JPH03261702A - Sustained release powder - Google Patents

Abstract

PURPOSE:To economically obtain sustained release powder of long working life including perfumes, insecticides, rust preventives, moth-proofing agents, dust-proofing agents, etc., by mixing a long-chain compound, sustained release material and urea. CONSTITUTION:A long-chain compound and a sustained release material are mutually mixed at the weight ratio (1:0.1)-(1:10) into a solution, which is then mixed with urea to obtain the objective sustained release powder. When the solution is sprinkled on the urea followed by slowly agitation, the mixture will become pasty and be expanded; however, after left at rest as it is, the mixture will gradually shrink into the present dry powder. The agitation temperature is 30-60 deg.C, the time required being 2-20hr. Said long-chain compound is >=100 in molecular weight (e.g. hexyl alcohol, capric acid), and the molar ratio of the urea to long-chain compound is (1:5)-(1:15).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing sustained release powder. More specifically, it is a method for producing a sustained-release powder, which is characterized by mixing a 4-compound of a long-chain compound and the sustained-release substance with urea. Sustained-release powders can gradually release fragrances, insect repellents, rust preventives, anti-bacterial agents, or antibacterial agents from within the powder over a long period of time, so they have a wide range of applications and have become a large industry. Sustained-release powders are being used more and more widely as people's lives improve.

(Prior art) Examples of clathrate compounds that incorporate various substances include hydroquinone, deoxycholic acid, and perhydrotriphenylene, but cyclodextrin is an clathrate compound that is turned into a powder and has considerable clathration ability. be. however,
Cyclotextrin requires a long time for the process of incorporating the sustained-release substance and the drying process for powdering, so it is time-consuming to obtain sustained-release powder. Moreover, it has a lower inclusion ability and is more expensive than the urea of the present invention.

(Problem to be solved by the invention) Through repeated research, the present inventors have come to invent a technology for economically producing a powder with longer-life sustained release properties. The feature of the present invention is that it uses urea and a long-chain compound, which was unthinkable in the method using clathrate compounds containing sustained-release substances.6 (Means for Solving the Problems) The purpose of the present invention is to Our objective is to provide a controlled and safe sustained release powder. More specifically, by using urea and a long-chain compound in combination, the problems of short life and high cost of conventional sustained release powders were solved. The key point of the present invention is to incorporate a sustained release substance into an adduct consisting of urea and a long chain compound.

It is well known that urea forms adducts with certain substances. However, even if urea and sustained-release substance are mixed, the sustained-release substance and urea do not form an adduct, but merely become a mixture, and the desired sustained-release powder is not obtained.5 Invention of the Invention As a result of their intensive research, they found that by mixing a sustained-release substance with a long-chain compound (first step) and then further mixing it with urea (second step), the sustained-release substance or urea and long-chain compound were combined. It was discovered that the compound can be incorporated into an adduct of a compound, and the present invention was completed.

(Function) Details of the present invention will be described below. Sustained-release substances as referred to in the present invention can be classified into the following types.

Long-chain compounds The long-chain compounds used in the present invention include those with a molecular weight of 100 or more, in which a functional group is bonded to a molecule with a repeating structure of methylene groups or oxyethylene groups, and the sustained-release substance is incorporated into the urea crystal. properties were recognized. This long-chain compound includes higher alcohol hexyl alcohol (Hexyl alcohol-of, CH, (CH2)
,OH), octyl alcohol (n-0ctyl
alcohol, CH3(CH2) 70H)
, ノ: Lefurco-/l/ (Nonyl alcoho
l, CH3(CH2), OH), Decyl alcohol, CHs(CH2)
, OH), undecyl alcohol (tlndecya
lcohol, CH3(CH2) 160H),
lauryl alcohol
, CH3 (CH2) ll0H) and the power of fatty acids 1 phosphorus a' (+1- Gapr+Cac+d,
) 8 C00ti), caproic acid (Gaproi(
acidCHI (CH2) -C00H), lauric acid (Lauricacid CH3(CH2) +
oCOOH), oleic acid (Ole-ICacld
C+s Hsa 02 ), linoleic acid (Lin0
1iCacld C+s H3202), stearin a (5tearicacid CH3 (CH2)
16cOOH) and the polymerizable monomer 1,6hexandiol diacrylate (16Hexandiol
diacrylate), 1.6 A, xanediol monoacrylate (1,6Hexandiol f
f1o-noacrylate), lauryl acrylate (C+5H2sO
□), caprolactone-modified 2-hydroxyethyl acrylate (2-Hydrox-yethyl acr
ylate, modified caprolac
In addition, there are other long-chain compounds that incorporate various substances into the urea adduct, as long as they have relatively little branching and have a molecular weight of 100 or more and form an adduct with urea. But that's fine.

