JPH08319472A - Slow-solubilizing agent - Google Patents

Abstract

PURPOSE: To obtain a slow-solubilizing agent for a solid fragrant detergent that has a good shape retentivity and can be used for even a urinal bowl for men by using an aromatic compound containing oxyethylene groups. CONSTITUTION: This agent comprises an aromatic compound (A) containing oxyethylene groups and having a melting point of 50 deg.C or higher or a mixture of the compound A with a water-soluble aliphatic compound (B). Examples of the compound A include ethylene oxide adducts of, e.g. an aromatic polycarboxylic acid of a high melting point, such as phthalic acid, and bisphenols, among which bis(2-hydroxyethyl) terephthalate is preferably used in particular. Examples of the compound B include aliphatic polyhydric alcohols and polyalkylene glycols, among which glycerin is preferably used in particular. This agent can be used together with additives, such as a surfactant, a coloring agent, a perfume, a deodorant or a bleaching agent, for both a solid fragrant detergent for a flush toilet and a material for preventing sliminess of a drain pipe.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slow-dissolving agent, and more particularly to a slow-dissolving agent that can be used as a solid fragrance cleaner for flush toilets, a solid anti-stickiness agent for drainage pipes of kitchen sinks, and the like.

[0002]

2. Description of the Related Art Solid fragrance cleaners for flush toilets are either put directly into the water tank of the flush toilet or installed in a hand-washing section on the water tank, and the detergent is gradually added by running water during flushing. It is a drug that dissolves or disperses in to keep the inside of the toilet bowl clean and masks the bad odor of manure and its decomposition products (deodorization). As such a solid fragrance cleaner, a solubilized component, a cleaning component, an fragrance component and a coloring component are generally mixed. Examples of the solubilizing component include high molecular weight polyethylene glycol, high molecular weight polyethylene glycol-based compounds such as those obtained by etherifying or esterifying hydroxyl groups at one or both ends of polyethylene glycol, and copolymers of ethylene oxide and propylene oxide (1 ) Are known (for example, JP-A-51-39705 and JP-A-55-13).
1098 and 57-179298).
Further, JP-A-6-277270 discloses a solid deodorant composition containing a metal sulfate, an aldehyde compound, and a deodorant fragrance in a base composed of a water-soluble base and a poorly water-soluble base (2 )
Is described. Here, as the water-soluble base, a high molecular weight such as polyethylene glycol or polyethylene glycol fatty acid ester (molecular weight 6000 to 20000)
A polyethylene glycol compound is mentioned, and it is described that the dissolution rate of a 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 (1) and the composition of (2) both use a high molecular weight polyethylene glycol compound as a slow-solubilizing component, contact with water Due to this, there is a problem in that the swelling causes the shape to collapse (the shape retention property is poor), and further becomes muddy, which flows into the drain port and clogs the drain pipe. Therefore, solid fragrance cleaners that use polyethylene glycol-based compounds as solubilizing components have never been used as solid fragrance cleaners for men's urinals, and men's toilet balls mainly consist of paradichlorobenzene. At present, sublimable deodorants are still used.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a sustained-solubilizing component having a specific composition is excellent in shape retention and dissolution sustainability, and is a solid fragrance cleaner for men's urinals. They have found that they can also be used as a gradual solution component of the present invention and reached the present invention. That is, the present invention has a melting point of 50 ° C.
A slow-dissolving agent comprising the above oxyethylene group-containing aromatic compound (A) or a combination system of (A) and a water-soluble aliphatic compound (B).

