JPH05430B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a slow solubilizing agent. [Prior Art] Conventionally, there have been automatic fragrance cleaning compositions for flushing toilets that contain a urethane compound obtained by reacting a polyoxyalkylene compound and an organic polyisocyanate compound as a slow-solubilizing agent [for example, Japanese Patent Application Laid-Open No. 1983-1992 Publication No. 131098]. [Problems to be Solved by the Invention] However, when the above compounds are blended, the slow solubility effect is not sufficient. [Means for Solving the Problems] The present inventors have conducted intensive studies on slow-solubilizing agents with excellent slow-solubilizing effects and compositions containing the same, and as a result, have arrived at the present invention. That is, the present invention
General formula Z[---(AO) _n ---(-YO) _o H-] _p (
1) (wherein Z is a residue of a p-valent active hydrogen-containing compound,
p is an integer of 1 to 8, A is an alkylene group having 2 to 4 carbon atoms, and Y is an integer of 1 to 8.

[Formula] or

[Formula] or

[Formula] or

[Formula] R, R' are hydrogen atoms, alkyl groups or halogen atoms, R'' is an alkyl group having 3 or more carbon atoms, m is 0
or an integer of 1 to 1000, n is 0 or an integer of 1 to 1000. However, at least one of p n is 1
That's all. ); a slow-solubilizing agent for agricultural chemicals consisting of the above-mentioned compound; a slow-solubilizing agent for automatic fragrance cleaners for flush toilets consisting of the above-mentioned compound; and a composition containing the above-mentioned slow-solubilizing agent. be. In the general formula (1), the alkyl groups for R and R' include alkyl groups having 1 to 4 carbon atoms (methyl, ethyl, etc.), and the halogen atoms include chlorine,
Examples include bromine atom. Of R and R', hydrogen atoms and methyl groups are preferred. R,
It is particularly preferred that at least one of R' is a hydrogen atom. The carbon number of R'' is preferably 4 to 50, particularly preferably 8 to 20. Specific examples of the active hydrogen-containing compound constituting the residue of the p-valent active hydrogen-containing compound of Z include alcohols such as 1 Alcohols such as aliphatic alcohols (alcohols with 1 to 20 carbon atoms, such as methyl alcohol and 2-ethylhexyl alcohol), aromatic alcohols (benzyl alcohol,
phenylethyl alcohol), dihydric alcohols such as aliphatic diols (ethylene glycol,
Propylene glycol, dipropylene glycol, diethyle glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, etc. )
and alicyclic diol (cyclohexane-1,4
-dimethanol, etc.), tri- to octahydric alcohols, such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, sucrose, etc. , and alkylene oxide [such as ethylene oxide (also referred to as E0) and/or propylene oxide (also referred to as P0)] adducts thereof;
Phenols include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), and bis(4-hydroxyphenyl).
Sulfone, (bisphenol S), 2,2 bis(4
Hydroquinone as a polyhydric phenol such as -hydroxy-3,5 dibromophenyl) propane,
Catechol, resorcinol, etc. and their alkylene oxides [ethylene oxide and/or
or propylene oxide, etc.] Adduct; Amines include ammonia, alkanolamines (mono-, di-, triethanolamine, tripropanolamine, aminoethylethanolamine, etc.), alkylamines having 1 to 20 carbon atoms, and 2 carbon atoms.
~6 alkylenediamines (ethylenediamine,
hexamethylenediamine, etc.), polyalkylene polyamines (diethylenetriamine, triethylenetriamine, etc.), aromatic amines (aniline,
phenylene diamine, diaminotoluene, xylylene diamine, methylene dianiline, diethyltolylene diamine, diphenyl ether diamine, etc.), alicyclic amines (isophorone diamine, cyclohexylmethane diamine, cyclohexylene diamine, etc.), heterocyclic amines ( Piperazine, aminoethylpiperazine, and other special public works 1986-21044
Adducts of alkylene oxides (such as ethylene oxide and/or propylene oxide), carboxylic acids such as monocarboxylic acids (acetic acid, propionic acid, lauric acid, cetearic acid, oleic acid, etc.), dicarboxylic acids ( Succinic acid, maleic acid, fumaric acid, itaconic acid, azelaic acid, mesaconic acid, ditraconic acid, sebacic acid, glutaconic acid, adipic acid, malonic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, nadic acid, methylnadic acid octylsuccinic acid, dodecenylsuccinic acid, etc.), alkylene oxide [ethylene oxide and/or propylene oxide, etc.] adducts such as tricarboxylic acids (tricarballylic acid, benzenetricarboxylic acid, etc.), and mixtures of two or more of these. It will be done. Among the above p-valent active hydrogen-containing compounds, preferred are divalent hydroxyl group-containing compounds,
Particularly preferred are aliphatic diols. In the general formula, the alkylene group of A is:
Examples thereof include alkylene groups having 2 to 4 carbon atoms, such as ethylene, propylene, butylene groups; and combination groups thereof. Alkylene groups A and Y together with 0 oxygen atoms form oxyalkylene groups (AO) and (YO) such as oxystyrene groups, and multiple oxyalkylene groups (AO) and (YO) may be the same or different. good. The addition type may be a block addition type, a random addition type, or a mixed type of both. Preferably, (AO) and (YO) are added to a p-valent active hydrogen-containing compound. m is preferably 100 to 600, particularly preferably
It is 300-500. When m exceeds 1000, (YO)
As a result, it becomes difficult to obtain a compound having the desired performance. n is preferably 1 to 300, particularly preferably 20 to
It is 100. When n exceeds 1000, the compound becomes insoluble in water and no slow solubilization effect is exhibited. 1 to 8 m and 1 to 8 n may be the same or different. The molecular weight of the compound represented by general formula (1) is usually
