JPH0437119B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a bleaching detergent composition with excellent storage stability. More specifically, the present invention relates to a bleaching detergent composition containing sodium percarbonate whose surface is coated with a coating agent containing a borate and a magnesium compound. Sodium percarbonate is known as a bleaching agent or oxidizing agent, and along with sodium perborate, it is a typical oxygen-based bleaching agent, and is generally produced by reacting hydrogen peroxide with soda carbonate. General formula 2Na ₂
It is expressed as CO _{3.3H 2} O ₂ . Soda percarbonate has slightly less bleaching power at room temperature than chlorine bleach, but it does not cause yellowing even when applied to synthetic fibers, animal fibers, resin-treated fibers, or fibers treated with fluorescent brighteners. It has the advantage of not causing any damage to the fabric, and it can also achieve a sufficient bleaching effect by applying heat or using a decomposition accelerator, so it is especially suitable for home and commercial use as a bleaching agent. It is used. The reason why soda percarbonate is attracting attention as a general detergent and household bleach is that its decomposition products are non-polluting and can be put to practical use in any way without any problems. However, compared to sodium perborate, sodium percarbonate has a major disadvantage in that it has considerably poorer storage stability and loses effective oxygen rather quickly during storage. Soda percarbonate has a strong affinity for water, so even the slightest amount of moisture causes its surface to absorb moisture and decompose, resulting in iron, copper, manganese,
When ions such as cobalt are present, the decomposition is further accelerated and its stability is inferior to that of sodium perborate. When sodium percarbonate is stored alone in an airtight container, its storage stability is no different from that of sodium perborate, but if it is mixed with detergent or left unopened, sodium percarbonate is highly hygroscopic. , its storage stability is poor. Furthermore, there is concern that sodium tripolyphosphate (STPP), which has been conventionally used as a builder in detergents, may cause eutrophication and cause environmental pollution, especially in closed water bodies. For this reason, the demand for low-phosphorus or no-phosphorus detergents is increasing.
Synthetic zeolite (aluminosilicate) is becoming widely used as a substitute for STPP in low-phosphorus and phosphorus-free detergents. However, the sodium percarbonate in detergents containing zeolite is extremely unstable, and the sodium percarbonate in phosphorus-free detergents containing zeolite rapidly loses effective oxygen and decomposes due to the catalytic decomposition action of zeolite. I will do it. For this reason, there has been a strong desire to develop a technology that can reduce the phosphorus content in detergents or eliminate phosphorus, and improve the storage stability of the sodium percarbonate used in detergents. Conventionally, methods proposed for stabilizing soda percarbonate include coating it with paraffin or polyethylene glycol with a molecular weight of 3,000 to 8,000, but the former greatly reduces its solubility in water. However, it is not practical, and although the latter is soluble in water, it is not effective for long-term stabilization because polyethylene glycol itself has considerable hygroscopicity. Another method is to include at least two stabilizers selected from phosphoric acids, silicic acids, ethylenediaminetetraacetate, and nitrilotriacetate in the hydrogen peroxide aqueous solution when producing sodium percarbonate. Although proposed, these stabilizers, while effective at temperature, have no practical stabilizing effect on moisture or detergent blends. There is also a method of uniformly coating soda percarbonate with sodium pyrophosphate, but this method also has a low decomposition rate against heat, but
It is not sufficient in its stabilizing effect on moisture and formulation in detergents. The object of the present invention is to provide a bleaching detergent containing sodium percarbonate that is stabilized even when blended with detergents, especially low-phosphorus or phosphorus-free detergents, until practical use. As a result of intensive research with this aim in mind, the present inventors have discovered that sodium percarbonate, which is incorporated into bleaching detergents, contains both borates and magnesium compounds such as magnesium sulfate, magnesium silicate, magnesium chloride, and magnesium oxide. The present invention was completed based on the discovery that the above object can be achieved by coating with a coating agent containing the following. That is, in the bleach cleaning agent according to the present invention, the sodium percarbonate compounded is stabilized by being coated with a coating agent containing a borate and a magnesium compound. The borate is preferably sodium boric acid, more preferably sodium metaborate, and the magnesium compounds include magnesium chloride, magnesium oxide,
