JP2787431B2 - Solubilizer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solubilizing agent, and more particularly to a solubilizing agent which can be used as a solid fragrance detergent for flush toilets, a solid anti-slime agent in a kitchen drain, and the like.

[0002]

2. Description of the Related Art A solid fragrance detergent for flush toilets is directly poured into a water tank of the flush toilet, or installed in a hand washing section on the water tank, and the detergent is gradually supplied by running water during flushing. It is a chemical that dissolves or disperses in the urine to keep the inside of the toilet clean and masks the odor of manure and its decomposition products. As such a solid aroma detergent, a solubilized component, a washing component, an aroma component, and a coloring component are generally blended. Examples of the solubilized component include a high molecular weight polyethylene glycol compound (1) such as a high molecular weight polyethylene glycol, a product obtained by etherifying or esterifying a hydroxyl group at one or both terminals of polyethylene glycol, or a copolymer of ethylene oxide and propylene oxide. ) Are known (for example, JP-A-51-39705 and JP-A-55-13).
1098 and 57-179298).
JP-A-6-277270 discloses a solid deodorant composition (2) containing a metal sulfate, an aldehyde compound and a deodorant fragrance in a base comprising a water-soluble base and a poorly water-soluble base. )
Is described. Here, as the water-soluble base, polyethylene glycol, polyethylene glycol fatty acid ester, or other high molecular weight (molecular weight 6,000 to 20,000)
It is described that the dissolution rate of the solid deodorant composition is controlled by combining polyethylene glycol compounds having different molecular weights. Examples of poorly water-soluble bases include alkylolamide nonionic surfactants and stearic acid.

[0003]

However, since the compound of the above (1) and the composition of the above (2) both use a high molecular weight polyethylene glycol compound as a solubilizing component, contact with water is difficult. As a result, there is a problem in that the resin swells and loses its shape (poor shape retention), and further forms mud, which flows into the drain port and clogs the drain pipe. Therefore, a solid fragrance detergent using a polyethylene glycol-based compound as a solubilized component has never been used as a solid fragrance detergent for a men's urinal, and a ball for a men's toilet mainly consists of paradichlorobenzene. At present, sublimable deodorants are still used.

[0004]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that a slowly-solubilizing component having a specific composition is excellent in shape retention and dissolution persistence, and is a solid fragrance detergent for male urinals. It has been found that it can also be used as a solubilized component of the present invention, and reached the present invention. That is, the present invention provides a melting point of 50 ° C.
It comprises a combined system of the oxyethylene group-containing aromatic compound (A) and the water-soluble aliphatic compound (B), wherein (A) is an ethylene oxide adduct of an aromatic polycarboxylic acid or ethylene of an aromatic polycarboxylic acid. It is a solubilizer that is a glycol ester.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As the oxyethylene group-containing aromatic compound (A) having a melting point of 50 ° C. or higher, for example, ethylene oxide (hereinafter abbreviated as EO) of a high melting point aromatic compound having a hydroxyl group and / or a carboxyl group in a molecule. ) Adducts. Specific examples thereof include EO adducts (or ethylene glycol esters) of aromatic monocarboxylic acids such as benzoic acid and salicylic acid (A1), and aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and benzenetricarboxylic acid. EO adduct (or ethylene glycol ester) of (A2), resorcinol,
Hydroquinone, bisphenol A, bisphenol F
And EO adducts of aromatic dihydric phenols having 6 to 20 carbon atoms (A3) and EO adducts of aromatic amines such as methylene dianiline. These compounds can be used alone or as a mixture of two or more. Of these, (A1) and (A2) are preferable, and (A2) is more preferable, because bis (2-hydroxyethyl) is preferred in terms of a good balance between shape retention and dissolution speed.
Isophthalate and bis (2-hydroxyethyl) terephthalate are preferred, and bis (2-hydroxyethyl) terephthalate is more preferred. As a property of the oxyethylene group-containing aromatic compound (A), the melting point is 50 ° C to 200 ° C.
° C, preferably from 50 to 150 ° C, and the solubility (g / 100gH ₂ O) at 20 ° C is usually from 0.0001 to
It is about 3 and preferably about 0.001 to 1. (A)
If the melting point is less than 50 ° C., the surface tends to be sticky,
Exceeding ° C requires a great deal of energy to melt and is uneconomical. On the other hand, when the solubility exceeds 3, the dissolution sustaining agent dissolution persistence becomes poor (the dissolving speed is increased), and when the solubility is less than 0.0001, the dissolving agent hardly dissolves.