Natural fragrance and synthetic fragrance The fragrance used in the present invention may be either a natural fragrance or a synthetic fragrance.The natural fragrance may be an animal fragrance or a vegetable fragrance, such as lavender oil, citronella oil, rose oil, lemon oil, etc. oil, jasmine oil, etc. can be used. Various synthetic fragrances can also be used, including acetophenone,
CaHaO), anisic aldehyde (AnlS
ICaldehyde, CaH802) AnlSOle, C7H+tO, Undecylenic aldehyde
dehyde, C,, H2,0), inamyl acetite (l5OaNyl-fOrlaj8, CaH
1202>, geranyl formate (Ceranyl
formato, CIIH1602>, inamyl acetate (C
7H1402) Demethylpencyl carbinyl acetate (Dine-thylbenzylcarb+nyl
acetate, CI2Hr602), vanillin (
van+ll1n, Cm Hll 03), inamyl propionate (Lsoamyl proplo
nate, C5H1602), Ethylpro-plonate, Cs H1
002), paramethylacetophenone p-5etby
l acetophenone, C9H+oO), in-amyl butyrate (ISOall/l butyra
te, C9H+gOz>, etc. can be used. Any other fragrance may be used as long as it forms an adduct with urea in the presence of a long-chain compound.

Insect repellents and insecticides In the present invention, the insect aids are those having insect repellent and insecticidal effects, such as Balajichlorobenzene (E)-dic.
o-dichlorobenzene, o-dichlorobenzene, dimethyl phthalate, etc. Any other substance may be used as long as it forms an adduct with urea in the coexistence with a long-chain compound. .

Rust preventive agent The rust preventive agent used in the present invention includes fatty acids and metal soaps, and the rust preventive oil may be spindle oil, turbine oil, or any other rust preventive agent or rust preventive oil.

Antifungal agent and fungicidal agent The antifungal agent used in the present invention includes toluene, which has antibacterial and bactericidal effects.
, 5-ethoxy-3-trichloromethyl-1,2,4-
Thiadiazole (5-ethoxy-3-trichl
oronethyl-1,2,4-thtadiaz
ol) -1,4-dichloro-2,5-dimethoxybenzene (1,4-Dichloro-2,5-diIIe
thoxybenzene), 2,6-dichloro-4
-tetroaniline (2,6-dichloro-4-n
1 troanilin, 7 inc ethylenebisdithiocarbon #zinc
thiocarbonate), but any other substance may be used as long as it forms an adduct with urea in the presence of a long-chain compound.

The manufacturing method will be described below.

The present invention consists of a first step of mixing a mixture of a long chain compound and the sustained release material with urea, and a second step of mixing it with urea.

The ratio of the long chain compound to the sustained release substance is l:o, 1 to 1:
10 (weight ratio), and this ratio varies depending on the molecular weight of the sustained-release substance. The larger the molecular weight, the lower the proportion of the sustained-release substance. If the proportion of long-chain compounds is too low, the uptake of the sustained-release substance will be reduced. Furthermore, if the proportion of long-chain compounds is too high, the concentration of the sustained-release substance in the adduct will be low, resulting in insufficient performance as a sustained-release powder.

The ratio of urea to long chain compound is 1:5 to 1:15 (molar ratio), preferably 1:8 to 1=11. If the proportion of urea is too low, it will be difficult to incorporate the sustained release substance, and if the proportion of urea is too high, the amount of urea that does not form adducts will increase, making it uneconomical.

The first step of mixing the sustained release substance with the long chain compound does not require any special addition method; if the sustained release substance is a liquid, it is dissolved in the long chain compound.