One or more types of magnesium sulfate, magnesium silicate, etc. are preferably used. The coating may also contain sequestering agents such as ethylenediaminetetraacetate, nitrilotriacetate, and the like. The ratio of coating agent to soda percarbonate to be blended is
The proportion of borate in the coating is preferably 10 to 95% by weight, and the proportion of magnesium compound is preferably 5 to 70% by weight. It is generally preferred that the amount of magnesium compound is equal to or less than the amount of borate. Magnesium compounds are substances widely used as peroxide stabilizers. Soda percarbonate is also known to be used as a stabilizer for the mother liquor during reaction crystallization, or to be stabilized by simply mixing it with sodium percarbonate. however,
These methods do not provide sufficient effects in the zeolite-containing phosphorus-free detergent described above. Also Tokko Akira
47-32519 describes that magnesium sulfate, magnesium oxide, and magnesium chloride are blended as stabilizers for sodium percarbonate, and that this blend is granulated using polyethylene glycol as a binder. Granulating sodium percarbonate with a binder as described therein is an effective means for stabilizing sodium percarbonate in zeolite-containing phosphorus-free detergents. In other words, the stabilizing effect of the magnesium compound and the stabilizing effect of granulation work synergistically, and excellent storage stability can be expected even in phosphorus-free detergents containing zeolite. However, when organic binders such as those found in the polyethylene glycol of Japanese Patent Publication No. 47-32519 are used with peroxides such as sodium percarbonate, there is a very high risk of ignition during the manufacturing process. It is also known to use boric acids as a peroxide-coated granulating agent to be incorporated into bleaching detergents. For example, British Patent No. 1575792 describes boric acid (orthoboric acid, metaboric acid,
Tetraboric acid) is disclosed. Also, special public service in 1977
In Japanese Patent No. 6760, metaboric acid is added to a hydrogen peroxide adduct to improve storage stability. However, these known publications do not disclose at all the coating of peroxide with borate as in the present invention. The present inventor first discovered that coating with borate has excellent spreadability and that coating efficiency of sodium percarbonate is extremely excellent, and that powdery or It has been found that the storage stability of granular sodium percarbonate is much better than that of boric acid. (Special application 1982-99826
However, as a result of further research, the present inventors found that
When a magnesium compound is used together with a borate, as described above, due to the synergistic effect of the coating ability of the borate and the stabilizing ability of the magnesium compound, coated soda percarbonate with even better storage stability is obtained, and this is powdered. By blending it into a bleaching detergent of the present invention, a bleaching detergent of the present invention having exceptionally excellent storage stability was completed. According to the present invention, by using a borate salt, it is possible to avoid the dangers in the manufacturing process, such as when using the above-mentioned organic binder. The borate and magnesium compounds used in the coating of sodium percarbonate according to the present invention include the following: That is, as borates, sodium tetraborate decahydrate (borax _{Na 2} O.2B ₂ O 3.10H ₂ O) and sodium tetraborate pentahydrate (Na _{2 O.2B 2} O 3.5H ₂ O), sodium tetraborate tetrahydrate (Na ₂ O・2B ₂ O ₃・4H ₂ O), (anhydrous)
Sodium tetraborate (Na ₂ O・2B ₂ O ₃ ), Sodium octaborate tetrahydrate (Na ₂ O・4B ₂ O ₃・4H ₂ O), Sodium pentaborate pentahydrate (Na ₂ O・5B ₂ O ₃・10H ₂
O), sodium metaborate tetrahydrate (NaBO ₂ 4H ₂
O), sodium metaborate dihydrate (NaBO ₂ 2H ₂
Among these, particularly preferred are sodium metaborate dihydrate and sodium metaborate 4
It is water salt. As the magnesium compound, anhydrous or hydrated salts of magnesium sulfate, magnesium chloride, magnesium oxide, magnesium hydroxide, magnesium silicate, magnesium nitrate, magnesium phosphate, magnesium carbonate, etc., or magnesium salts of various organic acids can also be used. Among these, particularly preferred are anhydrous or hydrated salts of magnesium sulfate, magnesium chloride, magnesium oxide, and magnesium silicate. The sodium percarbonate coating agent used in the present invention may contain various organic or inorganic compounds in combination with the above-mentioned borates and magnesium compounds. Examples include inorganic compounds such as soda carbonate and mirabilite, organic polymer compounds such as polyethylene glycol, polyvinylpyrrolidone, and hydroxypropyl cellulose, but metals such as nitrilotriacetate and ethylenediaminetetraacetate are included in the coating material. An ion sequestering agent may also be included. The amount of sequestering agent contained is preferably 