JPH0480956B2 - - Google Patents

Description

[Detailed description of the invention] B Industrial application field The present invention relates to a method for producing a drug-containing film.

More specifically, the present invention relates to a method for producing a drug-containing film that has excellent medicinal efficacy and long-lasting medicinal efficacy for drugs such as perfumes, fungicides, rust preventives, and insect repellents.

B. Conventional technology Conventionally, paper or film coated with liquid chemicals such as perfumes, antifungal agents, and rust preventives, or films made by directly kneading the chemicals into thermoplastic resins such as low-density polyethylene, or 43−6283
A sheet made of a composition in which odorants such as fragrances are adsorbed to adsorbent porous powder and dispersed in gas-permeable plastic, as described in Japanese Patent Publication No. 47-4295. As disclosed, a method has been proposed in which a hot melt mixture is prepared by uniformly mixing a volatile rust preventive agent, a polyolefin resin, and a polar resin, and a film is formed from this hot melt mixture.

However, paper or film coated with the above-mentioned liquid drug has drawbacks such as rapid volatilization of the drug and lack of long-lasting medicinal efficacy.

In addition, the easiest way to produce a film by directly kneading a liquid drug into a thermoplastic resin is to mix the thermoplastic resin pellets and the drug, and then feed the mixture into the raw material supply port of an extruder to form a film. However, the amount of liquid drug that can adhere to the surface of the pellet is about 1% by weight at most, and even if more than that amount is mixed, the excess will not be sent through the screw and will remain in the raw material supply port of the extruder. Therefore, in severe cases,
The chemicals vaporize and fill the space inside the factory. especially,
This phenomenon is significant when the compatibility between the resin and the liquid drug is poor. Therefore, with this method, it is not possible to obtain a film containing a high concentration of drugs.

On the other hand, in the method using the composition described in Japanese Patent Publication No. 43-6283, there are restrictions on the film forming method. In other words, since it contains adsorbent porous powder that adsorbs odorants, when molding a thin film at high speed by inflation molding method,
Not only is there a concern that problems such as membrane breakage may occur, but also a film containing a relatively high concentration of drug can be obtained, similar to the film described in Japanese Patent Publication No. 47-4295, but liquid drug If the evaporability of the chemical is significant, there is a risk that the chemical may be violently volatilized into the atmosphere due to heating in the extruder during kneading of the resin pellets and liquid chemical and/or film forming, or that the chemical may deteriorate due to heat. There are some problems.

C. Problems to be Solved by the Invention The present invention has been made to solve the above problems. That is, in the prior art, the drug volatilizes violently during the production of the drug-containing film, and the drug-containing film obtained does not maintain good efficacy. Furthermore, it has been difficult to produce a film containing a high concentration of a drug without volatilizing the drug.

Therefore, an object of the present invention is to provide a drug-containing film that does not require mixing operations and heating steps unlike conventional manufacturing methods, does not cause volatilization or deterioration of the drug, and does not contaminate the air inside the manufacturing plant. The present invention provides a method for manufacturing. Furthermore, the present invention provides a method for producing a drug-containing film in which the concentration of the drug and the persistence of drug efficacy can be easily adjusted.

D. Means for Solving the Problems The method for producing a drug-containing film of the present invention uses a soft resin A that is compatible with a drug, or a soft resin A that is compatible with a drug.
Thermoplastic resin B containing and incompatible with the drug
The method is characterized in that a liquid drug is introduced into the inside of a tubular film made of the composition described above to wet the inner surface of the tubular film, and then the tubular film is flattened to allow the drug to penetrate into the inside of the film. .

In the present invention, the soft resin A (hereinafter referred to as "soft resin") that is compatible with the above-mentioned drugs includes petroleum resin, polybutene, polyvinyl chloride resin, unvulcanized natural rubber or synthetic rubber, and carboxyl group-containing There are ethylene copolymers, and in particular, carboxyl group-containing ethylene copolymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer have good compatibility with thermoplastic resin B described later. Ethylene-vinyl acetate copolymer is particularly suitable.

