergent composition contains at least the aforementioned synthetic inorganic builder and / or its hydrate. The detergent composition is not particularly limited, but is used as a detergent for clothes, a softener, a detergent for tableware, a toothpaste, a detergent for the body, a detergent for metals and the like. The compounding amount of the synthetic inorganic builder and / or its hydrate is not particularly limited, but is usually 0.1 to 90% by weight, preferably 0.1.
It is 5 to 80% by weight, more preferably 1 to 75% by weight. If it is less than 0.1% by weight, sufficient cleaning performance will not be exhibited, and if it exceeds 90% by weight, dispersibility will be poor. In particular, the content of the inorganic builder of the present invention as a detergent for clothing is usually 0.5 to 70% by weight, preferably 1 to 60% by weight, more preferably 2 to 55% by weight. If it is less than 0.5% by weight, the performance of the inorganic builder is not exhibited as a composition, and if it exceeds 70% by weight, the blending amount of other components contained in the detergent is restricted, and the component balance as a detergent is balanced. Interfere with.

The detergent composition in the present invention usually contains a surfactant, and the surfactant is not particularly limited as long as it is generally used for detergents. Specifically, it is at least one selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. For example, it is possible to select only from the same kind as in the case of selecting a plurality of anionic surfactants, or to select various kinds from the case of selecting from anionic surfactant and nonionic surfactant respectively. You may select two or more.

In the present invention, various additives usually added to detergents can be added appropriately. Also in this case, there is no particular limitation as long as it is generally used as a detergent. For example, other inorganic builders such as zeolite, sodium tripolyphosphate, sodium metaphosphate; amorphous aluminosilicate, amorphous silicate, sodium carbonate, amorphous silica, clay mineral, bleaching agent, enzyme, etc. can do.

The above-mentioned detergent composition contains the above-mentioned components, but the method for producing the detergent composition is not particularly limited, and conventionally known methods can be used. For example, as a method for obtaining a high bulk density detergent, JP-A-61-69897 and JP-A-61-69 are known.
899, JP-A-61-69900, EP5
The method described in the 13824A specification is mentioned.

[0026]

EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples and the like. The measured values in the examples and comparative examples were measured by the following method. (1) Cation exchange capacity In Examples 1 to 36 and Comparative Examples 1 to 7, 0.1 g of a sample was precisely weighed, and a calcium chloride solution (concentration was CaC
O _{3 (} 1% as O ₃ ) is added to 50 ml, the mixture is stirred at 25 ° C. for 60 minutes, and then filtered using a type 5 C filter paper. 10 ml of the filtrate was taken, the amount of Ca in the filtrate was measured by EDTA titration, and the calcium ion exchange capacity of the sample was determined from the value. In Examples 37 to 63, 0.1 g of a sample was precisely weighed, added to 100 ml of an aqueous calcium chloride solution (concentration: 500 ppm as CaCO ₃ ), stirred at 25 ° C. for 60 minutes, and then a membrane filter having a pore size of 0.2 μm. (Advantech, made of nitrocellulose) is used for filtration, and the amount of Ca contained in 10 ml of the filtrate is EDTA.
It was measured by titration. The calcium ion exchange capacity (cation exchange capacity) of the sample was determined from the value. (2) Si elution amount 2 g of a sample was added to 100 g of ion-exchanged water, and the mixture was mixed at 25 ° C. for 3 hours.
The mixture is stirred for 0 minutes and then centrifuged, and the supernatant is filtered using a membrane filter having a pore size of 0.2 μm. The Si concentration in the filtrate was analyzed by plasma emission spectrometry (IC
P), and the amount of eluted Si was calculated in terms of SiO ₂ . (3) Raman peak intensity ratio Fourier transform Raman spectrophotometer (JEOL Ltd., J
SR-FT6500, excitation light: YAG laser, wavelength =
Raman spectroscopic measurement was performed using 1064 nm, detector: InGaAs), and in the obtained Raman scattering spectrum, the scattering intensities belonging to Q ₂ and Q ₃ were respectively calculated.
The relative intensity ratio of Q ₂ / Q ₃ was determined as the peak top value of the shift peaks appearing at 970 ± 20 cm ⁻¹ and 1070 ± 30 cm ⁻¹ .