0.01 to 3% by weight based on the sodium percarbonate. The coating process using a coating agent containing a borate of sodium percarbonate and a magnesium compound used in the present invention can be carried out by a conventional method. For example, a method may be used in which a coating solution or powder is uniformly mixed and adsorbed on wet or dry sodium percarbonate powder or granules, and then dried. The coated soda percarbonate is preferably a powder with an average particle size of 100 to 2000 microns, preferably 250 to 1000 microns. Soda percarbonate coated as described above has excellent storage stability even when incorporated into ordinary powder cleaning agents (spray-dried products), especially low-phosphorus or no-phosphorus detergents containing zeolite. shows. The bleaching detergent composition of the present invention is obtained by incorporating 1 to 40% by weight of the coated sodium percarbonate thus obtained into a powder detergent. Additionally, the coated sodium percarbonate used in the present invention has significantly improved storage stability and is therefore less susceptible to other detergent formulations coexisting in the detergent, such as fluorescent dyes, during the cleaning process. The effect on enzymes, bleach activators, etc. that act on the product can be minimized. Therefore, according to the present invention, detergent formulations that are susceptible to the decomposition of sodium percarbonate, such as enzymes, fluorescent dyes, bleach activators, etc., and detergent systems that use sodium percarbonate in combination, can reduce the effects of each formulation. Stability issues can be solved all at once. In other words, according to the present invention, a phosphorus-free detergent is provided in which an enzyme, a fluorescent dye, a bleach activator, etc. are combined with soda percarbonate, and each of them has excellent storage stability. The bleaching detergent composition of the present invention optionally contains water-soluble soap and anionic, nonionic or amphoteric surfactants, organic or inorganic builders or metal ions, which are ingredients well known in the art. It can contain a sequestering agent, a bulking agent such as mirabilite, an enzyme agent effective for cleaning, a bleach activator, a fluorescent whitening agent, a fragrance, etc., but these are not particularly limited and can be mixed according to the purpose. It may be done. Well-known ingredients such as these surfactants and builder ingredients are disclosed in Japanese Patent Application No. 1983-1983, which was filed by the applicant earlier.
Those exemplified in the specification of No. 99826 can be used as appropriate. Next, the present invention will be explained using Examples, but the present invention is not limited thereto. Example 1 Put 100g of soda percarbonate into a stirring mixer,
While stirring at 250 rpm, spray a 25% aqueous solution of 5 g of sodium metaborate tetrahydrate (NaBO ₂ 4H ₂ O) (prepared by heating and dissolving it) and a 25% aqueous solution of 1 g of anhydrous magnesium sulfate (MgSO ₄ ). After stirring for 10 minutes, the mixture was dried with hot air to obtain coated sodium percarbonate. For comparison, sodium percarbonate coated with only sodium metaborate (for 100g of soda percarbonate)
7.1 g of NaBO ₂ 4H ₂ O), sodium percarbonate coated with boric acid (3.4 g of boric acid per 100 g of sodium percarbonate), sodium percarbonate coated with boric acid and anhydrous magnesium sulfate ( 100g of soda percarbonate
(2.4 g of boric acid and 1 g of MgSO ₄ ) and sodium percarbonate coated only with anhydrous magnesium sulfate (3.4 g of MgSO ₄ per 100 g of sodium percarbonate) were also produced. A bleaching detergent was obtained by uniformly mixing 10% by weight of these coated sodium percarbonate into a phosphorus-free powder detergent having the following composition. Phosphorus-free bleaching detergent composition Weight% Sodium dodecylbenzenesulfonate 20.0 Synthetic zeolite (Type 4A) 20.0 Sodium silicate (JIS No. 2) 10.0 Sodium carbonate 5.0 Fluorescent dye 0.5 Sodium carboxymethyl cellulose 1.0 Enzyme (Alcalase) 0.3 Percarbonate Soda 10.0 Water 5.0 Sodium sulfate balance Sodium metaborate according to the present invention as described above and MgSO ₄ as percarbonate of soda to be added to the above composition
For comparison, a coating with sodium metaborate alone, a coating with boric acid, a coating with boric acid and MgSO ₄ , a coating with MgSO ₄ , and a coating with no coating. We conducted a storage stability test on a total of 6 types of soda-based products.
The results are shown in Table 1. [Test method] 10g of each of the above bleaching detergent compositions was added to 50c.c.
Place in a plastic container with a lid and heat at 40℃80%.
After being left under RH conditions for 14 days, the effective oxygen residual rate was determined using the following formula. Effective oxygen residual rate (%)=available oxygen after storage/available oxygen before storage×100 In addition, 0.1N potassium permanganate titration method was used to measure the effective oxygen.