500 to 300,000, preferably 1,000 to 100,000, particularly preferably 1,000 to 40,000. The slow-solubilizing agent of the present invention is used as a slow-solubilizing agent for granular agricultural chemical compositions, automatic fragrance cleaning compositions for flush toilets, and the like. The granular agricultural chemical composition consists of an agricultural chemical raw material, a carrier, a slow-solubilizing agent, and optionally auxiliary agents (penetrant, granulation improver, etc.). As the pesticide active ingredient, herbicides such as S-parachlorobenzyl-N,N-diethylthiocarbamate (common name: bentiocarb), 2-chloro-2',
6'-diethyl-N-(butoxymethyl)acetanilide (butachlor), 2,4,6-trichlorophenyl-4-nitrophenol (CNP), etc.; insecticides such as 0,0-dipropyl-0-
(4-Methylthiophenyl)phosphate (propaphos), 0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate (Diazinon), 0-ethyl 0-p
-Nitrophenyl phenyl phosphonothioate (EPN), 0,0-dimethyl-S-(N-methylcarbamoylmethyl) dithiophosphate (dimethoate), etc.; insecticides such as 3-allyloxy-1,2-benzo Thiazole-1,1-
Examples include carbon dioxide (probenazole). Examples of the carrier include bentonite, clay, talc, kaolin, calcium carbonate, and silica sand. Adjuvants (penetrants, granulation improvers, etc.) include sodium ligninsulfonate, sodium condensed naphthalenesulfonate, sodium alkylbenzenesulfonate, sodium dialkylsulfosuccinate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene Alkyl ether sulfates, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, etc. can be used. The amounts of each component in the granular agricultural chemical composition are in the following ranges. % is by weight. Pesticide active ingredient Usually 1 to 80%, preferably 1 to 50% Compound of general formula (1)
Usually 0.1-80% Preferably 1-50% Auxiliary Usually 0-5% Preferably 0.5-3% Carrier Remaining Total 100% In the above, the amount of the compound of general formula (1) is 0.1%
If it is less than 80%, the effect of reducing drug damage and the sustainability of the effect will not be sufficiently exhibited, and even if it exceeds 80%, little improvement in the effect will be observed. The granular agricultural chemical composition of the present invention can be produced by various conventional methods for producing granular agricultural chemicals, such as adsorption, coating, extrusion granulation, and the like. Empty balls prepared by blending the compound of the general formula with a carrier may be placed in a concrete mixer and mixed while adsorbing the raw material. Alternatively, the raw material and the compound of the general formula may be mixed using a solvent such as a lower alcohol if necessary. You may also mix the mixture and adsorb it onto the empty beads. In the coating method, a granular carrier such as silica sand is placed in a concrete mixer and coated with the base material while rotating.In this case, the base material and a compound of the general formula may be mixed and coated, or the base material may be coated with After that, a compound of the general formula may be coated. In the case of extrusion granulation,
The raw material, the compound of the general formula, the carrier, water and, if necessary, the auxiliary agent may be uniformly mixed in a kneader, granulated in a granulator, and then dried. Further, the automatic fragrance cleaning agent composition for flushing toilets consists of a coloring agent, a fragrance, and a slow-solubilizing agent. Examples of the coloring agent include blue or green dyes and pigments that give the flowing water a refreshing feel, and specific examples include Turg Blue G, Green No. 3, Blue No. 1, and Brilliant Blue FCF. The fragrance may be one commonly used, such as borneol, menthol, camphor,
Examples include terpineol and paradichlorobenzole. Furthermore, if necessary, anionic and nonionic surfactants (alkylbenzene sulfonates, alkyl sulfates, etc.) to improve cleaning performance, cationic surfactants such as benzalkonium chloride, and pentachlorophenol to provide bactericidal properties. Antibacterial components, higher saturated fatty acid alcohols such as stearyl alcohol, and solid compounds such as sorbitan monostearate may be added to adjust solubility. Further, water, an organic solvent (ethylene glycol, propylene glycol, glycerin, etc.), a filler such as a water-soluble resin, etc. may be added for molding.
In addition, ion sequestering agents [(ethylenediaminetetraacetate, etc.), deodorants (plant extract ingredients such as lauryl methacrylate, glyoxalic acid, glylosin, Apolide L, (Nippon Kasei), etc.)],
Insect repellents (paradichlorobenzene, naphthalene, camphor, etc.) can be added. The composition of the automatic fragrance cleaning agent composition for flushing toilets (hereinafter referred to as cleaning agent composition) is that the compound of general formula (1) is usually 1 to 80% based on the weight of the cleaning agent composition.
%, preferably 40-80%. If the number of compounds of general formula (1) is less than 1, the effect will not be sufficiently sustained;
Even if it exceeds 80%, there is hardly any improvement in effectiveness. The amount of colorant is usually 0-20%, preferably 1-10%, and the amount of fragrance is usually 1-30%, preferably 5-20%. A method for manufacturing the cleaning composition includes a mixing molding method. The mixing molding method is carried out by, for example, heating and dissolving a slow-solubilizing agent, adding colorants and fragrances, uniformly dispersing or dissolving them, and then cooling and molding them into a certain shape. It can also be molded. [Examples] The present invention will be further explained below with reference to Examples.
The present invention is not limited to this. "Parts" in Examples and Test Examples mean "parts by weight." Examples 1 to 3, Comparative Examples 1 to 3 Table 1 shows the slow solubilizer of the present invention and comparative products.

