JP3848757B2 - Inorganic composite - Google Patents

Description

【０１００】
実施例１１及び比較例６
以下の組成からなる洗浄剤組成物を調製した。
【０１０１】
（実施例１１の洗浄剤組成物）
ドデシルエーテル（ＥＯ付加モル７．０） １５％
直鎖アルキルベンゼンスルホン酸ナトリウム
（ＬＡＳ−Ｎａ） １５％
ゼオライト ４０％
実施例１で得られた無機複合体 ３０％
【０１０２】
（比較例６の洗浄剤組成物）
ドデシルエーテル（ＥＯ付加モル７．０） １５％
ＬＡＳ−Ｎａ １５％
ゼオライト ４０％
炭酸ナトリウム ３０％
【０１０３】
各洗浄剤組成物について、特開平７−２７０３９５号公報記載の製法で作成したグラビア汚染布を用い、洗浄時間１０分、洗浄剤濃度０．０６７％、水の硬度７１．４ｍｇＣａＣＯ₃ ／ｋｇ、水温２０℃で洗浄後、水道水で５分間すすぎを行い、洗浄前後の反射率の変化を自記色彩計（（株）島津製作所製）で測定後、以下の方法に従って洗浄率（Ｄ％）を求めた。その結果、比較例６の洗浄剤組成物中の炭酸ナトリウムの代わりに、実施例１で得られた無機複合体を使用した実施例１１の洗浄剤組成物の洗浄率は６５％であり、比較例６の洗浄剤組成物の洗浄率５５％と比較して優れた洗浄性能を示した。
【０１０４】
＜洗浄率の算出＞
Ｄ＝（Ｌ₂ −Ｌ₁ ）／（Ｌ₀ −Ｌ₁ ）×１００
Ｌ₀ ：グラビア原布の反射率
Ｌ₁ ：洗浄前のグラビア汚染布の反射率
Ｌ₂ ：洗浄後のグラビア汚染布の反射率
【０１０５】
【発明の効果】
本発明により、優れた水の軟化作用、酸抵抗性および保存安定性を有した無機複合体が提供される。かかる無機複合体は、例えば、脱硫剤、炭酸ガス除去剤、衣料用洗剤、柔軟剤、食器用洗剤、金属用洗浄剤、身体用洗剤、排水中和剤等の幅広い洗浄分野に使用することができる。
【図面の簡単な説明】
【図１】図１は実施例１で得られたＸ線回折の結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an inorganic composite mainly composed of an alkali carbonate and a cleaning composition containing the inorganic composite.
[0002]
[Prior art]
Conventionally, alkali carbonates having high saturation solubility in water have been used for a long time as various raw materials and alkali agents in each industrial field. However, the alkali carbonate generally has a disadvantage that its dissolution rate in water is slow.
[0003]
Among the alkali carbonates, potassium carbonate has a high dissolution rate in water, but has a high reactivity with moisture in the air and poor storage stability, so that it has a drawback that it is greatly restricted in use.
[0004]
In addition, sodium carbonate has a slow dissolution rate in water, but it is widely used as an alkali developer, for example, by utilizing the property of generating alkali ions and carbonate ions after formation of hydrates in water. Yes. However, since the alkalinity of the sodium carbonate is determined by the dissociation state of calcium carbonate in water, it is possible to increase the amount of sodium carbonate used in order to enhance the alkali expression effect with sodium carbonate alone. This has the disadvantage that it leads to an increase in the salt concentration in the water.
[0005]
Furthermore, when the sodium carbonate is used as a detergent for clothing that is becoming more compact, the theoretical calcium ion trapping capacity (Ca trapping capacity) is high, but the dissolution rate of sodium carbonate in water is low. As a result, there is a disadvantage that the Ca capturing speed is slow. For this reason, in order to enhance the alkali expression effect, it is necessary to increase the amount of sodium carbonate added, which is not practically preferable.
[0006]
In order to solve these problems, for example, Japanese Patent Application Laid-Open No. 59-190216 discloses a method for improving the dissolution rate in water by forming the sodium carbonate into a needle shape. However, this method has a disadvantage that it is inferior in storage stability because it reacts with moisture in the air.
[0007]
Japanese Patent Application Laid-Open No. 4-275400 discloses a method of preparing a cogranule of water glass and alkali carbonate in order to increase the dissolution rate in water. However, since water glass is inferior in hygroscopicity, it has a drawback that it is inferior in storage stability particularly under high humidity.
[0008]
In view of this, methods for adding calcium carbonate seed crystals to a detergent to increase the apparent reactivity of sodium carbonate are disclosed in JP-A-51-76198 and JP-A-62-240394. However, the method has drawbacks such as re-dissolution of calcium carbonate in water and re-adhesion of calcium carbonate to clothing.