[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 of a high-melting point aromatic compound having a hydroxyl group and / or a carboxyl group in the molecule (hereinafter abbreviated as EO) ) Examples include adducts. Specific examples thereof include EO adducts (or ethylene glycol esters) of aromatic monocarboxylic acids such as benzoic acid and salicylic acid (A1), aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and benzenetricarboxylic acid. EO adduct (or ethylene glycol ester) (A2), resorcinol,
Hydroquinone, Bisphenol A, Bisphenol F
And EO adducts of aromatic dihydric phenols having 6 to 20 carbon atoms (A3), EO adducts of aromatic amines such as methylenedianiline, and the like. These compounds can be used alone or as a mixture of two or more kinds. Of these, (A1) and (A2) are preferable, (A2) is more preferable, and bis (2-hydroxyethyl) is preferable among (A2) from the viewpoint of good balance of shape retention and dissolution speed.
Isophthalate and bis (2-hydroxyethyl) terephthalate are preferable, and bis (2-hydroxyethyl) terephthalate is more preferable. As a property of the oxyethylene group-containing aromatic compound (A), the melting point is 50 ° C to 200 ° C.
A ° C., preferably 50 to 150 ° C., the solubility at _{20 ℃ (g / 100gH 2 O} ) is usually 0.0001
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 become sticky and
If the temperature exceeds ℃, a large amount of energy is required for melting and it is uneconomical. If the solubility exceeds 3, the dissolution sustainability of the slow-dissolving agent becomes poor (dissolution speed becomes fast), and if it is less than 0.0001, the slow-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 more. Specific examples thereof include alkylene glycols having 2 to 6 carbon atoms (B, such as ethylene glycol, dipropylene glycol, trimethylene glycol, butylene glycol, and 1,6-hexylene glycol).
1); trivalent or more aliphatic polyhydric alcohols such as glycerin, diglycerin, and trimethylolpropane (B2);
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, such as polyalkylene glycol (B3). When the boiling point of (B) is less than 150 ° C., the shape of the slow-solubilizing agent tends to change (e.g. shrinkage, generation of voids) over time because it is likely to volatilize. Also, the solubility at 20 ° C (g / 1
When the amount of 00gH ₂ O) is less than 30, the slow-solubilizing agent is likely to swell with water, resulting in poor shape retention. Above (B1)-(B
Among 3), (B1) and (B2) are preferable because the shape retention property of the slow-solubilizing agent is good, and (B2) is more preferable.
Especially, glycerin is most preferable.

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 water-soluble aliphatic compound (B) is usually (B) / (A) in a weight ratio of ( 0/100) to (70/30), preferably (10
/ 90) to (60/40). When the weight ratio of (B) / (A) is larger than 70/30, the dissolution rate of the slow-solubilizing agent is increased and the dissolution persistence is deteriorated.

The slow-solubilizing agent of the present invention is usually one or more additives (C) such as a surfactant, a colorant, a fragrance, a deodorant, a bleaching agent and a bulking agent, and optionally other additives ( D)
Used with. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Among these, nonionic surfactants are preferable because they are easily mixed with the slow-solubilizing agent. The amount of the surfactant used is usually 0.5 to 50% by weight, preferably 1 to 20% by weight, based on the total amount of the slow-solubilizing agent [(A) + (B)]. Examples of colorants include methylene blue, cyanine blue, blue 1
No. 2, Blue No. 2, and aluminum lake products thereof. The amount of the colorant used is the slow-solubilizing agent [(A) + (B)].
It is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of. Examples of the fragrance include plant essential oils such as lavender, lemon oil, rose oil, and green oil; animal fragrances such as musk and civet; aldehydes,
Examples thereof include synthetic fragrances such as esters and ketones, and compounded fragrances thereof. The amount of the fragrance used is usually 0.05 to 10 with respect to the total amount of the slow-solubilizing agent [(A) + (B)].
% By weight, 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 extracted oil. The amount of the deodorant used is usually 1 to 50 with respect to the total amount of the slow-solubilizing agent [(A) + (B)].
%, Preferably 5 to 20% by weight. Examples of the bleaching agent include oxygen-based bleaching agents such as sodium perborate and sodium persulfate; chlorine-based bleaching agents such as chlorinated isocyanuric acid. The amount of bleach used is the slow-solubilizing agent [(A) +
It is usually 1 to 50% by weight, preferably 5 to 20% by weight, based on the total amount of (B)]. Examples of the filler include inorganic salts such as mirabilite, anhydrous mirabilite, potassium sulfate, sodium carbonate, calcium carbonate, calcium phosphate and boric acid; organic compounds such as urea. The amount of filler used is
It is usually 10 to the total amount of the slow-solubilizing agent [(A) + (B)].
It is 200% by weight, preferably 20 to 100% by weight.
Other additives (D) include builder such as sodium tripolyphosphate, sodium pyrophosphate and sodium silicate; filler such as talc and colloidal silica;
Reinforcing agents such as solid epoxy resins (for example, diglycidyl ether type of bisphenol A); ultraviolet absorbers, bactericides, insecticides, chemical pesticides, chemical fertilizers and the like. Examples of the method for producing a sustained-release agent (solid) such as a toilet solid aroma cleaner and a kitchen sink slime preventive agent (solid) using the slow-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 casting method and compression molding method (tablet molding method) can be applied.

