JPS63265963A - Medicated polymer - Google Patents

Abstract

PURPOSE:To make it possible to from a water-sensitive polymer which, when contacted with water, can release a medicament and can perform this release sustainedly, by incorporating a perfume and/or a medicament in a specified porous polymer bead. CONSTITUTION:This medicated polymer is formed by incorporating at least 0.01g, per g of this polymer, of a perfume and/or a medicament in a porous polymer bead having a water absorption rate of at least ten times its own weight. Said porous polymer bead includes one having an average particle diameter of about 1-500mu and a content of pores (continuous or discontinuous pores) >=about 0.01ml/g. Said medicament or perfume can be incorporated in said polymer by, for example, impregnating said polymer with it directly or after dilution with a solvent.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a water-absorbing polymer that swells when it comes in contact with water and has the function of effectively and sustainably releasing medicinal ingredients held in the pores inside the polymer. It concerns sensitive polymers.

[Conventional technology]

There is a desire to develop materials that release the active ingredients of agricultural chemicals, pharmaceuticals, perfumed cosmetics, etc. when they come into contact with water, sweat, or urine, and that have excellent long-lasting effects.

However, in reality, it is difficult to achieve a sustained effect that satisfies the above requirements, and for example, the current situation with pesticides is to spray more pesticides than necessary at one time or to increase the number of sprays.

However, with this method, pesticides run off in the rain and enter rivers, causing damage to fish and shellfish.In addition, in the case of herbicides, the rain spreads the pesticides deep into the soil, causing damage to crops. There are problems such as drug damage.

In addition, cosmetics contain moisturizers, oils, fragrances, disinfectants, ultraviolet absorbers, etc., but there is a problem that their effects are not sufficiently linked. Therefore, when increasing the amount of a specific component in the formulation 1 to increase the sustainability of the effect, problems arise such as stickiness, discomfort, and marked skin irritation.

On the other hand, Japanese Unexamined Patent Publication No. 57-25383 discloses high water absorption (
A plant growth promoter consisting of a phase-resistant powder is disclosed, and it is described that it is mixed with various fertilizers, pesticides, etc. when used. Furthermore, JP-A-61-10502 discloses a cosmetic containing a super absorbent resin and a polyhydric alcohol, and JP-A-61-22583 discloses a preservative containing a fragrance held in a fragrance-retaining carrier and a water-absorbing agent. Gel-like fragrance emitters have been described using mixtures with synthetic polymers. However, none of these can sustainably release medicinal ingredients when they come into contact with water.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a xylem-responsive polymer that releases a drug when it comes into contact with water and that releases a drug in a sustained manner.

[Means for solving problems]

In the present invention, when a specific polymer contains a fragrance and/or drug, the polymer swells when it comes into contact with water, reducing the ability to retain the fragrance and/or drug held inside, and causing the polymer to swell when it comes into contact with water. This was based on the knowledge that the drug was released in a sustained manner.

That is, the present invention provides bead-shaped porous polymers with a water absorption capacity of 10 times or more of their own weight.

Provided is a drug-containing polymer characterized in that it contains 0.01 g or more of fragrance and/or drug per gram.

The bead-shaped porous absorbent polyester used in the present invention can be synthesized by various methods. For example, (i) ○/W emulsion is mixed with an oil-soluble surfactant or a hydrophobic dispersion medium containing an oil-soluble polymer dispersant. In addition to (11), there is a method in which a ◯/W10 emulsion is subjected to strain polymerization, and (11) a method in which a water-soluble polymer is added to an aqueous monomer solution, and then a gas such as N2 or air is blown into the solution and then polymerized.

Among these, in the case of method (i), it is preferable to manufacture by the following method. That is, by using a water-soluble surfactant or a water-soluble polymer dispersant, an O/W emulsion is created in which the inner phase is a hydrophobic phase and the outer phase is an aqueous phase containing at least one water-soluble polymerizable monomer, In this method, the O/W/W emulsion is added to a hydrophobic dispersion medium containing an oil-soluble surfactant or an oil-soluble polymer dispersant to form an O/W/O emulsion, and then monomers are polymerized.