If the sustained-release substance is a solid, the amount of the sustained-release substance to be dissolved is increased by heating or the like, if necessary, and then dissolved in the long-chain compound.

The second step of mixing a mixture (liquid) of a sustained-release substance and a long-chain compound with urea does not require any special method; it is sufficient to sprinkle the liquid over urea and slowly mix it. In the early stages of stirring, it absorbs urea or liquid, becomes a paste, and expands in volume.

If this sample is left to stand still, its volume will gradually shrink and it will turn into a smooth powder. This powder is a sustained release powder. The time required for the second step is approximately 2 to 20 hours.

The stirring temperature is 20 to 80°C, preferably 3
The temperature is 0 to 60°C. There is no need to limit the stirring atmosphere, which is undesirable because decomposition of the urea adduct occurs at 80° C. or higher, but it is preferable to use a closed container to avoid dissipation of the sustained release substance.

Various compounding techniques commonly used in the technical field can be applied to the sustained-release powder obtained by the present invention, and various sustained-release powder products can be manufactured by various methods.

[Examples] Examples and comparative examples of the present invention will be described below.

Example 1 Insect repellent ortho-dichlorobenzene (D-dich
A sustained release powder of lorobenzene, o-DCB) was prepared. o-DCB does not form an inclusion compound with urea by itself, or is incorporated into an adduct of urea when a long-chain compound coexists with it.

1,47 grams of long-chain compound and 0.48 grams of o-DCB
When 4 grams of urea is added and stirred into a mixture of 4 grams of urea, it initially appears as a paste, but within 10 hours it becomes a smooth powder, yielding a sustained-release powder that incorporates the insect repellent. The sustained release test was conducted by determining the residual amount of 〇-DCB incorporated into the powder at each time when the powder was heated to 50°C. A comparative example is the residual amount of o -DCB in a mixture of 0.48 g of o -DCB and 4 g of urea at 50°C for each time without coexistence of a long chain compound. The shape of the mixture in this case is solid crystals of urea and liquid (o
-DCB) is not attached; only -DCB is sustainedly released. As this table clearly shows, long-chain compounds are present.
- It is clear that DCB is incorporated into the urea adduct and becomes a sustained release powder. All o from within the sustained release powder
- It took two days for the DCB to be released.

Example 1 Comparative Example 1 Time sustained release powder Urea and o-DCB mixture 4 hours
83% 70%8 6
5 4324 21
0 Example 2 A sustained release powder of Toluene, which is an anti-corporeal herb, was prepared. In this case, as in Example 1, toluene alone does not form an adduct with urea, or when urea is added to a mixture with a long-chain chemical, a sustained-release powder incorporating toluene can be formed. When 4 grams of urea is added to a mixture of 1.47 grams of a long-chain compound and 0.6 grams of toluene and stirred, a smooth sustained-release powder incorporating toluene is obtained within 10 hours. A comparative example is the residual amount of toluene at each time in a mixture of 0.6 grams of toluene and 4 grams of urea without the coexistence of a long-chain compound. It is clear that if a long chain chemical is present, it will be incorporated into the toluene or urea adduct and become a sustained release powder.

Example 2 Comparative Example 2 Time Sustained release powder Mixture of urea and toluene 4 hours
70% 56%8 58
42 24 26 0 Example 3 A sustained release powder of a synthetic fragrance with a chewing cam scent having a molecular weight of 100 was prepared. In this case, as in the examples, the fragrance alone does not form an adduct with urea, or when a long-chain compound coexists, it forms an adduct with urea, resulting in a sustained-release powder. 8.0 grams of urea is added to a mixture of 0.82 grams of fragrance and 1.85 grams of long-chain compound, and when stirred, it gradually changes from a paste-like state to a powder-like state in about 5 hours, incorporating the fragrance for sustained release. A solid powder is obtained. When left at room temperature, the scent of the fragrance lasted for more than three months.