Further, as the thermoplastic resin B to be mixed with the above soft resin, high, medium, and low density ethylene homopolymers, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-octene copolymer, etc. -1 copolymers such as α-olefins containing ethylene as the main component, polypropylene, copolymers with other α-olefins containing propylene as the main component, polybutene-1, poly-4
- Polyolefin resins such as methylpentene-1, and graft-modified products of these with extremely small amounts of polar monomers such as unsaturated carboxylic acids such as acrylic acid and maleic acid or derivatives thereof, nylon-6, nylon-6, 6. Polyamide resins such as nylon-12, polyvinyl alcohol resins, polyester resins, polystyrene resins,
There are saponified products of ethylene-vinyl acetate copolymers and mixtures thereof, and resins that have relatively high crystallinity and good processability such as film-forming properties are used. Among these resins, polyolefin resins are preferred from the viewpoints of versatility, low cost, and good processability.

The liquid drugs used in the method of the present invention include fragrances,
Rust inhibitors, fungicides, preservatives, insect repellents, rodent repellents, deodorants, insecticides, pest repellents, antifouling agents, antistatic agents, etc., including liquid agents themselves and liquid or solid agents. It includes solutions and dispersions in which drugs are dissolved or dispersed.

The fragrances used in the present invention include natural fragrances, synthetic fragrances, and blended fragrances.

Examples of natural fragrances include animal fragrances such as ziyaka, civet, castor, and ambergris, as well as lavender oil, peppermint oil, lemon oil, orange oil,
There are botanical fragrances made from plant essential oils such as rose oil, camphor oil, sandalwood oil, cypress oil, turpentine oil, lime oil, and agarwood.

Synthetic fragrances include hydrocarbons such as limonene (dipentene) and α- or β-pinene;
Alcohols such as dimethyl octanol, linalool, santalol, benzyl alcohol, β-phenylethyl alcohol and cinnamyl alcohol, ethers such as cineole, diphenyl oxide, thymol, anethole and β
- Phenols or phenyl ethers such as naphthyl methyl ether, aldehydes such as benzaldehyde, phenyl acetaldehyde, cinnamic aldehyde, ketones such as acetophenone, p-ethylacetophenone, benzylidene acetone, cinnamic acid, phenyl acetic acid, etc. Acids, γ-
Lactones such as nonalactone, γ-undecalactone and coumarin, esters such as ethyl butyrate, methyl benzoate, ethyl benzoate, ethyl acetate, methyl salicylate, methyl cinnamate, indole, tetrahydroquinoline, musk xylol, musketone, etc. Mention may be made of nitrogen-containing compounds as well as sulfur-containing compounds such as allyl isothiocyanate.

A blended fragrance is a mixture of two or more of the above-mentioned natural fragrances and synthetic fragrances, such as single-flower fragrances such as rose, diasmine, lilla, osmanthus, and carnation, or a combination of these. There are products prepared by adding various fragrances depending on the purpose.

As rust inhibitors, inorganic and organic acid salts of organic amines such as dicyclohexylammonium nitrite, cyclohexylammonium carbonate, isopropylammonium benzoate, diisopropylammonium succinate, etc., aromatic acids such as benzoic acid and naphtholic acid acids, fatty acids with 6 to 10 carbon atoms such as caprylic acid, pelargonic acid, and capric acid, heterocyclic amines such as benzotriazole and methylbenzotriazole, and nitro-substituted aromatic compounds such as m-dinitrobenzene and nitronaphthalene. , hexamethylenetetramine and its derivatives, and one or a mixture of two or more of these may be used.

Examples of antistatic agents include cationic quaternary ammonium salts and imidazoline derivatives; anionic alkyl sulfates, alkylaryl sulfates, and alkyl sulfonates; nonionic polyoxyethylene alkylamines and glycerin fatty acid esters; and amphoteric There are various types of surfactants such as alkyl betaines, among which polyoxyethylene alkyl amines and glycerin fatty acid esters are preferred.

In addition, specific examples of the other drugs mentioned above include:
Food preservatives such as sorbic acid and dehydroacetic acid,
Alternatively, thiabendazole, vinazine, alpha
- Antifungal agents such as bromucinnamaldehyde (BCA), insect repellents and insecticides such as DDT agents, BHC agents, drin agents, parathion agents, DDVP agents, PGP agents, formalin, salicylic acid, creosote, phenol, nitrofurazone, nitrofuryl Disinfectants such as acrylic acid amide, antifouling agents such as phenylmercuric acetate, phenylmercuric oleate, copper naphthenate, copper oleate, or naramycin (trade name, manufactured by Tanabe Seiyaku Co., Ltd.), ramtalin (trade name, Matsushita) Denko Co., Ltd.
(manufactured by Osaka Kasei Co., Ltd.) and cotomycin (trade name, manufactured by Osaka Kasei Co., Ltd.).