[0009]
Further, a method using a double salt obtained by mixing and baking sodium carbonate and calcium salt as a builder is disclosed in WO96 / 38524. According to the above method, the storage stability of calcium carbonate is improved, and CaCO is used as a seed crystal._ThreeAttempts have been made to improve the ability to capture Ca in water and improve detergency. However, according to the above method, although the decomposability of the carbonate is improved, the Ca exchange capacity is reduced due to the decrease in sodium carbonate that captures the Ca component in the water and the residual calcium carbonate. There is a disadvantage that the performance is low.
[0010]
Such conventional methods cannot improve all the physical properties such as Ca capturing ability, acid durability, and storage stability, and development of a material that improves all of these physical properties is desired.
[0011]
[Problems to be solved by the invention]
The inorganic composite of the present invention has been made in view of the above prior art, and an object thereof is to provide an inorganic composite having excellent water softening action, acid durability and storage stability. Another object of the present invention is to provide a cleaning composition containing the inorganic composite.
[0012]
[Means for Solving the Problems]
  That is, the gist of the present invention is as follows.
(1) As a general formula of anhydride,
aM¹ CO_Three・ BM² O · c (M¹ , M² ) (An) m
(Where M¹ Is an alkali metal, M²Is an alkaline earth metal, An is an anion, and is represented by 0 <(b + c) / a ≦ 100, 0 <c / b ≦ 200, and m is 0-20.X-ray diffraction has peaks at d values of 0.300 ± 0.050 nm and 0.210 ± 0.020 nm.Inorganic composites,
(2) M¹ Is Na and / or K, and the composition ratio is 0 ≦ K / Na ≦ 100(1) NotesListed inorganic composites,
(3) M² Is Mg and / or Ca, and the composition ratio is 0 ≦ Ca / Mg ≦ 100 (1)Or (2)The inorganic composite according to the description,
(4) 0 <(b + c) / a ≦ 50, 0 <c / b ≦ 100, 0.01 ≦ K / Na ≦ 50 and 0 ≦ Ca / Mg ≦ 50(3)Any one of the inorganic composites,
(5) An is an anion composed of an element selected from the group consisting of groups IVb, Vb, VIb and VIIb of the periodic table.(4)Any one of the inorganic composites,
(6) An is OH^- , CO_Three ^2-, SO_Four ^2-, SO_Three ^2-, Cl^- , NO_Three ^- And PO_Four ^3-It is one or more kinds of anions selected from the group consisting of (1) to (1) above(5)Any one of the inorganic composites,
(7) The anhydrous form of the inorganic composite is aNa₂ CO_Three・ BMgO ・ cMgCl₂The inorganic composite according to (1) above, wherein 0.05 ≦ b / a ≦ 50 and 0 <c / b ≦ 100, and
(8) Said (1)-(7)Cleaning composition comprising any one of the inorganic composites
About.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The inorganic composite of the present invention has a general formula of anhydride as follows:
aM¹CO_Three・ BM²O · c (M¹, M²) (An) m
(Where M¹Is an alkali metal, M²Is an alkaline earth metal, An is an anion, and is represented by 0 <(b + c) / a ≦ 100, 0 <c / b ≦ 200, and m is 0-20.
[0014]
In the general formula of the anhydride, M¹Is an alkali metal, among which sodium and potassium atoms are widely used as industrially inexpensive raw materials, and sodium and potassium atoms are preferred from the viewpoint of economy.
[0015]
M¹Is Na and / or K, the K / Na value (molar ratio) is preferably 0 ≦ K / Na ≦ 100, more preferably 0 ≦ K / Na ≦ 80, 0.01 ≦ K / Na ≦ 50 is particularly preferred. That is, K / Na is 0 or more from the viewpoint of solubility in water, preferably 0.01 or more, and 100 or less from the viewpoint of storage stability under high humidity. Preferably it is 80 or less, especially 50 or less.
[0016]
In the general formula of the anhydride, M²Is an alkaline earth metal, and among them, a magnesium atom and a calcium atom are preferable from the viewpoints of cost and safety to living organisms.
[0017]
M₂When Mg is Mg and / or Ca, the Ca / Mg value (molar ratio) is preferably 0 ≦ Ca / Mg ≦ 100, more preferably 0 ≦ Ca / Mg ≦ 80, and 0 <Ca / Mg ≦ 50. Particularly preferred. That is, Ca / Mg is preferably 0 or more from the viewpoint of acid durability and solubility in water, and 100 or less, preferably 80 or less, particularly 50 from the viewpoint of Ca capturing ability. The following is desirable.
[0018]
In the general formula, An includes, for example, an anion composed of an element selected from the group consisting of groups IVb, Vb, VIb and VIIb of the periodic table. Among these, dispersibility in water and water From the viewpoint of solubility of OH^-, CO_Three ^2-, SO_Four ^2-, SO_Three ^2-, Cl^-, NO_Three ^-And PO_Four ^3-Is preferred.
