JPH09194881A - Water-soluble solid base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble solid base material which is entirely dissolved after a long time, dissolves sustainedly, resists to deformation and is useful as a base material for e.g. solid deodorant/cleaners for flush toilets. SOLUTION: This material is prepared by reacting a polyethyleneglycol-chain- containing compound (e.g. polyethylene glycol) having at least two hydroxyl groups and 50, desirably 50-500, more desirably 80-250 ethylene oxide units with a fatty acid (e.g. stearic acid), desirably an 8C, desirably 12-50C saturated straight-chain fatty acid, a dibasic acid, desirably a cyclic acid anhydride (e.g. phthalic anhydride) and a 4C or higher, desirably 10-16C hydrocarbon-group- containing glycidyl ether (e.g. decyl glycidyl ether).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-soluble solidified base material useful as a base material for a solid deodorant cleaner for flush toilets.

[0002]

2. Description of the Related Art Polyethylene glycol derivatives have been often used as a base material for solid deodorant cleaners for flush toilets. For example, JP-A-53-31709 discloses a flush toilet solid detergent containing polyethylene glycol and polyoxyethylene nonylphenyl ether.
JP-A-58-168699, JP-A-57-179
No. 298 discloses that ethylene oxide unit is 50 to 50.
There is described an example in which a compound having a hydrocarbon group ester or ether at one or both ends of polyethylene glycol of No. 0 is used as a solid deodorant cleaner for flush toilets.
JP-B-5-38039 discloses a detergent for flush toilets in which an ethylene oxide adduct of polyhydric alcohol is reacted with another alkylene oxide, and JP-A-58-33916 discloses polyethylene glycol and polyisocyanate. As a reaction product of a compound, JP-A-51-39705 proposes to use a composition prepared by mixing an ethylene oxide-propylene oxide copolymer and urea or a special inorganic salt as a cleaning agent for flush toilets.

However, each of the conventionally proposed water-soluble solidified base materials for flush toilet cleaners has many drawbacks. For example, polyethylene glycol as a main material has a drawback that the dissolution disappearance time is too fast,
Polyethylene glycol in which one or both ends are blocked with a hydrophobic group has a long dissolution disappearance time, but loses its shape over time and has a problem in shape retention. Further, a copolymer of ethylene oxide and propylene oxide has properties in between, but at the same time, neither is satisfied.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water-soluble solidified base material for flush toilets, which has a long dissolution disappearance time, is continuously dissolved, and is hard to lose its shape.

[0005]

The present invention is a compound having two or more hydroxyl groups and having a polyethylene glycol chain of 50 or more in ethylene oxide units; fatty acids having 8 or more carbon atoms; dibasic acids and carbonization having 4 or more carbon atoms. The present invention relates to a water-soluble solidified base material containing a compound obtained by reacting a glycidyl ether having a hydrogen group, and a method for producing the same.

As a compound having two or more hydroxyl groups and a polyethylene glycol chain having ethylene oxide units of 50 or more (hereinafter simply referred to as PEG compound), polyethylene glycol, polyhydric alcohols such as propylene glycol, glycerin, pentaerythritol, Examples include trimethylolpropane, sorbitol, and the like to which ethylene oxide is added. Another alkylene glycol chain such as a propylene glycol chain or a butylene glycol chain may be bonded to the polyethylene glycol chain. This combination may be block or random. The ethylene oxide unit is 50 to 500, preferably the ethylene oxide unit is 80 to 250.
When the ethylene oxide unit is less than 50, the melting point of the reaction product becomes low, which causes a problem in solubility. When the ethylene oxide unit exceeds 500, the shape retention property in water with time deteriorates.