【table】

[Table]
As shown in Table 1, sodium metaborate and
The bleaching detergent of the present invention containing sodium percarbonate and using MgSO ₄ for coating had a higher effective oxygen residual rate than those of Comparative Examples 1 to 5, and clearly had a superior coating effect. In addition, the bleaching detergent of this example is a phosphorus-free detergent that contains no phosphorus and contains zeolite, but the bleaching detergent of the present invention has excellent coating stabilizing effects with sodium metaborate and MgSO ₄ . It shows good stability. Example 2 Sodium percarbonate was coated using the same coating method as in Example 1, except that the type of Mg compound used in combination with sodium metaborate was changed. The coating material used is shown below. NaBO ₂・4H ₂ O, 5% + MgSO ₄ (anhydrous solids) 1% NaBO ₂・4H ₂ O, 5% + MgCl ₂ (anhydrous solids) 1% NaBO ₂・4H ₂ O, 5% + 2MgO・3SiO ₂ ( Anhydrous solid content) 1% NaBO ₂ 4H ₂ O, 5% + MgO (anhydrous solid content)
1% NaBO ₂ 4H ₂ O, 7.1% A total of 6 types of the above 5 types of coated sodium percarbonate and uncoated sodium percarbonate were added to a phosphorus-free bleaching detergent with the same composition as in Example 1 (each containing 1% sodium percarbonate and 6 types of uncoated sodium percarbonate). 10% by weight
The storage stability test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

[Table] As shown in Table 2, the products of the present invention exhibit extremely excellent storage stability due to the mutual effect of the coating ability of the borate and the stabilizing ability of the Mg compound. Example 3 Using the same coating method as in Example 1, sodium percarbonate was coated using a combination of sodium metaborate, magnesium sulfate, and other coating agents. The coating material used is shown below. Incidentally, the amount of the coating agent used is expressed in percent by weight based on the sodium percarbonate. NaBO ₂・4H ₂ O, 5% + MgSO ₄ (anhydrous solid content) 1% + polyethylene glycol (PEG,
Molecular weight = 6000) 5% NaBO ₂ 4H ₂ O, 5% + MgSO ₄ (anhydrous solids) 1% + soda carbonate, 5% NaBO ₂ 4H ₂ O, 5% + MgSO ₄ (anhydrous solids) 1% + ethylenediamine Tetraacetic acid (EDTA)
2Na salt 0.5% NaBO ₂ 4H ₂ O, 5% + MgSO ₄ (anhydrous solid content) 1% + EDTA 2 triethanolamine (2TEA) salt 0.5% NaBO ₂ 4H ₂ O, 5% + MgSO ₄ (anhydrous solid content) 1% + nitrilotriacetic acid (NTA) 3Na salt
0.5% A total of 6 types of the above 5 types of coated soda percarbonate and uncoated sodium percarbonate were mixed into a phosphorus-free bleaching detergent with the same composition as in Example 1 (each with 10% by weight of sodium percarbonate).
The storage stability test was conducted in the same manner as in Example 1, and the results are shown in Table 3.

〔Test method〕

<Solubility> Tap water 1 was placed in a beaker (1 volume), 1 g of granular sodium percarbonate was added, and stirring was performed at a rotation speed of 200 rpm. After the start of stirring, the time required until the electrical conductivity of the solution stopped changing was measured, and this time was taken as the dissolution time. <Compressive strength> This is the load required to compress a certain amount of sample by 1 cm after filling it under specified conditions and applying a load using an autograph. <Disintegrability> Sample (12 meshes permeable to 80 meshes impermeable)
Transfer 100g to a 500ml wide-mouth plastic container, put 50g of stainless steel ball (3φ) in it, and seal it. Fix this container on a shaking machine and shake at an amplitude of 4.5 cm and a shaking frequency of 360 times/min.
Shake for 10 minutes and express in weight % of 80 mesh transmission. A smaller number (%) is desirable.