Example 1 No. 2 sodium silicate (SiO ₂ / Na ₂ O = 2.5) 100
23.1 parts by weight of sodium hydroxide was added to parts by weight, and the mixture was stirred with a homomixer to dissolve the sodium hydroxide. To this, 14.3 parts by weight of finely ground anhydrous calcium carbonate was added and mixed using a homomixer. An appropriate amount of the mixture was placed in a nickel crucible, fired at 700 ° C. in air for 1 hour, quenched, and the fired body obtained was pulverized to obtain an inorganic builder 1 of the present invention. The cation exchange capacity of this powder is as high as 264CaCO ₃ mg / g, and the elution amount of Si is 5
It was 9.1 SiO ₂ mg / g and was excellent in water resistance. The powder X-ray (CuKα) diffraction pattern of the obtained fired product showed a diffraction pattern different from that of the mixture before firing, and was a substance having a novel crystal structure. The Q ₂ / Q ₃ intensity ratio of the Raman scattering spectrum was 6.67.

Examples 2 to 8 Inorganic builders 2 to 8 were obtained in the same manner as in Example 1 except that the composition shown in Table 1 was changed by changing the addition amount of anhydrous calcium carbonate. . The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 1. As with the inorganic builder 1, the cation exchange capacity and water resistance were excellent. Further, the powder X-ray (CuKα) diffraction patterns of the obtained fired bodies all showed diffraction patterns different from those of the mixture before firing, and were substances showing a novel crystal structure.

Examples 9 to 16 In Example 1, instead of No. 2 sodium silicate, silica stone powder of 325 mesh pass and potassium hydroxide were used, and anhydrous calcium carbonate was used to obtain the composition shown in Table 1. Inorganic builders 9 to 16 were obtained in the same manner as in Example 1 except for the above. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 1. As with the inorganic builder 1, the cation exchange capacity and water resistance were excellent. In addition, powder X-ray (Cu
The Kα) diffraction patterns each showed a diffraction pattern different from that of the mixture before firing, and were substances showing a novel crystal structure.

Examples 17 and 18 10 g of the anhydride obtained in Examples 2 and 12 was dispersed in 500 ml of ion-exchanged water for 1 hour and filtered through a 0.2 μm membrane filter, and the residue on the filter was 100%.
After drying at 16 ° C. for 16 hours, inorganic builders 17 and 18, which are hydrates of those obtained in Examples 2 and 12, were obtained. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 1. As with the inorganic builder 1, the cation exchange capacity and water resistance were excellent. In addition, powder X-ray (CuK
The α) diffraction patterns each showed a diffraction pattern different from that of the mixture before firing and were substances showing a novel crystal structure.

[0031]

[Table 1]

Example 19 No. 2 sodium silicate (SiO ₂ / Na ₂ O = 2.5) 100
23.1 parts by weight of sodium hydroxide was added to parts by weight, and the mixture was stirred with a homomixer to dissolve the sodium hydroxide. Here, pulverized anhydrous magnesium carbonate 12.0
Parts by weight were added and mixed using a homomixer. An appropriate amount of the mixture was placed in a nickel crucible, fired at 700 ° C. in air for 1 hour, quenched, and the fired body obtained was pulverized to obtain an inorganic builder 19 of the present invention. The cation exchange capacity of this powder was as high as 260 CaCO ₃ mg / g, and the amount of Si eluted was 59.6 SiO ₂ mg / g, which was excellent in water resistance. In addition, powder X-ray (CuK
The α) diffraction pattern showed a diffraction pattern different from that of the mixture before firing, and was a substance having a novel crystal structure. In the Raman scattering spectrum, only a shift peak derived from Q ₂ was observed in the range of 900 to 1200 cm ⁻¹ .

Examples 20 to 26 Inorganic builders 20 to 26 were obtained in the same manner as in Example 19 except that the composition shown in Table 2 was changed by changing the addition amount of anhydrous magnesium carbonate. . The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 2. As with the inorganic builder 19, the cation exchange capacity and water resistance were excellent. In addition, powder X-ray (Cu
The Kα) diffraction patterns each showed a diffraction pattern different from that of the mixture before firing, and were substances showing a novel crystal structure.