[Table] Examples 4 to 6, Comparative Examples 4 to 6 Example 4 5 parts of propafos, 40 parts of bentonite, 52 parts of talc
and 10 parts of the compounds (1 to 3) listed in Table 1 were placed in a kneader, 17 parts of water was added, and the mixture was thoroughly kneaded. The mixture was then granulated using a basket-type extrusion granulator having a screen of 0.9 mm in diameter, dried and sieved to obtain a 5% propafos granular agricultural chemical composition of 16 to 32 mesh. Example 5 90 parts of 16 to 32 mesh silica sand was placed in a concrete mixer and while rotating, 10 parts of a 30% aqueous solution of 5 parts of propaphos (1 to 3) and 2 parts of synthetic hydrated silicic acid fine powder were each added in two parts and sequentially coated. , and dried to obtain a 5% propafos granular agricultural chemical composition. Example 6 Benthiocarb 7 parts, cymetrine 1.5 parts, bentonite 40 parts, talc 48.5 parts and compounds (1 to
3) 3 parts were placed in a kneader, 17 parts of water was added, and the same method as in Example 1 was carried out to obtain a granular agricultural chemical composition containing 7% Benthiocarb and 1.5% Cymetrine. Comparative Example 4 A propafos 5% granular agricultural chemical composition was obtained in the same manner as in Example 4 except that 3 parts of Comparative Products 1 to 3 were used instead of Examples 1 to 3. Comparative Example 5 A 5% propafos granular agricultural chemical composition was obtained in the same manner as in Example 2 except that 10 parts of a 30% aqueous solution of Comparative Products (1-3) was used in place of Examples 1-3. Comparative Example 6 A granular agricultural chemical composition containing 7% Benthiocarb and 1.5% Simetrine was obtained in the same manner as in Example 3 except that 3 parts of Comparative Products (1-3) were used instead of Examples 1-3. Test Examples 1-2 Comparative tests on chemical damage of granular agricultural chemical compositions obtained in Examples 4-6 and Comparative Examples 4-6 (Examples 4-2)
5, Comparative Examples 4 to 5) and a weed control rate comparison test (Example 6, Comparative Example 6). The test method and test results are shown below. Test Example 1 (Comparative test on chemical damage) Rice fir was sown in a seedling nursery box (60 x 30 x 30 cm), and immediately after 35 days had passed, water was poured over the seedlings. ~2 Propaphos 5% granular pesticide composition (Propaphos 5% granules)
Spread it evenly and shake off the granules adhering to the rice.
After some time, we moved to the rice fields. Table 2 shows the drug damage test results after 5 days.