Examples of water-soluble polymerizable monomers used here include vinyl monomers having polymerizable unsaturated groups such as olefinically unsaturated carboxylic acids, olefinically unsaturated sulfonic acids, olefinically unsaturated amines, and olefinically unsaturated ethers. . Among these, examples of vinyl monomers having a sulfonic acid group include unsaturated sulfonic acids such as acrylamide methylpropanesulfonic acid and allylsulfonic acid, and examples of vinyl monomers having an amino group include unsaturated sulfonic acids such as dimethylamine ethyl methacrylate. Examples include saturated amines. In addition, as carboxylate or a vinyl monomer having a carboxylate group,
For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid, unsaturated carboxylic acid esters such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid, such as methoxypolyethylene glycol methacrylate, phenoxypolyethylene glycol methacrylate, etc. Examples of water-soluble salts such as acrylic acid and methacrylic acid include unsaturated carboxylic acid salts such as alkali metal salts, alkaline earth metal salts, and ammonium salts. In the above method, it is preferable to use only the above-mentioned water-soluble monomer as the polymerizable monomer;
Add unsaturated carboxylic acid ester monomers such as methacrylic acid, maleic acid, and fumaric acid to 50% of the total monomer weight (
(hereinafter abbreviated as %), for example, 1 to 50%.

0/W emulsion (so-called Oil in lla)
Examples of the water-soluble surfactant that forms the ter-type emulsion include anionic surfactants, such as sulfates having a prime number of 10 to 24, such as sodium lauryl sulfate, sodium polydiethylene lauryl sulfate, HL B
Examples of nonionic surfactants having a molecular weight of 7.0 or higher include fatty acid esters such as monolauryl sucrose ester, monostearate polyoxyethylene glycol ester, monoisostearate polyoxyethylene glycerin ester, and holioquine ethylene rosin ester. In addition, water-soluble polymer dispersants include polyvinyl alcohol with a degree of saponification of 60 to 95 mol% and a degree of polymerization of 100 to 3000, modified polyvinyl alcohol in which a sulfonic acid group or a carboxylic acid group is introduced into polyvinyl alcohol, and polyethylene oxide. , hydroxyethylcellulose, gum arabic, and the like.

The 0/W type emulsion has, for example, a concentration of the polymerizable monomer of 30% or more, preferably 35 to 50%, a water-soluble surfactant of 0,001 to 20% relative to the monomer,
Preferably, an aqueous solution containing 0.01 to 10% is prepared, and a hydrophobic organic compound is added thereto and stirred to form a ◯/W type emulsion.

Here, as the hydrophobic organic compound, n-pentane, n-
Aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, aliphatic alcohols with 4 to 6 carbon atoms such as n-butyl alcohol, aliphatic ketones such as methyl ethyl ketone, and ethyl acetate. Add aliphatic esters, etc. to the monomer aqueous solution by 2 to
', preferably in the range of 50%.

Prior to starting the above polymerization, a known polymerization initiator was added in advance to the polymerization 0/W emulsion relative to the monomers.
．． It is desirable to add it in an amount of 0.001 to 10%, preferably 0.01 to 5%.

The O/W/○ type emulsion is formed by adding the O/W emulsion to a hydrophobic dispersion medium containing an oil-soluble surfactant or an oil-soluble polymer dispersant.

The oil-soluble surfactant used here is a nonionic surfactant with an HLB of 7 or less, such as sorbitan oleate,
Preferred are sorbitan fatty acid esters such as sorbitan laurate, sucrose fatty acid esters, and phthalates such as cetyl stearylnosium phthalate.

In addition, as oil-soluble polymer dispersants, ethyl cellulose,
cellulose ethers, cellulose acetate, nato cellulose esters and mylenated α-olefins,
Unsaturated carboxylic acid esters such as acrylic acid and methacrylic acid having an alkyl group having 6 to 24 carbon atoms, hydrophobic monomers such as styrene, and hydrophilic monomers having acrylic acid, glycidyl methacrylate, dimethylaminoethyl methacrylate, and polyethylene glycol chains. A copolymer with and the like can be used. These oil-soluble surfactants or polymeric dispersants are preferably added in advance to the hydrophobic dispersion medium in an amount of 1 to 25%. Incidentally, as the hydrophobic dispersion medium, the hydrophobic organic compounds exemplified in the section of the above O/W emulsion can be used.

The amount of hydrophobic dispersion medium C is preferably 10 to 500 parts by weight per 100 parts by weight of the O/W emulsion.

Next, polymerization is started after or simultaneously with the formation of the O/W/O emulsion. The initiation of polymerization can be carried out by a conventional method, but it is preferable that the polymerization temperature is 50°C or higher and the reaction time is in the range of 30 minutes to 6 hours.

This method uses known crosslinking agents such as polyallyl compounds, polyvinyl compounds, polyglycidyl ethers, haloepoxy compounds, polyaldehydes, polyols, polyamines,
Hydroxyvinyl compounds, as well as inorganic or organic metal salts that produce polyvalent ions such as calcium, magnesium, zinc and aluminum, can be added.

Furthermore, monoglycidyl compounds such as phenol polyoxyethylene glycidyl ether can be used as a modifier. When using the above-mentioned crosslinking agent or monoglycidyl compound, it can be used as desired depending on the desired properties of the final product polymer, but it is usually in the range of 0.01 to 10% based on the resulting polymer. It is preferable to do so.