Examples 27 to 34 In Example 19, 325 was used instead of No. 2 sodium silicate.
Inorganic builder 27 was prepared in the same manner as in Example 19 except that silica stone powder of mesh pass and potassium hydroxide were used, and anhydrous magnesium carbonate was used to obtain the composition shown in Table 2.
~ 34 were obtained. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 2. As with the inorganic builder 19, the cation exchange capacity and water resistance were excellent. Further, the powder X-ray (CuKα) diffraction patterns of the obtained fired bodies all showed diffraction patterns different from those of the mixture before firing, and were substances showing a novel crystal structure.

Examples 35 and 36 500 g of 10 g of the anhydride obtained in Examples 20 and 30
Dispersed in ion-exchanged water for 1 hour and filtered through a 0.2 μm membrane filter to remove residue on the filter for 10 hours.
It was dried at 0 ° C. for 16 hours to obtain inorganic builders 35 and 36, which are hydrates of those obtained in Examples 20 and 30, respectively. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 2. As with the inorganic builder 19, the cation exchange capacity and water resistance were excellent. Further, the powder X-ray (C
The uKα) diffraction patterns each showed a diffraction pattern different from that of the mixture before firing, and were materials exhibiting a novel crystal structure.

[0036]

[Table 2]

Example 37 An inorganic builder 37 of the present invention was obtained in the same manner as in Example 1 except that the composition shown in Table 3 was used. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent. The cation exchange capacity of this powder was as high as 270 CaCO ₃ mg / g, and the amount of eluted Si was 48.3 SiO ₂ mg / g, which was excellent in water resistance. Also, the Q of Raman scattering spectrum
_{The 2} / Q ₃ intensity ratio was 0.16.

Example 38 In Example 1, No. 1 sodium silicate (SiO ₂ / Na ₂ O = 2.14, water content 44.9) was used instead of No. ₂ sodium silicate.
%) Was used to obtain the composition shown in Table 3, and the inorganic builder 38 of the present invention was obtained in the same manner as in Example 1.
The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent. The cation exchange capacity of this powder was as high as 251CaCO ₃ mg / g, and the amount of eluted Si was 91.1SiO ₂ mg / g, which was excellent in water resistance. In addition, Q ₂ / Q of Raman scattering spectrum
_{The 3} intensity ratio was 0.14.

Example 39 An inorganic builder 39 of the present invention was obtained in the same manner as in Example 38 except that anhydrous magnesium carbonate was used in place of anhydrous calcium carbonate to obtain the composition shown in Table 3. It was The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3.
It was excellent in both cation exchange capacity and water resistance. The cation exchange capacity of this powder is 321CaCO ₃ mg / g
And the elution amount of Si was 96.5 SiO ₂ mg / g, which was excellent in water resistance. The Q ₂ / Q ₃ intensity ratio of the Raman scattering spectrum was 0.50.

Example 40 Powdery No. 1 sodium silicate (SiO ₂ / Na ₂ O = 2.1)
1, water 22.1%), 1.8 parts by weight of sodium hydroxide, 0.9 parts by weight of anhydrous calcium carbonate and 1.5 parts by weight of magnesium hydroxide were added and mixed using a ball mill. Appropriate amount of the mixture into a nickel crucible, 600
After firing in air at a temperature of ° C for 1 hour and quenching, the fired body obtained was ground to obtain an inorganic builder 40 of the present invention. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent. The cation exchange capacity of this powder was as high as 242CaCO ₃ mg / g, and the amount of Si eluted was 87.4SiO ₂ mg / g, which was excellent in water resistance. The Q ₂ / Q ₃ intensity ratio of the Raman scattering spectrum was 0.11.