Examples of fatty acids having 8 or more carbon atoms include saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid.
Examples thereof include unsaturated fatty acids such as oleic acid, linoleic acid, and erucic acid. If desired, an oxycarboxylic acid such as ricinoleic acid or hydroxystearic acid may be used. The fatty acid may have a side chain, but is preferably a saturated straight chain fatty acid having 12 to 50 carbon atoms. When the number of carbon atoms is less than 8, the solubility in water becomes strong and the durability is lowered. When the carbon number is more than 50, the fatty acid is expensive and not economical. You may use these fatty acids in mixture of 2 or more types. The fatty acid may be selected in consideration of the molecular weight of polyethylene glycol to be used, the durability in water required for the water-soluble solidified base material, the solubility, and the like. The amount of fatty acid used is 0.3 to 1 equivalent of hydroxyl group in the PEG compound.
It is 0.7 equivalent, and more preferably 0.4 to 0.6 equivalent. If it is less than 0.3 equivalent, it is necessary to increase the amount of the acid anhydride used, and as a result, the cost becomes high. I am going to lose my way. on the other hand,
If the amount exceeds 0.7 equivalents, the shape retention tends to decrease with time in water.

Dibasic acids include aliphatic dibasic acids such as maleic acid, citraconic acid, succinic acid, glutaric acid,
Aromatic dibasic acids such as adipic acid, for example, phthalic acid, isophthalic acid, terephthalic acid and the like are exemplified, but cyclic acid anhydrides such as maleic anhydride, citraconic anhydride and phthalic anhydride are particularly preferable. These cyclic acid anhydrides have excellent reactivity, and compared with linear ones,
It is particularly preferable because it gives high shape retention in water. The amount of dibasic acid used is 1.4 per equivalent of hydroxyl group of the PEG compound.
~ 0.6 equivalents, preferably 1.2-0.8 equivalents.
If the amount of the dibasic acid is more than 1.4 equivalents, the cost will be high, and instead of gradually dissolving, it will be dissolved in such a way that tatters and lumps will come off. 0.
When it is less than 6, the dissolution time is shortened and the shape retention property is deteriorated with time in water.

The amounts of the above-mentioned monovalent fatty acid and divalent fatty acid are basically 0.5 equivalents of the former and 1.0 equivalents of the latter with respect to 1 equivalent of the hydroxyl group of the PEG compound, and the total of both is equivalent to the hydroxyl equivalent of the PEG compound. Make an excess of 0.5 equivalent. However, this is only a guide and is not limited to this. Typically, the total equivalent of both acids may be about 1.2 to 1.7, especially 1.4 to 1.6 in excess of that of the hydroxyl group. The equivalent of each of the above acids may be selected within that range.

Glycidyl ether is reacted with excess carboxyl groups. The glycidyl ether is preferably an ether compound having a hydrocarbon group having 4 or more carbon atoms, preferably 10 to 16. The hydrocarbon group may be an alkyl group or an aryl group. Further, it may be a cycloalkyl group or an aralkyl group. The alkyl group may have a side chain and may have an unsaturated group. Examples thereof include a tersialybutyl group, a 2-ethylhexyl group, a cetyl group, an oleyl group and a stearyl group. The aryl group may have a substituent. Typically, it is a phenyl group or a naphthyl group. The cycloalkyl group is a cyclopentyl group, a cyclohexyl group, etc., and the aralkyl group is a benzyl group. It is not limited to these.

The amount of glycidyl ether used is 0.5 to 1.0 equivalent, and more preferably 0.8 to 1.0 equivalent, based on 1 equivalent of the excess carboxyl group. The residual carboxyl group may be esterified with another appropriate alcohol, if necessary, or may be formed into an appropriate salt such as an alkali metal salt or an alkaline earth metal salt.

The water-soluble solidified substrate of the present invention may further contain other components in addition to the above ester compound. When the water-soluble solidified base material is used as a cleaning agent for flush toilets, these other components include dyes, germicides, fragrances, deodorants, cleaning agents, dissolution rate modifiers, shape retention agents, thickeners. Agents, anti-fading agents for dyes, solubilizing agents for oil-soluble aromatic components, extenders, chelating agents and the like may be added.