[0019]
In the general formula of the anhydride, (b + c) / a value (molar ratio) is preferably 0 <(b + c) / a ≦ 100, more preferably 0 <(b + c) / a ≦ 50, 0.01 ≦ ( b + c) / a ≦ 50 is particularly preferable, and 0.05 ≦ (b + c) / a ≦ 40 is more preferable. That is, (b + c) / a is greater than 0, more preferably 0.01 or more, and even more preferably 0.05 or more, from the viewpoint of improving acid durability. Further, from the viewpoint of suppressing the amount of Ca and Mg eluted into water, it is desirable that the amount is 100 or less, preferably 50 or less, particularly 40 or less.
[0020]
In the general formula of the anhydride, the c / b value (molar ratio) is preferably 0 <c / b ≦ 200, more preferably 0 <c / b ≦ 100, and particularly preferably 0.01 ≦ c / b ≦ 100. Preferably, 0.03 ≦ c / b ≦ 50 is more preferable. That is, c / b is larger than 0, preferably 0.01 or more, particularly 0.03 or more, from the viewpoint of dispersibility in water and storage stability, and ionic strength in water. In view of the above, it is desirable that it is 200 or less, preferably 100 or less, particularly 50 or less.
[0021]
In the general formula of the anhydride, (M¹, M²) (An) m is M¹(An) m₁・ M²(An) m₂(M₁, M₂Is a number greater than or equal to 0 and m₁+ M₂= M. However, m₁, M₂Both are not zero. ), M¹(An) m₁, M²(An) m₂Each may have a single composition or two or more compositions. For example, M¹(An) m₁When there are two or more types, the total number of (An) is m₁It becomes. M²(An) m₂Similarly, when there are two or more, the total of (An) is m₂It becomes.
[0022]
The inorganic composite of the present invention is not particularly limited as long as it satisfies the above general formula. Among these, as examples of suitable ones, aNa₂CO_Three・ BMgO ・ cMgCl₂In which 0.05 ≦ b / a ≦ 50 and 0 <c / b ≦ 100.
[0023]
The inorganic composite of the present invention preferably has peaks at d values of 0.300 ± 0.050 nm and 0.210 ± 0.020 nm in X-ray diffraction. The inorganic compound having such characteristics is surprisingly excellent in physical properties such as water softening action, acid durability, and storage stability.
[0024]
As long as the inorganic composite having such a configuration does not impair the performance of the inorganic composite of the present invention, an inorganic compound may be further combined within a range that balances the charge of the inorganic composite.
[0025]
The inorganic compound is not particularly limited, and examples thereof include inorganic compounds containing elements such as Al, B, Si, C, Zn, Ag, Au, Fe, Zr, Ti, and Y. Examples thereof include sulfates, chlorides, nitrates, phosphates, silicates, carbonates, hydroxides of these elements, and clay minerals such as zeolite, talc, and alum. The inorganic compound can be usually combined alone or in combination of two or more with the inorganic composite or by reacting with the inorganic composite.
[0026]
The inorganic composite of the present invention is excellent in Ca trapping capacity, Ca trapping speed, acid durability and storage stability.
[0027]
The Ca trapping capacity is the amount of calcium ions trapped by 1 g of the inorganic composite after adding the inorganic composite to the calcium chloride aqueous solution and stirring, and expressed in mg in terms of calcium carbonate. The Ca capture capacity of the inorganic composite of the present invention is 50 mg CaCO._Three/ G or more, preferably 100 mg CaCO_Three/ G or more is more preferable.
[0028]
The Ca trapping rate is the amount of calcium ions trapped per minute by 1 g of the inorganic composite expressed in mg in terms of calcium carbonate. The Ca capture rate of the inorganic composite of the present invention is 40 mg CaCO._Three/ G / min or more, 50 mg CaCO_Three/ G / min or more, preferably 60 mg CaCO_ThreeMore preferably, it is at least / g / min.
[0029]
Acid durability is 0.1 mol / dm in a solution containing an inorganic composite.^ThreeWhen hydrochloric acid is added dropwise, the amount of hydrochloric acid added to reach pH of 10 is expressed. The acid durability of the inorganic composite of the present invention is 50 ml / g or more, preferably 60 ml / g or more, more preferably 65 ml / g or more.
[0030]
The storage stability is determined by adding an inorganic composite stored for 24 hours under an atmospheric temperature of 30 ° C. and an atmospheric humidity of 80 RH relative to the sieve after adding it to water, and drying the inorganic composite remaining on the sieve. Expressed as a percentage by weight. The storage stability of the inorganic composite of the present invention is preferably less than 4%, more preferably less than 2%, based on the dry weight of the remaining inorganic composite.
[0031]
Examples of the raw material used for producing the inorganic composite of the present invention include inorganic compounds containing alkali metals such as sodium and potassium and inorganic compounds containing alkaline earth metals such as magnesium and calcium.