[Table] Test Example 2 (Weed Control Rate Comparison Test) Paddy soil containing a large amount of various weed seeds and perennial roots was prepared in a concrete pot (50 x 50 cm) in a paddy state, and paddy rice transplant cultivation was carried out based on the general management method. . Example 3 and Comparative Example 3 5 days after paddy rice transplantation
Benthiocarb 7%/Simetrine made in
The 1.5% granules were uniformly sprayed at 400 g/10 are of active ingredient. 30 and 90 days after treatment, all weeds that had grown in each pot were sampled and the weed control rate was calculated using the following formula. Weed control rate (%) = Weed weight in untreated area - Weed weight in treated area / Weed weight in untreated area x 100 The test results are shown in Table 3.

[Table] Examples 7 to 9, Comparative Examples 7 to 9 Cleaning compositions of the present invention and comparative cleaning compositions were obtained using the formulations shown in Table 4. 30g of each of these cleaning compositions was heated and dissolved, then poured into a cylindrical mold with a diameter of 3.5cm and solidified to form a product.The product was poured 10 times per day with the amount of water used 10 times per day, and the state of dissolution in water was observed. The number of days until dissolution was completed was measured. The results are also shown in Table 4. The colorants and fragrances used in Examples 7 to 9 and Comparative Examples 7 to 9 are as follows. Coloring agent Blue No. 1 fragrance Borneol

[Table] [Effects of the Invention] The slow-solubilizing agent of the present invention has an excellent slow-solubilizing effect. Specifically, as a slow solubilizer for granular agricultural chemicals,
It is more effective in reducing drug damage than conventional technology,
Its durability is excellent. Furthermore, with regard to weeding, it is possible to maintain the weeding effect for a long period of time. As a slow-solubilizing agent for automatic fragrance cleaners for flushing toilets, it produces an average fragrance over a long period of time.

Claims (1)

[Claims] 1 General formula Z[---(AO) _n ---(-YO) _o H-] _p (
1) (wherein Z is a residue of a p-valent active hydrogen-containing compound,
p is an integer of 1 to 8, A is an alkylene group having 2 to 4 carbon atoms, Y is [Formula] or [Formula] or [Formula] or [Formula], and R and R' are hydrogen atoms, alkyl groups, or halogens. Atom, R'' is an alkyl group having 3 or more carbon atoms, m is 0 or an integer from 1 to 1000, and n is 0 or an integer from 1 to 1000. However, at least one of the p n's is 1 or more. 2. A slow solubilizing agent for agricultural chemicals consisting of the compound according to claim 1. 3. A slow solubilizing agent for agricultural chemicals comprising the compound according to claim 1. 3. Containing the slow solubilizing agent according to claim 2 in an amount of 0.1 to 80% based on the weight of the composition. Pesticide composition. 4. A slow-solubilizing agent for automatic fragrance cleaners for flushing toilets comprising the compound according to claim 1. 5. A flushing toilet containing 0.1 to 95% of the slow-solubilizing agent according to claim 4 based on the weight of the composition. Auto fragrance cleaner composition for use.