Example 41 Inorganic builder 41 of the present invention was prepared in the same manner as in Example 40 except that the composition shown in Table 3 was obtained by changing the amounts of anhydrous calcium carbonate and magnesium hydroxide added. Got The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent. The cation exchange capacity of this powder is 299CaCO
High as ₃ mg / g and Si elution amount is 1.5 SiO ₂ mg / g
The water resistance was excellent. The Q ₂ / Q ₃ intensity ratio of the Raman scattering spectrum was 0.17.

Examples 42 to 44 Silica sand (SiO ₂ purity 99.7%), potassium carbonate, anhydrous calcium carbonate and magnesium hydroxide were mixed in the same manner as in Example 40 to give the composition shown in Table 3, This mixture was melted at a temperature of 1300 ° C. for 20 hours and then rapidly cooled to obtain a cullet. 1 part by weight of 100-mesh cullet and 4 parts by weight of ion-exchanged water are put into a nickel crucible in an appropriate amount, and at a temperature of 600 ° C, 2
After firing for a period of time and quenching, the fired body obtained was pulverized to obtain the inorganic builders 42 to 44 of the present invention. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent.

Examples 45 to 46 The same as Example 1 except that potassium carbonate was added to sodium carbonate and anhydrous magnesium carbonate was added to anhydrous magnesium carbonate so that the compositions shown in Table 3 were obtained. To obtain the inorganic builders 45 to 46 of the present invention. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent.

Examples 47 to 48 Example 38 and Example 38, except that potassium hydroxide was added to sodium hydroxide, magnesium hydroxide was added to anhydrous calcium carbonate to obtain the composition shown in Table 3. Similarly, the inorganic builders 47 to 48 of the present invention were obtained. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent.

Examples 49 to 53 Inorganic builders 49 to 49 of the present invention were prepared in the same manner as in Example 40 except that potassium hydroxide was used in addition to sodium hydroxide so that the composition shown in Table 3 was obtained. 5
3 was obtained. Cation exchange capacity and S of the obtained powder
The i elution amount was measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were excellent.

Examples 54 to 58 Example 3 is the same as Example 31 except that sodium carbonate is added to potassium carbonate, and anhydrous calcium carbonate and magnesium hydroxide are used to obtain the compositions shown in Table 3.
Inorganic builders 54 to 58 of the present invention were obtained in the same manner as in 1. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent.

Examples 59 to 63 Example 4 was repeated except that the composition shown in Table 3 was obtained by using sodium carbonate in addition to potassium carbonate and anhydrous calcium carbonate and magnesium hydroxide.
Inorganic builders 59 to 63 of the present invention were obtained in the same manner as in 2. The cation exchange capacity and Si elution amount of the obtained powder were measured, and the results are shown in Table 3. The cation exchange capacity and water resistance were both excellent. Further, regarding the inorganic builder 61 obtained in Example 61, a Fourier transform Raman spectrophotometer (JSR-FT) manufactured by JEOL Ltd.
6500 N type) was used for Raman spectroscopic measurement, the obtained spectrum (FIG. 1 (a)) was compared with the spectrum of sodium disilicate (Na ₂ Si ₂ O ₅ ) obtained in Comparative Example 1 (FIG. 1). FIG. 1 shows a comparison with (b)). From FIG. 1, it was suggested that the inorganic builder 61 is a substance exhibiting a chain structure, since the main shift peak derived from the Q ₂ unit was observed at 970 ± 20 cm ⁻¹ .

[0048]

[Table 3]

Comparative Example 1 Sodium hydroxide 4.2 was added to 100 parts by weight of No. 2 sodium silicate.
Parts by weight were added, and sodium hydroxide was dissolved using a homomixer. Take an appropriate amount of this in a nickel crucible,
It was calcined in air at a temperature of 0 ° C. for 1 hour. After rapid cooling, crushing was performed to obtain Comparative Builder 1. The cation exchange capacity of this powder was 224CaCO ₃ mg / g. The amount of Si eluted was 133 SiO ₂ mg / g, which was poor in water resistance. The poor water resistance is considered to be because Ca or Mg having the function of structural stability in water of the comparative builder is not contained.