[0032]
Examples of the inorganic compound containing an alkali metal include carbonates such as sodium carbonate, potassium carbonate, sodium potassium carbonate, sesquicarbonate, potassium sesquicarbonate; bicarbonates such as sodium bicarbonate, potassium bicarbonate; sodium chloride Chlorides such as potassium chloride; nitrates such as sodium nitrate and potassium nitrate; sulfates such as sodium sulfate and potassium sulfate; sulfites such as sodium sulfite and potassium sulfite; silicates such as sodium silicate and potassium silicate; sodium phosphate and phosphoric acid Examples thereof include phosphates such as potassium; hydroxides such as sodium hydroxide and potassium hydroxide; oxides such as sodium oxide and potassium oxide; minerals such as alum. The said inorganic compound is normally independent, or 2 or more types can be used, and when using 2 or more types, it can be used in arbitrary ratios.
[0033]
Examples of the inorganic compound containing an alkaline earth metal include carbonates such as magnesium carbonate and calcium carbonate; hydrogen carbonates such as magnesium hydrogen carbonate and calcium hydrogen carbonate; bases such as basic magnesium carbonate and basic calcium carbonate Carbonates; chlorides such as magnesium chloride and calcium chloride; nitrates such as magnesium nitrate and calcium nitrate; sulfates such as magnesium sulfate and calcium sulfate; sulfites such as magnesium sulfite and calcium sulfite; magnesium silicate and calcium silicate Examples thereof include silicates; phosphates such as magnesium phosphate and calcium phosphate; hydroxides such as magnesium hydroxide and calcium hydroxide; oxides such as magnesium oxide and calcium oxide; minerals such as dolomite, talc and forsterite. The inorganic compounds can be used singly or in combination of two or more. When two or more are used in combination, they can be used in any ratio.
[0034]
The inorganic composite of the present invention can be obtained by mixing and mixing the various raw material compounds in a predetermined ratio. About the ratio of a mixing | blending, it determines suitably by the composition of the desired desired inorganic composite.
[0035]
As a method of blending the raw materials, any method that is generally used may be used, for example, either dry or wet, and as a state at the time of blending, for example, a powder state, a paste state, a slurry state, Examples include a solution state.
[0036]
In the case of wet processing, the raw material and liquid may be mixed. The liquid is not particularly limited as long as it is generally used. For example, water is preferable from the viewpoint of economy and the environment.
[0037]
Next, the blend is mixed. The method used for mixing the compound is not particularly limited as long as it is a generally used method. For example, a mixer including a medium such as a Henschel mixer, a high speed mixer, a ball mill, an attrition mill, etc. Etc. The temperature of the atmosphere at the time of mixing is preferably within the range where the blend exhibits fluidity, and is usually at room temperature or higher, but can be mixed while heating to about 50 ° C. as necessary.
[0038]
When mixing a compound, it is preferable to carry out in a carbon dioxide gas concentration atmosphere of 0.03% by weight or more from the viewpoint of suppressing decomposition of the resulting inorganic composite. The mixing time is not particularly limited, but it is preferably 0.5 to 24 hours. Moreover, in order to improve the reactivity of the said compound, you may bubble atmospheric gas, such as a carbon dioxide gas, in a mixture.
[0039]
If necessary, the raw material compounds may be melted and mixed uniformly. The conditions for melting the raw material are not particularly limited as long as the composition of the resulting inorganic composite as an anhydride can be maintained, and need not be completely melted. The uniform mixing operation is usually performed for 0.5 to 24 hours in an atmosphere containing a carbon dioxide gas concentration of 0.03% by weight or more.
[0040]
Moreover, when a liquid is included in the mixing, the blend may be dried so that the mixing operation is facilitated. In this case, it is usually preferable to dry so that the liquid concentration is 20% by weight or less. The drying method is not particularly limited, and examples thereof include freeze-drying, vacuum drying, hot air drying, and the like. Specifically, the composition is granulated using a spray dryer, a rotary drum dryer, or the like. Can be dried to form.
[0041]
Next, the mixture obtained as described above may be heat-treated for the purpose of improving the performance of the obtained inorganic composite. Although the temperature of the heat treatment varies depending on the elements constituting the mixture, these are reacted to precipitate a reaction product of the solid solution or the elements of the mixture, and from the viewpoint of acid durability, it is 200 ° C. or higher, and 300 ° C. or higher. In view of the decomposability and operability of the inorganic composite, it is preferably 1000 ° C. or less, preferably 900 ° C. or less, and preferably 800 ° C. or less. More preferably it is.
[0042]
Moreover, it is preferable to perform heat processing for 0.5 to 24 hours in carbon dioxide gas concentration atmosphere 0.03 weight% or more from a viewpoint which suppresses decomposition | disassembly or decomposition | disassembly of the inorganic composite produced | generated by reaction.
[0043]
As a heating method at the time of heat treatment, for example, a method of heating a furnace by an internal heating method using electricity, gas or the like, an external heating method, or the like can be given. The form of the furnace is not particularly limited as long as it is generally used, and examples thereof include a rotary kiln, a shuttle kiln, a tunnel kiln, and a fluidized bed kiln.