Examples of the water-soluble aliphatic compound (B) include compounds having low volatility (boiling point of 150 ° C. or higher) and solubility at 20 ° C. (g / 100 g H ₂ O) of 30 or higher. Specific examples thereof include alkylene glycols having 2 to 6 carbon atoms such as ethylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, and 1,6-hexylene glycol (B
1); trihydric or higher aliphatic polyhydric alcohols (B2) such as glycerin, diglycerin, and trimethylolpropane;
Polypropylene glycol (molecular weight 250 or less), polyethylene glycol (molecular weight 3000 or less) poly (propylene-ethylene) glycol (molecular weight 3000 or less)
And the like. When the boiling point of (B) is lower than 150 ° C., the shape of the solubilizing agent tends to change (for example, shrinkage or voids) easily with the passage of time because it is easily volatilized. The solubility at 20 ° C. (g / 1
In 00gH ₂ O) is less than 30, Xu solubilizing agent becomes liable to swell with water, the shape retaining property becomes poor. (B1) to (B)
Among 3), (B1) and (B2) are preferable in that the shape-retaining property of the solubilizer is good, and (B2) is more preferable.
Glycerin is particularly preferred.

In the present invention, the amount of the oxyethylene group-containing aromatic compound (A) having a melting point of 50 ° C. or higher and the amount of the water-soluble aliphatic compound (B) are usually expressed by a weight ratio of (B) / (A). 0/100) to (70/30), preferably (10/100)
/ 90) to (60/40). If the weight ratio of (B) / (A) is larger than 70/30, the dissolution speed of the solubilizer will increase, and the dissolution durability will deteriorate.

The solubilizing agent of the present invention is usually composed of one or more additives (C) such as a surfactant, a coloring agent, a fragrance, a deodorant, a bleaching agent, a bulking agent, and, if necessary, other additives ( D)
Used with Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. Among these, nonionic surfactants are preferred because they are easily miscible with the solubilizer. The amount of the surfactant to be used is generally 0.5 to 50% by weight, preferably 1 to 20% by weight, based on the total amount of the solubilizer [(A) + (B)]. Examples of the coloring agent include methylene blue, cyanine blue, and blue 1
No. 2, Blue No. 2 and aluminum lake products thereof. The amount of the colorant used is the solubilizer [(A) + (B)]
Is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of Examples of the flavor include plant essential oils such as lavender, lemon oil, rose oil and green oil; animal flavors such as musk and civet; aldehydes;
Synthetic fragrances such as esters, ketones and the like, and compounded fragrances thereof are exemplified. The amount of the fragrance is usually 0.05 to 10 with respect to the total amount of the solubilizer [(A) + (B)].
%, Preferably 0.1 to 2% by weight. Examples of the deodorant include aldehyde compounds such as glyoxal; metal compounds such as zinc sulfate and zinc lactate; and known deodorants such as plant extraction oils. The amount of the deodorant used is usually 1 to 50 with respect to the total amount of the solubilizer [(A) + (B)].
%, Preferably 5 to 20% by weight. Examples of the bleaching agent include oxygen bleaching agents such as sodium perborate and sodium persulfate; chlorine bleaching agents such as chlorinated isocyanuric acid. The amount of the bleaching agent used is that of the solubilizing agent [(A) +
(B)], and is usually 1 to 50% by weight, preferably 5 to 20% by weight. Examples of the extender include inorganic salts such as sodium sulfate, anhydrous sodium sulfate, potassium sulfate, sodium carbonate, calcium carbonate, calcium phosphate, and boric acid; and organic compounds such as urea. The amount of filler used is
Usually 10 to the total amount of the solubilizer [(A) + (B)].
It is 200% by weight, preferably 20 to 100% by weight.
Other additives (D) include builders such as sodium tripolyphosphate, sodium pyrophosphate and sodium silicate; fillers such as talc and colloidal silica;
Reinforcing agents such as solid epoxy resin (for example, diglycidyl ether type of bisphenol A); UV absorbers, bactericides, insecticides, chemical pesticides, chemical fertilizers, and the like. Examples of the method for producing a sustained-release drug (solid) such as a solid fragrance cleaning agent for toilets and an anti-slime agent for kitchen sinks using the solubilizing agent of the present invention include, for example, an extrusion molding method, an injection molding method, and a liquid. Known molding methods such as a casting method and a compression molding method (tablet molding method) can be applied.