Comparative Example 2 No. 2 sodium silicate was added to 100 parts by weight of sodium hydroxide 10.
6 parts by weight was added, and sodium hydroxide was dissolved using a homomixer. Take an appropriate amount of this in a nickel crucible,
It was calcined in air at a temperature of 00 ° C. for 1 hour. After rapid cooling, pulverization was performed to obtain Comparative Builder 2. The cation exchange capacity of this powder was as high as 450 CaCO ₃ mg / g, but the amount of Si eluted was 324 SiO ₂ mg / g, which was poor in water resistance.

Comparative Example 3 325 mesh pass silica stone powder and potassium hydroxide are shown in Table 4.
The mixture was mixed with a V-type mixer so as to have the composition shown in (4), and an appropriate amount of this was mixed into a crucible made of nickel and baked at 700 ° C. in the air for 1 hour. After rapid cooling, crushing was performed to obtain Comparative Builder 3. The cation exchange capacity of this powder is 462 CaCO ₃ mg / g.
However, the Si elution amount was 531SiO ₂ mg / g, which was poor in water resistance.

Comparative Example 4 Slaked lime was mixed in an aqueous solution of sodium silicate, and hydrothermally synthesized in a 300 ml autoclave at 180 ° C. for 20 hours, and Table 4
Comparative builder 4 having the composition shown in was obtained. As shown in Table 4, the amount of Si eluted from this powder was small and the water resistance was excellent, but the cation exchange capacity was 175 CaCO ₃ mg / g.
And the cation exchange capacity was insufficient. Despite the excellent water resistance, the low cation exchange ability was attributed to the decrease in cation exchange sites due to the excessive presence of Ca, which has the function of structural stability in water of the comparative builder. To be judged.

Comparative Example 5 Magnesium hydroxide and lithium hydroxide were mixed in a sodium silicate aqueous solution, and the mixture was placed in an autoclave of 300 ml for 180 times.
Hydrothermal synthesis was carried out at 0 ° C. for 20 hours to obtain Comparative Builder 5 having the composition shown in Table 4. As shown in Table 4, the amount of Si eluted from this powder was small and the water resistance was excellent, but the cation exchange capacity was as low as 62 CaCO ₃ mg / g and the cation exchange capacity was insufficient. . Despite the excellent water resistance, the low cation exchange capacity is attributed to the decrease in cation exchange sites due to the excessive presence of Mg, which has the function of structural stability in water, of the comparative builder. To be judged.

Comparative Example 6 An appropriate amount of a mixture of potassium hydroxide in a No. 2 sodium silicate aqueous solution having the composition shown in Table 4 was taken in a nickel crucible and baked at 650 ° C. for 1 hour in the air. . After rapid cooling, pulverization was performed to obtain Comparative Builder 6. As shown in Table 4, the cation exchange capacity of this powder is 200 CaCO ₃ mg / g.
As described above, the amount of Si eluted was as large as 309 SiO ₂ mg / g and the water resistance was poor.

Comparative Example 7 An appropriate amount of potassium hydroxide, anhydrous calcium carbonate and magnesium hydroxide mixed in an aqueous solution of sodium silicate No. 1 so as to have the composition shown in Table 4 was taken in a nickel crucible,
It was calcined in air at a temperature of 00 ° C. for 1 hour. After rapid cooling, crushing was performed to obtain Comparative Builder 7. As shown in Table 4, the amount of Si eluted from this powder was small and the water resistance was excellent, but the cation exchange capacity was 200 CaCO ₃ mg / g or less, and the cation exchange capacity was insufficient. there were.

[0056]

[Table 4]

Preparation Example 1 of Detergent Composition Detergent having the composition shown in Table 5 (Formulations 1-A and 1-B are products of the present invention containing the inorganic builder of the present invention;
C represents a comparative product not containing C) was produced by the following method. That is, powder raw materials (sodium silicate, sodium carbonate, salt cake, amorphous silica, inorganic builders 1-A, 1-B) were put in a stirring type rolling granulator (Ledige mixer) to obtain polyoxyethylene dodecyl ether. Polyethylene glycol was added to obtain a powder detergent having an average particle size of 352 to 407 μm. The inorganic builders 1-A and 1-B used here are the inorganic builders obtained in Examples 2 and 5, respectively.