[0044]
Since the particle diameter of the inorganic composite of the present invention varies depending on the application, it cannot be generally limited. For example, in applications where the performance of the inorganic composite needs to be expressed quickly, it is 5.0 mm or less. Is preferred. Moreover, the inorganic composite of this invention can be granulated by drying to the granular form of arbitrary magnitude | sizes from a viewpoint of improving a dispersibility and the solubility to water. Specific examples of the granulation method include apparatuses such as a spray dryer and a rotary drum dryer.
[0045]
During granulation, a binder component can be blended within a range that does not impair the performance of the inorganic composite. Examples of the binder component include surfactants, fatty acids, carboxymethylcellulose, polyethylene glycol, polyacrylates, starches and other polysaccharides, polyvinyl alcohol and other organic binders, amorphous silicates, smectite group inorganic binders, and the like. Can be given. In addition, these binder components can be used alone or in combination of two or more. When two or more are mixed and used, they can be used in any ratio.
[0046]
In addition, the inorganic composite of the present invention is easily dispersed in an inorganic substance such as alumina or silica, an organic substance such as PVA, cellulose, or starch, or a separately granulated particle, for example, a granulated product of a powder detergent. Can be coated.
[0047]
The inorganic composite of the present invention has excellent water softening action, high resistance to acid, and excellent storage stability.For example, a desulfurizing agent, a carbon dioxide removing agent, a detergent for clothing, It can be used in a wide range of fields such as softeners, dishwashing detergents, metal cleaners, body cleaners, and wastewater neutralizers.
Next, the cleaning composition containing the inorganic composite of the present invention will be described.
[0048]
The blending amount of the inorganic composite in the cleaning composition is 0.5% by weight or more, preferably 1% by weight or more from the viewpoint of the form of the product, the acid load under the environment used, and the amount of the hardness component. In addition, from the viewpoint of imparting a function with other additives, it is preferably 90% by weight or less, and preferably 80% by weight or less.
[0049]
In addition to the inorganic composite, the cleaning composition includes surfactants, amorphous and / or crystalline silicates, amorphous and / or crystalline aluminosilicates, inorganic electrolytes such as sodium sulfate, tripolyphosphoric acid Chelating agents such as sodium, EDTA, aminopolyacetate, polyacrylate, anti-staining agents such as carboxymethylcellulose, enzymes such as protease, lipase, cellulase, amylase, such as tertiary butylhydroxytoluene, monostyrenated cresol, mono Antioxidants such as styrenated phenols, for example, fluorescent dyes such as Whiteex SA (manufactured by Sumitomo Chemical Co., Ltd.), Chino Pearl CBS (manufactured by Ciba Geigy), Japanese Patent Publication No. 49-8005, Japanese Patent Publication No. 49-26286 And a bluing agent described in JP-B-53-45808, etc. Is the perfume can be formulated as needed perfumes described in, for example JP 63-101496 Patent Publication.
[0050]
Moreover, as a surface modifier, inorganic powders, such as an aluminosilicate and a calcium carbonate, can be mix | blended suitably, for example. When the detergent composition is used as a bleach detergent, for example, bleaching agents such as sodium percarbonate, sodium pernitrate monohydrate and sodium pernitrate tetrahydrate, and stabilization of peroxides such as magnesium silicate For example, a bleaching activator described in JP-A-59-22999, JP-A-63-258447, JP-A-6-316700 and the like can be blended. Moreover, you may mix | blend the inorganic composite of this invention by converting into a peroxide.
[0051]
Examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more at any ratio. Can be used.
[0052]
Specific examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethyl salts.
[0053]
Specific examples of the anionic surfactant include, for example, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt, alkyl or alkenyl. Examples include ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, and the like.
[0054]
Specific examples of the nonionic surfactant include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene glycol fatty acid Examples include alkyl esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene castor oil, polyoxyethylene alkylamines, glycerin fatty acid esters, higher fatty acid alkanolamides, alkyl glucosides, alkyl glucose amides, and alkyl amine oxides.
[0055]
Specific examples of the amphoteric surfactant include a carboxy type or a sulfobetaine type.
[0056]
The blending amount of the surfactant in the cleaning composition of the present invention cannot be generally limited depending on the type of the surfactant, but is, for example, 0.5% by weight or more and 1% by weight from the viewpoint of cleaning properties. Preferably, the amount is 3% by weight or more, more preferably 99% by weight or less and 80% by weight or less from the viewpoint of imparting other functions such as water softening action. Preferably, it is 70% by weight or less.
[0057]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by this Example etc.
[0058]
In addition, (1) Ca capturing capacity and (2) acid durability were measured and evaluated by the following methods. The results are shown in Table 1.