Example 4 A sustained release powder of pine resin fragrance having a molecular weight of about 1.30 was prepared. In this case as well, when the fragrance alone is used, no adduct is formed even when urea is added, but when a long-chain compound is present, an adduct with urea is formed. 1.85 grams of long chain compounds and 0.0 grams of fragrance.
When 8 grams of urea is added to the mixed solution with 82 grams of urea, stirred and left for about 5 hours, the paste-like state changes to a powder-like state, and a sustained-release powder incorporating fragrance is obtained. This urea adduct had a pine tar fragrance smell that lasted for more than three months.

From the above 11 examples, it is clear that when a long chain compound is present, the sustained release substance is incorporated into the urea adduct to form a sustained release powder.

Example 5 Synthetic fragrance isobutyl acetate
A sustained release powder of IBA) was prepared. J
I3A by itself is urea and i! ! , #does not form compounds, but is incorporated into urea adducts when long-chain compounds coexist.

When 6g of urea is added to a mixture of 1.891;l of oleic acid and 18^0.78a and stirred, it initially appears as a slurry, but after 5 hours it turns into a smooth powder and the fragrance is absorbed. An incorporated sustained release powder is obtained.

The sustained release test was carried out by determining the residual amount of 18A incorporated into the powder at each time when it was left at room temperature using a gravimetric method.6 As a comparative example, oleic acid was not present and IBA 0.78a was used. This is the residual amount of a mixture of 6 g of urea and 6 g of urea at each time. The shape of this mixture is that the IBA flavor is attached to the urea. No oleic acid is released from the sustained release powder, and only 18^ is sustained release. As is clear from this table, it is clear that when oleic acid is present, IBM is incorporated into the urea adduct and becomes a sustained release powder.

Example 5 Comparative Example 5 Time sustained release powder Mixture of urea and IBA 5 hours
86.7% 83.4%27
51, 1 29.945 3
0, 2 067 16, 6 Example 6 IBA, a synthetic fragrance, was incorporated into urea crystals using lauryl acrylate as a long-chain compound.

The preparation method and sustained release test for the urea adduct were exactly the same as in Example 5, but the amount of lauryl acrylate was 1°619. In this case as well, when the mixture of lauryl acrylate and IBM is mixed with urea, it initially appears as a slurry, but
It will turn into powder for 10 hours.

In sustained release tests, it is clear that the presence of lauryl acrylate causes IBA to be incorporated into the urea adduct, resulting in a sustained release powder.

Example 6 Comparative Example 6 Time sustained release powder Mixture of urea and IBA 5 hours
83.1% 89.6%27
39.4 29.045 22
, 2 067 20.1 Example 7 Preparation method and sustained release properties of a urea adduct using caprolactone-modified 2-hydroxyl acrylate (trade name Aronix 154) as a long chain compound and incorporating IBA, a synthetic fragrance, into the urea adduct The test was conducted in the same manner as in Example 5. The Aronix 154 used is 1.540.

In this case as well, the mixture of Aronix 154 and 18^ added to urea is in the form of a slurry, but over time it changes into a sustained-release powder in which 18A is incorporated into the urea adduct. As is clear from this result, since IBA is slowly released, it is clear that IBM is incorporated into the urea adduct.
No release of 54 was observed.

Example 7 Comparative Example 7 Time sustained release powder Mixture of urea and 18A 5 hours
88.7% 89.6%27 55
．． 5 29.945 35, 8
067 27.5

Claims (7)

[Claims] 1. A method for producing sustained-release powder, which comprises mixing a mixture of a long-chain compound and a sustained-release substance with urea. 2. The ratio of urea to long chain compound is 1:5 (molar ratio) to 1
:15. 3. 2. The method according to claim 1, wherein the ratio of the long-chain compound to the sustained release substance is from 1:0.1 (weight ratio) to 1:10. 4. 2. The method according to claim 1, wherein the long-chain compound has a molecular weight of 100 or more. 5. A method according to claim 1, characterized in that the sustained release substance is selected from the group of: (A) Natural fragrances (B) Synthetic fragrances (C) Insect repellents and insecticides (D) Rust inhibitors (E) Fungicides (F) Antibacterial agents 6. 2. The method according to claim 1, wherein one or more types of different long-chain compounds are mixed. 7. 2. The method according to claim 1, wherein the sustained release substance selected from the above group is used alone or in combination.