[0058]

[Table 5]

Similarly, the detergents having the compositions shown in Table 6 (Formulations 1-D and 1-E are the products of the present invention containing the inorganic builder of the present invention, and Formula 1-F are the comparative products not containing them). ) Was manufactured. Here, an aqueous slurry of components other than the inorganic builder was prepared at 60 ° C. and made into a dry powder by a spray dryer. Put this in a centrifugal tumbling granulator (high speed mixer), add a little water and granulate to obtain an average particle size of 36
A powder detergent of 0 to 388 μm was obtained.

[0060]

[Table 6]

Test Example 1 Formulation 1-obtained according to Preparation Example 1 of the above-mentioned detergent composition
A cleaning test was performed using A to 1-F by the following method. (1) Dirty dirt-contaminated cloth (artificial-contaminated cloth): Kanuma gardening red tama soil was dried at 120 ° C ± 5 ° C for 4 hours and then crushed and then 150 mesh (100μ)
m) After drying the pass one at 120 ° C ± 5 ° C for 2 hours, soil 15
Disperse 0 g in 1000 liters of perkren, gold width # 2023
A cloth is contacted with this liquid and brushed to remove the dispersion liquid and remove excess adhered dirt (Japanese Patent Laid-Open No. 55-26473). (2) Sebum / Carbon Stain Contamination Cloth (Artificial Stain Cloth): (Model Sebum / Carbon Stain Composition) Carbon Black 15% Cottonseed Oil 60% Cholesterol 5% Oleic Acid 5% Palmitic Acid 5% Liquid Paraffin 10% 1 kg of the above composition Dissolve and disperse in 80 liters of Perkren, dip a cloth of gold # 2023 to attach dirt, and then dry and remove Perkren.

(3) Washing conditions: 5 liters of 10 cm × 10 cm cotton dirt soiled cloth or sebum / carbon soiled soiled cloth (artificial soiled cloth) are put in 1 liter of the detergent aqueous solution for evaluation, and 100 rpm is applied with a tergo meter. Was washed under the following washing conditions. (Washing conditions) Washing time 10 minutes Washing concentration 0.133% Water hardness 4 ° Water temperature 20 ° C Susugi 5 minutes with tap water (4) Evaluation method of washing test: Detergency is raw cloth before contamination and contamination before and after washing The reflectance of the cloth at 460 nm was measured using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was calculated by the following formula. Cleaning rate (%) = (reflectance after cleaning-reflectance before cleaning) /
(Reflectance of original fabric-reflectance before washing) x 100 The obtained results are shown in Table 7. By using the detergent composition of the present invention, excellent washing performance was recognized.

[0063]

[Table 7]

Preparation Example 2 of Detergent Composition Detergent having the composition shown in Table 8 (Formulations 2-A and 2-B are products of the present invention containing the inorganic builder of the present invention;
C represents a comparative product not containing C) was produced by the same method as in Preparation Example 1 of the detergent composition. However, inorganic builder 2
-A and 2-B are the inorganic builders obtained in Examples 20 and 23, respectively.

[0065]

[Table 8]

Similarly, detergents having the compositions shown in Table 9 (formulations 2-D and 2-E are products of the present invention containing the inorganic builder of the present invention, and formulation 2-F is a comparative product not containing them). ) Was manufactured.

[0067]

[Table 9]

Test Example 2 Formulation 2 obtained in Preparation Example 2 of the above-mentioned detergent composition
A cleaning test was performed using A to 2-F in the same manner as in Test Example 1. The obtained results are shown in Table 10, and excellent cleaning performance was recognized by using the cleaning composition of the present invention.