[0059]
(1) Ca capture capacity
A sample 0.04 g is precisely weighed and an aqueous calcium chloride solution (concentration is CaCO_ThreeAs 100 ppm), and after stirring at 20 ° C. for 10 minutes, filtration is performed using a membrane filter (Advantech, manufactured by Nitrocellulose) having a pore size of 0.2 μm, and the amount of Ca contained in 10 ml of the filtrate is determined. Measured by EDTA titration. From this value, the calcium ion exchange capacity (cation exchange capacity) of the sample was determined as the Ca trapping capacity.
[0060]
Based on the following criteria, the value of each sample was evaluated in three stages of A to C in descending order of Ca capture capacity.
[0061]
A: 100 mg CaCO_ThreeLarger than / g.
B: 50-100 mg CaCO_Three/ G.
C: 50 mg CaCO_Three/ G or less.
[0062]
(2) Acid durability
Calcium chloride is dissolved in ion-exchanged water so that it is 71.4 mg / kg in terms of calcium carbonate, 1000 ml of the calcium chloride aqueous solution is kept at a water temperature of 20 ° C., and 0.17 g of a sample is added thereto for 2 minutes. After stirring, 0.1 mol / dm at 30 second intervals^ThreeThe hydrochloric acid was added dropwise every 0.5 ml, and the acid durability of the sample was shown by the amount of hydrochloric acid required for the pH of the aqueous solution to be 10.
[0063]
Based on the following criteria, the value of each sample was evaluated in three stages of A to C in descending order of acid durability.
[0064]
A: Larger than 60 ml / g.
B: 50-60 ml / g.
C: Less than 50 ml / g.
[0065]
Example 1
After mixing 11.4 g of magnesium hydroxide powder, 39.8 g of 10% magnesium chloride hexahydrate aqueous solution and 114 g of 20% sodium carbonate aqueous solution with stirring, the mixture was heated to 400 ° C. in a hot air dryer ( Heat treatment was performed for 2 hours in Motoyama Co., Ltd. (DC-6060).
[0066]
38 g of the obtained powdery inorganic composite was pulverized with an agate mortar so that the particle diameter was 125 μm or less. The particle size was measured using a laser diffraction particle size distribution measuring device (LA-710, manufactured by Horiba, Ltd.).
[0067]
The composition of the obtained inorganic composite is M¹Is the sodium atom, M²Is magnesium atom, An is Cl^-(B + c) / a is 1 and c / b value is 0.1, and when X-ray diffraction was performed using an X-ray diffractometer (RAD-C, manufactured by Rigaku Corporation), The d value had peaks at 0.296 nm and 0.205 nm. The X-ray diffraction chart is shown in FIG. The same X-ray diffraction apparatus was used in the following examples.
[0068]
The obtained inorganic composite has a Ca trapping capacity of 185 mg CaCO._Three/ G, acid durability was 89 ml / g. Moreover, the dispersibility in water was also favorable.
[0069]
Example 2
Magnesium hydroxide powder 8.4 g, magnesium carbonate powder 6.0 g and 20% aqueous sodium carbonate solution 114 g were mixed with stirring to obtain 33 g of a powdery inorganic composite in the same manner as in Example 1.
[0070]
The composition of the obtained inorganic composite is M¹Is the sodium atom, M²Is magnesium atom, An is CO_Three ^2-(B + c) / a was 1 and the c / b value was 0.5, and the X-ray diffraction had peaks at d values of 0.297 nm and 0.216 nm.
[0071]
The obtained inorganic composite has a Ca capture capacity of 178 mg CaCO._Three/ G, acid durability was 91 ml / g, and dispersibility in water was also good.
[0072]
Example 3
2.9 g of magnesium hydroxide powder, 21.2 g of magnesium carbonate powder and 80 g of 20% aqueous sodium carbonate solution were mixed with stirring, and in the same manner as in Example 1, 37 g of a powdery inorganic composite was obtained.
[0073]
The composition of the obtained inorganic composite is M¹Is the sodium atom, M²Is magnesium atom, An is CO_Three ^2-(B + c) / a is 2 and c / b value is 5, and X-ray diffraction has peaks at d values of 0.297 nm and 0.218 nm.
[0074]
The obtained inorganic composite has a Ca trapping capacity of 153 mg CaCO._Three/ G, acid durability was 95 ml / g, and dispersibility in water was also good.
[0075]
Example 4
As Mg raw materials, 0.2 g of magnesium hydroxide powder, 1.8 g of magnesium sulfate powder and 150 g of 20% aqueous sodium carbonate solution were mixed with stirring, and 28 g of powdered inorganic composite was obtained in the same manner as in Example 1. .
[0076]
The composition of the obtained inorganic composite is M¹Is the sodium atom, M²Is magnesium atom, An is SO_Four ^2-(B + c) / a was 0.1 and c / b value was 10, and in X-ray diffraction, peaks were observed at d values of 0.302 nm and 0.221 nm.
[0077]
The obtained inorganic composite has a Ca capturing capacity of 230 mg CaCO._Three/ G, acid durability was 51 ml / g, and dispersibility in water was also good.