Furthermore, a compound such as a polymerization accelerator may be added to each phase of the ○/1N/○ emulsion.

The polymer produced as described above is dried directly after polymerization or after removing the solvent by decantation or centrifugation using a means such as a vacuum dryer or a fluidized fluid dryer.
It can be used after being pulverized and granulated if necessary.

On the other hand, in method (11), after dissolving a water-soluble polymer in an aqueous monomer solution to give it viscosity, N
A method was used in which a viscous solution having pores was prepared by blowing an inert gas such as No. 2 into it, and then polymerization was carried out.

The monomers used here are the same as those described above, and examples of water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, carboxyethyl cellulose, and the like.

As the absorbent polymer produced by the above method, bead-shaped polymers of any particle size can be used in the present invention, but those with an average particle size of 1 to 500 μm, preferably 2 to 200 μm are preferably used. 0.01 mβ72 or more on facing 3, preferably 0.02 to 0.5 mjl! /g of pores. Note that the pores existing inside may be continuous pores or discontinuous pores.

In the present invention, the drug contained in the polymer may be any component as long as it is soluble in water or alcohol, or emulsifiable or dispersible with a surfactant. Examples include active ingredients such as humectants, fungicides, herbicides, plant growth promoters, poultices, antihistamines, anti-inflammatory analgesics, insect repellents, herbal medicines, and athlete's foot treatments.

Specifically, moisturizers such as glycerin, sorbitol, sodium pyrrolidone carboxylate, glucosamine, and pebquid, oils such as squalane, swaalene, liquid paraffin, fatty acids, and higher alcohols, benzalkonium chloride,
Bactericidal agents such as chlorhexidine and triclosan, P-aminobenzoic acid, phenyl salicylate, 2-hydroquine-
Examples include one type or a mixture of two or more types of ultraviolet absorbers such as 4-methoxybenzophenone and homomenthyl salicylate.

2. As pesticides, triazine type (simazine, atrazine, etc.), dinitroaniline type (trifluarine, etc.)
, phenoxyacetic acid type (2,4-D, 2.4-PA, etc.)
, amide type (butachlor), diphenyl ether type (bifenox, clomethocinyl, etc.), urea type (diuron, methyldimeron, DCMU, etc.), aryloxypropionic acid type (fluazifob, etc.),
Carbamate herbicides (IPC, etc.), organophosphorus herbicides (
Examples include one type or a mixture of two or more types of insecticides such as ECP agents, EPN agents, ESP agents, MEP agents, etc.), pyrethroid insecticides, and chlorine insecticides (chlorzine, Kelsen agents, etc.).

Examples of fragrances that can be contained in the polymer in the present invention include rose, jasmine, rose, orange, and lemon oil.
Examples include species or a mixture of two or more species.

In addition, in order to promote the release of drug components, surfactants,
For example, about 0.01 to 5% of nonionic surfactant, anionic surfactant, cationic surfactant, etc. may be added.

In the present invention, the drug or fragrance can be contained in the polymer in any form, but (i) the absorbent polymer is impregnated with the drug or fragrance directly or diluted with a solvent, or (ii) O/ When adding the W emulsion to a hydrophobic dispersion medium containing an oil-soluble surfactant or an oil-soluble polymer dispersant to create a ○/W/○ emulsion and polymerizing it, it is necessary to It is best to add it after diluting it with a solvent. In the present invention, the amount of drug and/or fragrance contained in the polymer is 0.0 per 1 g of polymer.
The amount is 1 g or more, preferably 0.02 to 0.3 g. or,
The polymer to be used preferably has a water absorption amount of 10 times or more, preferably 20 to 1000 times its own weight.

In the present invention, the polymer containing the fragrance or drug can be used as it is or by adding it to cosmetics, medicines, and agricultural chemicals.

〔Effect of the invention〕

According to the present invention, a water-absorbing sensitive polymer is provided that swells by absorbing water, sweat, and urine, and gradually releases scents and drugs.

Therefore, if the polymer of the present invention is applied to the field of agriculture and horticulture,
It is possible to obtain a pesticide- and fertilizer-supporting material that has a large water-holding capacity, is resistant to rain, and is long-lasting. Excessive diffusion can be prevented and the effective use of chemicals can be achieved.

In addition, when applied to external medicines such as medicinal ointments and soap preparations, it is particularly effective when used on moist surfaces with a lot of secretion, such as eczema and athlete's foot.

When applied to cosmetics and toilet cleaner products, it can be used in a wide range of applications such as antiperspirants, sunscreen creams, powder foundations, body powders, and deodorizing disposable diapers and napkins by incorporating fragrances, UV protection agents, and pigments. .

Next, the present invention will be explained by examples, but the present invention is not limited thereto.