[0069]

[Table 10]

Preparation Example 3 of Cleaning Agent Composition Formulations 3-1 to 73 Examples 37, 19, 9, 57, 60, 61 and 17 described above.
Using the inorganic builders 3-A to 3-G obtained in Table 1, Table 1
A detergent composition having the composition shown in Tables 1 to 16 was produced by the following method. That is, in Formulations 3-1 to 3-14, the components other than the inorganic builder were made into a 60% solid content aqueous slurry, and the particles obtained by spray-drying this were mixed with the inorganic builder. Formulation 3-15 to 3-25, Formulation 3-3
In 9 to 3-68, 6 consisting of components other than inorganic builders
The 0% solid content slurry was spray-dried, the obtained particles were placed in a stirring type granulator, and an inorganic builder in an amount corresponding to the compounding amount was further put in to perform granulation. In Formulations 3-26 to 3-38, the powder raw materials were put into a stirring type rolling granulator, and the liquid nonionic surfactant was gradually added, and mixed granulation was performed. In this way, a powdery detergent composition having an average particle size of 200 to 500 μm was obtained.

Blending Comparative Examples 3-1 to 3-10 Using Zeolite 4A in place of the inorganic builder,
Alternatively, a cleaning composition having the compositions shown in Tables 11 to 15 was produced in the same manner as in the above formulation example except that the inorganic builder was not used.

Blending Comparative Examples 3-11 to 3-12 Zeolite 4A or citric acid 3 instead of the inorganic builder.
Same as Formulations 3-61 to 3-68 except that Na · 2H ₂ O was used and the compounding amount was adjusted so that the cleaning rate and the pH before and after the cleaning were the same as those in Formulations 3-61 to 3-68. A cleaning composition having the composition shown in Table 16 was produced.

Test Example 3 Using the cleaning compositions obtained in Formulations 3-1 to 14 and Formulation Comparative Examples 3-1 and 3-2, a cleaning test was conducted under the following conditions. (Preparation of artificially contaminated cloth) A cotton cloth of 10 cm × 10 cm was contaminated with fats and oils having the following composition and a trace amount of carbon black. Cottonseed oil 60% Cholesterol 10% Oleic acid 10% Palmitic acid 10% Liquid and solid paraffin 10% (Washing conditions) Using a two-tub type washing machine (Toshiba Corp., Galaxy), washing time 10 minutes, temperature 20 ℃, water used 3 ° DH
(Ca / Mg = 3/1), washing with running water for 8 minutes, and detergent concentration of 0.133% were performed. (Calculation of Washing Rate) The reflectance at 550 mμ before and after washing was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the washing rate D (%) was calculated by the following formula. The results are shown in Table 1.
1 is also shown. _{D = (L 2 -L 1)} / (L 0 -L 1) × 100 (%) L 0: reflectance of original cloth L _1: reflectance before washing soiled cloth L _2: reflectance after washing soiled cloth

[0074]

[Table 11]

The contents of the abbreviations in the table are shown below together with those used in the other tables below. LAS-Na: Linear sodium alkylbenzene sulfonate AS-Na: Sodium alkyl sulfate AOS-Na: Sodium α-olefin sulfonate AOS-K: Potassium α-olefin sulfonate α-SFE-Na: Sodium α-sulfo fatty acid methyl ester Salt CMC-Na: Carboxymethyl cellulose sodium salt ES-Na: Sodium alkyl ether sulfate TAED: Tetraacetylethylenediamine

Test Example 4 Using the detergent compositions obtained in Formulations 3-15 to 3-25 and Comparative Formulation Examples 3-3 and 3-4, only the cleaning conditions were changed as follows, and Test Example 3 was performed. The test was conducted in the same manner as. (Washing conditions) Using a fully automatic washing machine (Matsushita Electric Industrial Co., Ltd., Aizuma), temperature 20 ° C, water 3.5 ° DH
(Ca / Mg = 3/1), detergent concentration 0.0833%,
Washed on the standard course. The results are also shown in Table 12.

[0077]

[Table 12]

Test Example 5 Using the detergent compositions obtained in Formulations 3-26 to 3-38 and Comparative Formulation Examples 3-5 and 3-6, only the cleaning conditions were changed as follows, and Test Example 3 was performed. The test was conducted in the same manner as. (Washing conditions) Rotation speed is 10 using a tergotometer.
0 rpm, washing time 10 minutes, temperature 20 ° C, water 3 ° D
Washing was performed with H (Ca / Mg = 3/1) and a detergent concentration of 0.0833%. The results are also shown in Table 13.