[0078]
Example 5
1.3 g of magnesium hydroxide powder, 15.0 g of calcium sulfate powder and 70 g of 20% aqueous sodium carbonate solution were mixed with stirring, and in the same manner as in Example 1, 27 g of a powdery inorganic composite was obtained.
[0079]
The composition of the obtained inorganic composite is M¹Is the sodium atom, M²Is magnesium atom and calcium atom, An is SO_Four ^2-(B + c) / a is 1 and c / b value is 5, and X-ray diffraction has peaks at d values of 0.300 nm and 0.217 nm.
[0080]
The obtained inorganic composite has a Ca trapping capacity of 157 mg CaCO._Three/ G, acid durability was 63 ml / g, and dispersibility in water was also good.
[0081]
Example 6
Magnesium hydroxide powder (1.8 g), calcium hydroxide powder (11.7 g) and 20% aqueous sodium carbonate solution (100 g) were mixed with stirring to obtain 30 g of a powdery inorganic composite as in Example 1.
[0082]
The composition of the obtained inorganic composite is M¹Is the sodium atom, M²Is magnesium atom and calcium atom, An is OH^-(B + c) / a is 1 and c / b value is 5, and X-ray diffraction has peaks at d values of 0.297 nm and 0.215 nm.
[0083]
The obtained inorganic composite has a Ca trapping capacity of 152 mg CaCO._Three/ G, acid durability was 95 ml / g, and dispersibility in water was also good.
[0084]
Example 7
Magnesium carbonate powder 19.9 g, calcium hydroxide powder 17.5 g and 20% aqueous sodium carbonate solution 50 g were mixed with stirring to obtain 42 g of a powdery inorganic composite in the same manner as in Example 1.
[0085]
The composition of the obtained inorganic composite is M¹Is the sodium atom, M²Is magnesium atom and calcium atom, An is CO_Three ^2-(B + c) / a is 5 and c / b value is 1, and in X-ray diffraction, peaks were observed at d values of 0.299 nm and 0.213 nm.
[0086]
The obtained inorganic composite has a Ca trapping capacity of 103 mg CaCO._Three/ G, acid durability was 105 ml / g, and dispersibility in water was also good.
[0087]
Example 8
20 g of 20% potassium carbonate aqueous solution as K raw material and 2.0 g of magnesium carbonate and 1.4 g of magnesium hydroxide as Mg raw material together with 50 g of 20% sodium carbonate aqueous solution, mixed and ground for 24 hours with a ball mill, and then using a Ni crucible Then, baking was performed at 500 ° C. for 2 hours in an electric furnace to obtain 12 g of an inorganic composite.
[0088]
The composition of the obtained inorganic composite is M¹Are sodium and potassium atoms, M²Is magnesium atom, An is CO_Three ^2-(B + c) / a was 0.5 and c / b value was 1, and in X-ray diffraction, peaks were observed at d values of 0.304 nm and 0.214 nm.
[0089]
The obtained inorganic composite has a Ca capturing capacity of 155 mg CaCO._Three/ G, acid durability was 86 ml / g, and dispersibility in water was also good.
[0090]
Example 9
K raw material 3.3g 20% potassium carbonate aqueous solution and Mg raw material 66.3g magnesium carbonate and 9.2g magnesium hydroxide together with 50% 20% sodium carbonate aqueous solution 50g mixed and ground for 24 hours in a ball mill, then Ni crucible Used and baked at 500 ° C. for 2 hours in an electric furnace to obtain 77 g of an inorganic composite.
[0091]
The composition of the obtained inorganic composite is M¹Are sodium and potassium atoms, M²Is magnesium atom, An is CO_Three ^2-(B + c) / a is 10 and c / b value is 5, and in X-ray diffraction, they have d values of 0.305 nm and 0.215 nm.
[0092]
The obtained inorganic composite has a Ca trapping capacity of 85 mg CaCO._Three/ G, acid durability was 141 ml / g, and dispersibility in water was also good.
[0093]
Example 10
3.3 g of 20% potassium carbonate aqueous solution and 22.9 g powder of 10% magnesium hydroxide slurry, 58.4 g of magnesium nitrate and 5 g of 20% sodium carbonate aqueous solution were mixed with stirring. An inorganic composite 58 g was obtained.
[0094]
The composition of the obtained inorganic composite is M¹Are sodium and potassium atoms, M²Is magnesium atom, An is NO_Three ^-(B + c) / a is 50 and c / b value is 5, and the X-ray diffraction has peaks at d values of 0.302 nm and 0.212 nm.
[0095]
The obtained inorganic composite has a Ca trapping capacity of 65 mg CaCO._Three/ G, acid durability was 150 ml / g, and dispersibility in water was also good.