Dyes, germicides, fragrances, deodorants, extenders, chelating agents and the like may be appropriately selected from those conventionally used. Examples of the detergent include, but are not limited to, nonionic surfactants, particularly alkylene oxide addition type surfactants such as alkylphenol ethylene oxide adducts and higher alcohol ethylene oxide adducts. The HLB of the nonionic surfactant is preferably 10-18, more preferably 12-16. Many of the cationic surfactants and amphoteric surfactants act as bactericidal detergents, and these may be used, but many are insufficient in detergency. As the anionic surfactant, a commonly used substance such as POE alkyl ether sulfate is used as it is. As the fatty acid soap, sodium or potassium soap having up to 18 carbon atoms is used. The content of the detergent is generally 5 to 40% with respect to the total amount. Dissolution rate modifiers include various glycols, polyols, ether polyols, solvents such as cellosolves (alkylene glycol alkyl ethers), organic solvents such as esters thereof, organic compounds such as urea and melamine, and sodium sulfate. Inorganic compounds such as sodium chloride, sodium phosphate, and borax are exemplified. Glycols such as ethylene glycol and propylene glycol, polyols such as glycerin, pentaerythritol, trimethylene glycol, polyglycerin, glucose and sorbitol, ether polyols such as diethylene glycol, dipropylene glycol and triethylene glycol, and cellosolves. Examples include ethylene glycol butyl ether and ethylene glycol methyl ether, and examples of esters include sorbitan mono-, di-, or tri-chelates such as monostearate and monoglyceride.
Examples include diethylene glycol laurate and the like. Water-soluble inorganic compounds such as borax often contribute to the shape retention of the water-soluble solidified substrate in water.

As the shape-retaining agent, various alkanolamides are used. Sodium thiosulfate or the like is used as the anti-fading agent of the dye. The flush toilet cleaner may be prepared by mixing the water-soluble solidified base material and the above additives in a heat-melted state. The order of mixing is arbitrary. Volatile fragrances are preferably added as cold as possible in the final step. Minor components such as dyes and fragrances may be mixed in advance with other liquid components or low melting point components to prepare a masterbatch, and this may be mixed with other components. Alternatively, they may be microencapsulated and then mixed.

When the water-soluble solidified substrate of the present invention is used for flush toilets, a molecular weight of 4,000 to 20,000, more preferably 6,000 to 12,000 is suitable.

The amount of the water-soluble solidified base material of the present invention in the detergent for flush toilet is preferably 30 to 90% by weight, more preferably 40 to 80% by weight. The amount of the cleaning agent is 5 to 40% by weight, and the amount of the dissolution rate adjusting agent is generally 0 to 2, though it depends on the desired dissolution rate and the solubility of the water-soluble solidified substrate to be used.
0% by weight, more typically 5-15% by weight. The amount of dye is 0 to 10% by weight The amount of fragrance is 0 to 20% by weight The amount of shape retention agent is 5 to 20% by weight

The water-soluble solidified base material of the present invention is used as a base material for a cleaning agent for flush toilets, a slow-dissolving algae agent for ponds, a fertilizer for hydroponic cultivation, and a fungicide for fireproof reservoirs. Is also good.

Hereinafter, examples will be described. In the examples,
Unless stated otherwise,% or parts are by weight.

Example 1 Preparation of water-soluble solidified base material (1) Polyethylene glycol (PEG) 6000 (100 parts) and stearic acid (3.5 parts) were placed in a four-necked flask and heated at 180 ° C. in a nitrogen stream. And reacted for 8 hours. Phthalic anhydride (1.8 parts) was added to this, and the mixture was further reacted at 180 ° C. for 4 hours in a nitrogen stream. The temperature of the reaction mixture was lowered to 150 ° C., and phenylglycidyl ether (2 parts) was further reacted for 4 hours in a nitrogen stream. A pale yellow flake-like product with a melting point of 55 ° C. was obtained. Acid value of product: 0.9, hydroxyl value:
6.6

Example 2 Preparation of water-soluble solidified base material (2) PEG2000 (100 parts) and behenic acid (13.6 parts) were added to 4 parts.
The mixture was placed in a one-necked flask and reacted at 180 ° C. for 8 hours in a nitrogen stream. Add succinic anhydride (5 parts) to this and add 1 in a nitrogen stream.
It is 80 ° C. The reaction was continued for another 4 hours. The temperature of the reaction mixture is lowered to 150 ° C. and decyl glycidyl ether 1
2.5 parts of it was added and reacted for 4 hours in a nitrogen stream to obtain a pale yellow solid wax having a melting point of 58 ° C. Acid value of product: 1.2, hydroxyl value: 31.5