[Table] As shown in Table 4, even when coated with sodium percarbonate by the method of the present invention, the solubility, compressive strength,
The disintegration properties were almost the same as uncoated soda percarbonate. Example 5 20 kg of wet soda percarbonate was mixed with a centrifugal diffusion mixer (Lödeige mixer, FKM-130D, T.M.
Engineering Co., Ltd., and while stirring, the coating powder was added and mixed for a total of 10 minutes. Thereafter, the coated sodium percarbonate was taken out and dried with hot air. The following coating materials were used. Sodium metaborate (NaBO ₂ 4H ₂ O) 5%
+MgSO ₄ (anhydrous solid content) 1% + EDTA・
2TEA, 0.5% Borax (Na ₂ B ₄ O ₇・10H ₂ O) 4.54% +
MgSO ₄ (anhydrous solid content) 1% + EDTA・2TEA,
0.5% Boric acid (H ₃ BO ₃ ) 2.4% + MgSO ₄ (anhydrous solid content) 1% + EDTA・2TEA, 0.5% (% is weight % based on sodium percarbonate) These three types of coated soda percarbonate (in accordance with the present invention) According to 2
A total of four types of seeds, one comparative example) and uncoated soda percarbonate were mixed at 10% by weight in the following phosphorus-free bleaching detergent composition in the same manner as in Examples 1 and 2, and a storage stability test was conducted. (The method was the same as in Example 1), and the results are shown in Table 5. The residual activity of the enzyme (Alcalase 2.0M) blended at the same time was also measured, and the residual rate of enzyme activity was measured using the following formula and is also shown. Enzyme activity residual rate (%) = Enzyme activity after storage / Enzyme activity before storage × 100 For the measurement method of enzyme residual activity, refer to JBC 244.
(4) 1969, pp. 789-793, Analyst 96 1971, 159-
It is described on page 163. Phosphorus-free bleaching detergent composition Weight% Sodium dodecylbenzenesulfonate 20.0 Synthetic zeolite (4A type) 20.0 Sodium silicate (JIS No. 2) 10.0 Sodium carbonate 5.0 Fluorescent dye 0.5 Carboxymethylcellulose sodium salt 1.0 Enzyme (Alcalase 2.0M) 0.3 Soda carbonate (coated) 10.0 Moisture 5.0 Sodium sulfate balance total 100

[Table] As shown in Table 5, although the phosphorus-free bleaching detergent of the present invention contains zeolite, the stability of the sodium percarbonate is very good, and at the same time, the stability of the enzyme is was also excellent. Example 6 The coated soda percarbonate according to the present invention prepared in Example 5 (coated with NaBO ₂ 4H ₂ O and Na ₂ B ₄ O ₇ 10H ₂ O, respectively, and MgSO ₄ ) and the two comparative examples (H ₃ BO ₃ /MgSO ₄ coated and uncoated sodium percarbonate) were mixed at 10% by weight each in powdered bleaching detergent having the following composition, and a storage stability test was conducted to determine the residual effective oxygen content of sodium percarbonate. Table 6 shows the results of the residual rate of enzyme activity of Alcalase 2.0M. The test method was the same as in Examples 1 and 5. Bleach cleaning agent composition Weight% Sodium dodecylbenzenesulfonate 20.0 Sodium tripolyphosphate 18.0 Sodium silicate (JIS No. 2) 10.0 Sodium carbonate 5.0 Fluorescent dye 0.5 Sodium carboxymethyl cellulose 0.5 Enzyme (Alcalase 2.0M) 0.3 Sodium percarbonate 10.0 Water 5.0 Sulfuric acid Soda remaining total 100

[Table] This example is a bleaching detergent composition containing conventional STPP, and the composition according to the present invention showed very excellent storage stability. This shows that the bleaching detergent according to the present invention has excellent storage stability regardless of the zeolite content. Comparative Example A storage stability test was conducted in the same manner as in Example 1 for cleaning agents A, B, and C having the following compositions. Note that the numbers are in percent by weight.

【table】

【table】 The results are shown in Table 7.

[Table] As is clear from the comparison between Table 1 and Table 7, in the bleaching detergent according to the present invention, the borate and magnesium compounds are not simply blended into the detergent, but the sodium percarbonate that is blended is coated. By combining them in the form of is almost never seen.

Claims (1)

[Scope of Claims] 1. A bleaching detergent composition comprising soda percarbonate whose surface is coated with a coating agent containing at least both a borate and a magnesium compound. 2 The amount of coating agent is 0.1 to
30% by weight, the borate is 10-99.5% by weight in the coating and the magnesium compound is 0.5-50% by weight. 3. The bleaching detergent composition according to claim 1 or 2, wherein the borate is a sodium salt of boric acid. 4. The bleaching detergent composition according to claim 1, 2, or 3, wherein the magnesium compound is one or more of magnesium sulfate, magnesium chloride, magnesium oxide, and magnesium silicate. 5. The bleaching detergent composition according to claim 3 or 4, wherein the sodium salt of boric acid is sodium metaborate. 6. The bleaching detergent composition according to any one of claims 1 to 5, wherein the coating agent contains a sequestering agent. 7. The bleaching detergent composition according to claim 6, wherein the sequestering agent is ethylenediaminetetraacetate or nitrilotriacetate. 8 The average particle size of the coated soda percarbonate is 100
A bleaching detergent composition according to any one of claims 1 to 7, which has a particle size of 2000μ to 2000μ, preferably 250-1000μ. 9. The bleaching detergent composition according to any one of claims 1 to 8, wherein the amount of the coated sodium percarbonate is 1 to 40% by weight of the composition.