[0096]
Comparative Examples 1-5
Sodium carbonate (Comparative example 1), Sodium potassium carbonate (K / Na = 1) (Comparative example 2), Potassium carbonate (Comparative example 3), Magnesium carbonate (Comparative example 4), Calcium carbonate (Comparative example 5) (All ( Each physical property value was measured in the same manner as in Example 1 using Wako Pure Chemical Industries, Ltd.).
[0097]
Ca capture capacities were 234, 233, 234, 0 and 0 mg CaCO in Comparative Examples 1-5, respectively._Three/ G. The acid durability was 47, 47, and 47 ml / g in Comparative Examples 1 to 3, respectively. Further, in X-ray diffraction, no peak was observed at d value of 0.210 ± 0.020 nm in Comparative Examples 1 to 3.
[0098]
The evaluation results of Examples 1 to 10 and Comparative Examples 1 to 5 are shown in Table 1. From these results, the inorganic composites obtained in Examples 1 to 10 have acid durability compared to Comparative Examples 1 to 5. It can be seen that it is excellent not only in Ca but also in Ca capturing capacity.
[0099]
[Table 1]

[0100]
Example 11 and Comparative Example 6
A cleaning composition having the following composition was prepared.
[0101]
(Cleaning agent composition of Example 11)
Dodecyl ether (EO addition mole 7.0) 15%
Sodium alkylbenzene sulfonate
(LAS-Na) 15%
Zeolite 40%
30% inorganic composite obtained in Example 1
[0102]
(Cleaning composition of Comparative Example 6)
Dodecyl ether (EO addition mole 7.0) 15%
LAS-Na 15%
Zeolite 40%
Sodium carbonate 30%
[0103]
For each detergent composition, using a gravure-contaminated cloth prepared by the method described in JP-A-7-270395, washing time 10 minutes, detergent concentration 0.067%, water hardness 71.4 mgCaCO_Three/ Kg, after washing at a water temperature of 20 ° C., rinsing with tap water for 5 minutes, and measuring the change in reflectance before and after washing with a self-recording colorimeter (manufactured by Shimadzu Corporation), followed by the washing rate (D %). As a result, the cleaning rate of the cleaning composition of Example 11 using the inorganic composite obtained in Example 1 instead of sodium carbonate in the cleaning composition of Comparative Example 6 was 65%. The cleaning performance of the cleaning composition of Example 6 was excellent as compared with a cleaning rate of 55%.
[0104]
<Calculation of cleaning rate>
D = (L₂-L₁) / (L₀-L₁) × 100
L₀: Reflectivity of gravure fabric
L₁: Reflectivity of gravure-contaminated cloth before cleaning
L₂： Reflectance of gravure-contaminated cloth after washing
[0105]
【The invention's effect】
The present invention provides an inorganic composite having excellent water softening action, acid resistance, and storage stability. Such inorganic composites can be used in a wide range of cleaning fields such as desulfurization agents, carbon dioxide removal agents, detergents for clothing, softeners, tableware detergents, metal cleaners, body cleaners, and wastewater neutralizers. it can.
[Brief description of the drawings]
FIG. 1 is a graph showing the results of X-ray diffraction obtained in Example 1. FIG.

Claims (8)

As a general formula of anhydride,
_{^{aM 1 CO 3 · bM 2 O}} · c (M 1, M 2) (An) m
(In the formula, M ¹ represents an alkali metal, M ² represents an alkaline earth metal, An represents an anion, 0 <(b + c) / a ≦ 100, 0 <c / b ≦ 200, and m is 0 to 20). in represented in X-ray diffraction, inorganic complexes you characterized by having a peak at d values 0.300 ± 0.050nm and 0.210 ± 0.020nm. M ¹ is Na and / or K, an inorganic composite of claim 1 Symbol mounting, characterized in that the composition ratio is 0 ≦ K / Na ≦ 100. The inorganic composite according to claim 1 or 2, wherein M ² is Mg and / or Ca, and the composition ratio is 0 ≦ Ca / Mg ≦ 100. 0 <(b + c) / a ≦ 50,0 < claim 1-3, wherein any one, which is a c / b ≦ 100,0.01 ≦ K / Na ≦ 50 and 0 ≦ Ca / Mg ≦ 50 Inorganic composite. An inorganic complex according to any one of claims 1 to 4 , wherein An is an anion composed of an element selected from the group consisting of groups IVb, Vb, VIb and VIIb of the periodic table. An is one or more anions selected from the group consisting of OH ⁻ , CO ₃ ²⁻ , SO ₄ ²⁻ , SO ₃ ²⁻ , Cl ⁻ , NO ₃ ⁻ and PO ₄ ^3−. Item 6. The inorganic composite according to any one of Items 1 to 5 . 2. The inorganic composite according to claim 1, wherein the anhydrous formula of the inorganic composite is aNa ₂ CO ₃ .bMgO.cMgCl ₂ , and 0.05 ≦ b / a ≦ 50 and 0 <c / b ≦ 100. body. Detergent composition comprising inorganic composite according to any one of claims 1-7.

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