[0009]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. In the following, parts and% indicate parts by weight and% by weight, respectively. Abbreviations and compositions of the raw materials used in the examples of the present invention are shown below. (1) BHET bis (2-hydroxyethyl)
Terephthalate (2) BP-E2 bisphenol A ethylene oxide 2.1 mol adduct (3) PG propylene glycol (4) GLC glycerin (5) activator 1 sorbitan oleate ester ethylene oxide 7 mol adduct (nonionic surfactant) (6) Activator 2 Pluronic-type nonionic surfactant (polyoxyalkylene glycol having a molecular weight of 2200 obtained by adding ethylene oxide to polypropylene glycol having a molecular weight of 1700) (7) Fragrance Rose oil (8) Colorant Aluminum rake

The test methods used in the examples and comparative examples are described below. (1) Melting point Measured with a micro-melting point measuring device manufactured by Yanagimoto Seisakusho Co., Ltd. (2) Duration and shape retention A cylindrical solid net solubilizer (30 g) molded into a cylindrical shape is a stainless steel cylindrical net cage (diameter 40 mm, height 60 mm) ), Placed in a 15 L still water tank (water temperature: 25 ° C.), the weight of the solid solubilizing agent was measured every 5 days, and the number of days when the weight of the solid solubilizing agent was less than 5 g was defined as the duration. . In addition, the shape retention of the solid solubiliser up to the duration (presence of cracks, swelling, etc.)
Was observed. The water in the aquarium was replaced with fresh water once a day.

Examples 1 to 3 The components shown in Table 1 were melt-mixed, cooled, solidified, and then pulverized. Next, this fine powder was solidified into a columnar solid (about 30 mm in diameter and 25 mm in height) using a tableting machine.
g), and the above-described performance evaluation was performed. Table 1 shows the results. Comparative Example 1 The same evaluation as in Examples 1 to 4 was performed for a commercially available solid aroma detergent. Table 1 shows the results. Example 4 Among the components shown in Table 1, the solubilized component was first heated and uniformly mixed at about 80 ° C., and a colorant was further added and mixed. Next, the fragrance was added, and after stirring and mixing at the same temperature for 10 seconds, the mixture was poured into a 30 ml polypropylene cup. After leaving to cool indoors (about 20 ° C) for 24 hours,
Demolding gave a solid. The performance of the solid was evaluated in the same manner. Table 1 shows the results.

[0012]

[Table 1]

As is clear from Table 1, the solubilizing agent of the present invention has good shape-retaining properties and has the advantage that the duration can be varied widely.

[0014]

EFFECTS OF THE INVENTION The solubilizer of the present invention does not swell or become muddy even when it is in contact with water for a long time, and its duration can be varied widely. It can be used not only for applications but also as a solubilizing agent for men's urinals, which has been considered technically difficult so far, such as deodorants and aroma cleaners. Further, the solubilizing agent of the present invention is excellent not only for use as a toilet as described above, but also as an anti-slime agent for kitchen sink drains and for pools, due to its excellent shape retention and sustainability properties. It can be applied to other uses such as sustained-release fungicides, sustained-release pesticides, and sustained-release fertilizers, and its practical value is extremely high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/50 C11D 3/50

Claims (5)

(57) [Claims] An oxyethylene group-containing aromatic compound (A) having a melting point of 50 ° C. or higher and a water-soluble aliphatic compound (B) are used in combination, wherein (A) is an ethylene oxide adduct of an aromatic polycarboxylic acid, Or a solubilizer which is an ethylene glycol ester of an aromatic polycarboxylic acid. 2. The solubilizer according to claim 1, wherein the aromatic polycarboxylic acid is terephthalic acid. 3. The slow-solubilizing agent according to claim 1, wherein (B) is an alkylene glycol having 2 to 6 carbon atoms and / or an aliphatic polyhydric alcohol. 4. The solubiliser according to claim 3, wherein (B) is glycerin. 5. The weight ratio of (B) / (A) is (10/9)
The sustaining agent according to any one of claims 1 to 4, which is 0) to (60/40).