[0079]

[Table 13]

Test Example 6 Using the detergent compositions obtained in Formulations 3-39 to 3-49 and Formulation Comparative Examples 3-7 and 3-8, only the cleaning conditions were changed as follows, and Test Example 3 was performed. The test was conducted in the same manner as. (Washing conditions) Fully automatic washing machine (US Whirlpool
Manufactured by Model LA5580XT) at a temperature of 35 ° C., water 8 ° DH (Ca / Mg = 2/1), and a detergent concentration of 0.1%. The results are also shown in Table 14.

[0081]

[Table 14]

Test Example 7 Formulations 3-50 to 3-60 and Formulation Comparative Examples 3-9 and 3-10
A test was performed in the same manner as in Test Example 3 except that the cleaning conditions were changed as described below using the cleaning composition obtained in (1). (Washing conditions) Fully automatic washing machine (BOSCH WFK400
0, drum type), temperature 60 ° C, water 16 °
DH (Ca / Mg = 2/1) and a detergent concentration of 0.8% were used for washing in a standard course. The results are also shown in Table 15.

[0083]

[Table 15]

Test Example 8 Using the detergent compositions obtained in Formulations 3-61 to 3-68 and the detergent compositions obtained in Formulation Comparative Examples 3-11 to 3-12, the same as in Test Example 3 A washing test was similarly performed under washing conditions. The results are also shown in Table 16 together with the total amount of the cleaning composition, the amount used, the degree of concentration, and the pH before and after cleaning.

[0085]

[Table 16]

From the results shown in Tables 11 to 15, the detergent composition of the present invention was used in the case of using zeolite which has been conventionally used as a builder for detergents (Compounding Comparative Example 3-
It was found that the cleaning rate was equivalent to that of 1, 3, 5, 7, 9). Further, the cleaning rate was considerably improved as compared with the case where the inorganic builder was not used (Compounding Comparative Examples 3-2, 4, 6, 8, 10). Further, from the results of Table 16, the detergent composition (formulation 3-61 to 3-68) of the present invention is equivalent to the conventional formulation (formulation comparative example 3-11 to 3-12) in a smaller amount used. The cleaning performance of can be obtained. This is because the inorganic builder in the present invention is a multi-functional one having excellent ion exchange ability and alkaline ability. This is because the same cleaning performance can be obtained with a compounding amount smaller than the total amount.

[0087]

INDUSTRIAL APPLICABILITY The synthetic inorganic builder of the present invention is excellent in both cation exchange ability and water resistance, and is therefore useful as a water softening agent and an alkali adjusting agent used in, for example, detergents. Therefore, the detergent composition containing this,
It has excellent cleaning effect and is suitable for concentration of cleaning agent.

[Brief description of drawings]

FIG. 1 shows a spectrum obtained by Raman spectroscopy measurement. In the figure, (a) shows the inorganic builder 61 obtained in Example 61, and (b) shows the sodium disilicate (Na ₂ Si ₂ ) obtained in Comparative Example 1.
O ₅ ).

Claims (5)

(57) [Claims] 1. Anhydride is represented by the general formula: xM ₂ O.ySiO ₂
ZM 'O (however, M represents Na and / or K, and M'
Represents Ca and / or Mg, and y / x = 0.5 to 2.
0 and z / x = 0.005-1.0. ) In a synthetic inorganic builders having a composition represented, 900 cm ^-1
In Raman scattering spectra for a range of ~1200cm ^-1, synthetic inorganic builders showing a main shift peaks at least 970 ± 20 cm ^-1. 2. The synthetic inorganic builder according to claim ^{1, wherein} the main shift peak at 970 ± 20 cm ⁻¹ has an intensity ratio of 0.1 to 100 with respect to the shift peak at 1070 ± 30 cm ⁻¹ . 3. A cation exchange capacity of 200 to 600 Ca
The synthetic inorganic builder according to claim 1, which has CO ₃ mg / g. 4. The amount of Si eluted into water is 12 in terms of SiO _2.
The synthetic inorganic builder according to claim 1, which has an amount of 0 mg / g or less. 5. A hydrate of the synthetic inorganic builder according to claim 1.