Example 3 Preparation of water-soluble solidified substrate (3) : PEG4000 (100
Part) and lauric acid (8 parts) were placed in a four-necked flask and reacted in a nitrogen stream at 180 ° C. for 8 hours. Maleic anhydride (2 parts) was added thereto, and the mixture was further reacted at 180 ° C. for 4 hours in a nitrogen stream. The temperature of the reaction mixture was lowered to 150 ° C., 3.8 parts of 2-ethylhexyl glycidyl ether was added, and the reaction was continued for 4 hours in a nitrogen stream to obtain a pale yellow solid wax having a melting point of 50 ° C. Product acid value: 1.0, hydroxyl value: 15.0

Example 4 Preparation of water-soluble solidified substrate (4) : PEG 20000 (100
Part) and capric acid (1.2 parts) into a four-necked flask,
The reaction was carried out at 180 ° C. for 8 hours in a nitrogen stream. Methylenesuccinic anhydride (0.3 parts) was added thereto, and the mixture was further reacted at 180 ° C. for 4 hours in a nitrogen stream. The temperature of the reaction mixture is 150 ° C
Then, 0.4 part of butyl glycidyl ether was added and the reaction was continued for 4 hours in a nitrogen stream to obtain a pale yellow solid wax having a melting point of 53 ° C. Product acid value: 0.7, hydroxyl value: 3.2

Example 5 Solubility test 1. Heat and melt the material at about 80 ℃, and add 15g (W ₀ ) to 3
Mold in a 0 ml cylindrical plastic container (φ50 × H15 mm). 2. Place the 500 ml poly beaker (1) on the magnetic stirrer (2) as shown in Fig. 1 and stirrer piece.
(Length 50 mm, diameter 8 mm) (3) is placed, and the insect screen (4) is hung on the edge of the polybeaker. Put 500 ml of tap water in a poly beaker and put the data on the center of the insect screen (4). 3. The magnetic stirrer is rotated at 250 to 300 rpm while maintaining tap water at 25 ° C., the weight (Wt) of the sample is measured with time, and the dissolution rate is measured by the following formula. Dissolution rate (%) = {(W ₀ −Wt) / W ₀ } × 100 The obtained results are shown in Table 1. In Table 1, Δ indicates an increase in weight. The water-soluble solidified base materials used in Comparative Examples 1, 2 and 3 are as follows: Comparative Example 1: PEG 20000 Comparative Example 2: PEG 6000 Distearate Comparative Example 3: Ethylene oxide / Propylene oxide block (8)
0/20) copolymer (molecular weight 3250)

[0024]

[Table 1]

The test results are shown as an average of 5 pieces for each material. Shape retention test The appearance of the materials used in the dissolution rate test was visually evaluated.
The evaluation criteria are as follows. Table 2 shows the results.

[0026]

[Table 2]

Preferred embodiments of the present invention are summarized below. (A) The water-soluble solidified substrate according to claim 1, wherein the compound having a polyethylene glycol chain is polyethylene glycol having 50 to 500 ethylene oxide units. (B) 0.3 to 0.7 equivalent of fatty acid and 1. 1 of acid anhydride with respect to 1 equivalent of hydroxyl group of the compound having a polyethylene glycol chain.
The water-soluble solidified base material according to claim 1, wherein 4 to 0.6 equivalents and 0.8 to 1.2 equivalents of glycidyl ether are reacted with 1 equivalent of excess carboxyl groups.

[0028]

EFFECTS OF THE INVENTION The water-soluble solidified substrate of the present invention is excellent in dissolution sustainability in water and is hard to lose its shape.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus used for a dissolution rate test.

[Explanation of symbols]

 1 Magnetic stirrer 2 Polybeaker 3 Stirrer piece 4 Insect repellent 5 Material

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Claims (2)

[Claims] 1. A compound having two or more hydroxyl groups and a polyethylene glycol chain having 50 or more ethylene oxide units; a fatty acid having 8 or more carbon atoms; a dibasic acid and a glycidyl ether having a hydrocarbon group having 4 or more carbon atoms. A water-soluble solidified base material obtained by reaction. 2. A method for producing a water-soluble solidified base material in which a compound having a polyethylene glycol chain is first reacted with a fatty acid, the obtained ester is reacted with an acid anhydride, and then glycidyl ether is reacted.