[0009]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, parts and% mean parts by weight and% by weight. The 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) 2.1 mol ethylene oxide adduct of BP-E2 bisphenol A (3) PG propylene glycol (4) GLC glycerin (5) Activator 1 7 mol ethylene oxide adduct of oleic acid ester of sorbitan (nonionic surfactant) Agent) (6) Activator 2 Pluronic type nonionic surfactant (polyoxyalkylene glycol having a molecular weight of 2200, which is obtained by adding ethylene oxide to polypropylene glycol having a molecular weight of 1700) (7) Perfume rose oil (8) Colorant Food additive blue No. 1 Aluminum rake

The test methods used in Examples and Comparative Examples are shown below. (1) Melting point Measured with a trace melting point measuring device manufactured by Yanagimoto Seisakusho Co., Ltd. (2) Duration and shape retention A cylindrical solid net dissolution agent (30 g) molded in a cylindrical shape is used as a stainless steel cylindrical net basket (diameter 40 mm, height 60 mm). ), And put into a still water tank (water temperature 25 ° C.) of 15 L, and the weight of the solid slow-solubilizing agent is measured every 5 days, and the number of days when the weight of the solid slow-solubilizing agent is less than 5 g is defined as the duration. . In addition, the shape retention of the solid slow-solubilizing agent up to the duration (presence or absence of cracking, swelling, etc.)
Was observed. The water in the water tank was replaced with fresh water once a day.

Examples 1 to 4 The ingredients shown in Table 1 were melt mixed, cooled, solidified, and then finely pulverized. Next, this fine powder was compressed with a tableting machine into a cylindrical solid substance having a diameter of 38 mm and a height of 25 mm (about 30 mm).
It was molded into g) and the above performance evaluation was performed. Table 1 shows the results. Comparative Example 1 The same evaluation as in Examples 1 to 4 was performed on a commercially available solid fragrance detergent. Table 1 shows the results. Example 5 Of the blended components shown in Table 1, first, the slowly-solubilized components were heated and uniformly mixed at about 80 ° C., and then a colorant was further added and mixed. Next, after adding a fragrance | flavor and stirring at the same temperature for 10 seconds and mixing, the mixed liquid was poured into the polypropylene cup of 30 ml. Allow to cool in the room (about 20 ℃) for 24 hours,
The mold was removed to obtain a solid. The performance of the solid material was evaluated in the same manner. Table 1 shows the results.

[0012]

[Table 1]

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

[0014]

EFFECTS OF THE INVENTION The slow-solubilizing agent of the present invention does not swell or become muddy even if it is brought into contact with water for a long time, and its duration can be widely changed. It can be used not only for applications but also as a slow-dissolving agent for deodorants for men's urinals and aroma cleaners, which had been considered technically difficult until now. Furthermore, the slow-dissolving agent of the present invention is excellent not only in the shape-retaining property but also in the long-lasting property, so that it is not only used for the toilet as described above, but also as an anti-smearing agent for kitchen drainage pipes and for pools. It can be applied to other applications such as sustained-release fungicides, sustained-release pesticides, sustained-release fertilizers, etc., and its practical value is extremely high.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C11D 3/50 C11D 3/50

Claims (6)

[Claims] 1. A sustained solution characterized by comprising an oxyethylene group-containing aromatic compound (A) having a melting point of 50 ° C. or higher, or a combination system of (A) and a water-soluble aliphatic compound (B). Agent. 2. The slow-solubilizing agent according to claim 1, wherein (A) is an ethylene oxide adduct of an aromatic polycarboxylic acid or an ethylene glycol ester of an aromatic polycarboxylic acid. 3. The slow-solubilizing agent according to claim 2, wherein the aromatic polycarboxylic acid is terephthalic acid. 4. 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. 5. The method according to claim 1, wherein (B) is glycerin.
The slow-solubilizing agent according to any one of 1. 6. The weight ratio of (B) / (A) is (0/10).
0)-(70/30), The slow-solubilizing agent in any one of Claims 1-5.