〔Example〕

Example 1 30 cyclohexane was added to a 1P four-bottle flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet tube.
0 g and 3 g of ethyl cellulose (manufactured by Vercules, trade name N-50) were added, stirred, nitrogen gas was blown in to drive out dissolved oxygen, and the temperature was raised to 70°C. In another flask, 43 g of sodium hydroxide was dissolved in 159 g of water, and 100 g of acrylic acid was added to the resulting aqueous solution, and 0.16 g of ammonium persulfate (APS) and carboxylated polyvinyl alcohol (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., Trade name T-350) 3, Og, and 80 g of cyclohexane were added and stirred, and nitrogen gas was blown to drive out dissolved oxygen to prepare an aqueous monomer solution (0/W emulsion).

Next, the dispersion medium in the four-hole flask was thoroughly stirred at a speed of 40 rpm, and the aqueous monomer solution was added dropwise thereto over 2 hours. The reaction was further maintained at 70°C for 2 hours to complete the reaction.

Then, 0.3 g of ethylene glycol diglycidyl ether (trade name, Nagashio Sangyo Denacol EX-810) was added to 2
．． It was dissolved in 7 g of water and added, reacted with stirring at 70°C for 2 hours, removed cyclohexane, and dried at 80°C under reduced pressure to obtain spherical particles with internal pores and an average particle size of 150μ. . (Absorbent polymer A) Automatic porosimeter using mercury intrusion method (manufactured by Shimadzu Corporation, Autopore 9200:Q
The total pore volume (pore volume) determined by ~40000ρsia) is 0.21 mβ per 1 g of polymer, and
Water absorption rate! It was 350g per t1g.

Transfer this to an evaporator and add 2.4g of lemon oil.
A solution prepared by dissolving 100 g of ethanol was added to sufficiently impregnate the internal pores. Next, while rotating the flask in the evaporator, the flask was solidified to produce 8 samples.

Example 2 A polymer was synthesized in the same manner as in Example 1, except that 2.4 g of lemon oil was used instead of 80 g of cyclohexane when preparing the monomer aqueous solution (○/W emulsion) in Example 1. A bead-like porous polymer having an average particle size of 200 μm and containing perfume dispersed in a spherical manner was obtained. The water absorption amount of the polymer was 320 g per 1 g of polymer, and 0.02 g of perfume was impregnated per 1 g of polymer.

Comparative Example A polymer was synthesized in the same manner as in Example 1, except that 80 g of cyclohexane was removed when preparing the monomer aqueous solution (0/W emulsion), and the average particle size was 2.
A comparative polymer of 00μ was obtained. When measured in the same manner as in Example 1, no internal pores were found. The water absorption capacity of this product was 280 g per 1 g of polymer.

This was impregnated with lemon oil in the same manner as in Example 1.

Evaluation method: 2 g of each of the above polymers was placed in a 100 ml beaker, 20 g of urine from a 3-year-old baby was added thereto, and the deodorizing effect was examined after a certain period of time had elapsed.

The results are shown in Table 1, and the numerical values in the table are expressed as 3rd and 8th of the sustained effects among the 10 panelists.

From Table 1, it can be seen that the products of the present invention have good deodorizing effects, and are particularly excellent in deodorizing and connecting effects compared to the comparative examples.

Example 3 Instead of the lemon oil used in Example 1, the following chemicals were impregnated into a polymer according to Example 1.

In addition to this, the sustained release properties of the drug were investigated.

As a result, it was confirmed that the drug had sustained release properties over a long period of time.

Drug △ (humectant) Glycerin drug B (bactericide) Triclosan (Chiha Geigy Co., Ltd.; trade name Irgasan D
P-300) Drug C (herbicide) Butachlor (Japan Monsando Co., Ltd.; trade name Marchet), Tekuroku Seisho 63.3.15 Showa year, month, day 1 case indication 1986 patent application No. 1 (10!10)
2 No. 2, Title of the invention Drug-containing polymer 3, Interaction with the person making the amendment Name of applicant (676) Lion Co., Ltd. 4, Agent 5, Date of amendment order Voluntary 6 Subject of arrest Description of the specification Detailed Description of the Invention (View 7, Contents of Amendment (1)) "Monolauric acid" in line 6 on page 7 of the specification is corrected to "monolauric acid."

Claims (3)

[Claims] (1) A drug-containing polymer characterized in that a bead-like porous polymer with a water absorption capacity of 10 times or more its own weight contains 0.01 g or more of fragrance and/or drug per 1 g of the polymer. (2) The polymer according to claim (1), wherein the bead-like porous polymer has pores of 0.01 ml/g or more. (3) The polymer according to claim (1), wherein the polymer is impregnated with a fragrance and/or a drug.