When the above drug is in liquid form, it can be used as is or diluted with a solvent. On the other hand, if the drug is in solid or paste form, it may be used by heating it to make it into a liquid state, or by dissolving or dispersing it in a solvent.

In the method for producing a drug-containing film of the present invention,
The method for wetting the inner surface of the tubular film is not particularly limited, but a preferred method is to use the tubular film during inflation film molding. That is, a liquid drug is introduced into the space inside the pinch of the tubular film during inflation molding and allowed to stagnate, thereby wetting the inner surface of the tubular film.Then, the tubular film is pinched to make it flat, and the drug is removed. This is a method of penetrating the inside of the film.

As other specific measures, for example,
The drug of the present invention can be produced by partially modifying the device for dispersing powder onto the inner surface of an inflation tube, which is described in Publication No. 21434 and Publication No. 47-34033, to create a device capable of spraying liquid powder. It can be used in a method for producing a containing film.

The manner in which the method of the present invention is carried out using the illustrated apparatus will be described below.

FIG. 1 is an explanatory diagram of a process in which the method of the present invention is carried out using a conventional top blowing inflation device.

First, a tubular film 2 is formed by blowing air into the molten resin discharged from a die 1 of an inflation device. The tubular film 2 is flattened through a guide plate 3 and a nip roll 4, and then passed through a nip roll 6 again.
and 8 to form a tubular film 2'. In this state, the liquid drug 7 is introduced into the tubular film 2', and the drug 7 is retained as shown in the figure. After the tubular film 2' is wetted with the chemical inside, it is pinched with a nip roll 8 and wound up on a winder 10 as a flattened film.

On the other hand, FIG. 2 is an explanatory diagram of the bottom blow inflation method, which is the simplest method of the present invention.

In FIG. 2, the molten resin discharged from the annular die 11 is expanded to a desired size and formed into a tubular film 12.
is formed, and the liquid drug 13 is introduced into it.
The drug 1 retained on the inner surface of the tubular film 12
3 is attached. After flattening this tubular film 12 with a nip roll 14, a winder (not shown)
Wind it up.

The liquid drug may be retained in the tubular film by introducing only the liquid drug into the tubular film as described above, or by using a support such as a mandrel, a liquid reservoir, or the like.

The content of the above-mentioned drug varies depending on the purpose and use of the product, but can be appropriately adjusted by the pinch pressure of a pinch roll depending on the type of drug, the type of soft resin and thermoplastic resin, etc.

For example, when perfume is used as a drug, soft resin A is made of ethylene-vinyl acetate copolymer (hereinafter referred to as "EVA").
), the fragrance content is EVA
It is approximately proportional to the vinyl acetate (VA) content of That is, if the VA content is 30% by weight, it is possible to impregnate approximately 30% by weight of fragrance. The strength of the fragrance increases as the amount of fragrance contained increases, but it is sufficient if the final product contains about 0.01 to 1% by weight.
When diluting EVA 10 to 100 times,
It is sufficient to impregnate EVA with about 1 to 10% by weight of fragrance.

On the other hand, the sustainability of drug efficacy such as aroma depends on the VA content, the mixing ratio of soft resin A that is compatible with the drug and thermoplastic resin B that is incompatible with the drug, and the presence or absence of a barrier layer. For example, according to the experiments of the present inventors, EVA impregnated with 10% by weight of fragrance
(VA15% by weight), if low density polyethylene is used as thermoplastic resin B and diluted from 1 to 10 times the amount, the fragrance will last for 0.5 to 1 year, and when diluted from 10 to 100 times the amount It maintains its fragrance for about 0.1 to 0.5 years. The persistence of these properties also varies depending on the type of drug, the type and carboxyl group content of soft resin A, the type of thermoplastic resin B, etc., but the same trends apply to other drugs, so
It may be selected appropriately depending on the purpose and use.

In the method of the present invention, by the time the tubular film is opened and used, the liquid drug adhering to the inner surface of the tubular film permeates into the inside of the film, so that no liquid drug remains on the inner surface of the film. However, for this purpose, it is preferable to leave the bag wound on the winding machine for a period of time after wetting it with a chemical and pinching it until it is opened and used. Also, if you want to shorten the leaving time,
Penetration can be effectively promoted by placing the rolled product in a heating chamber (oven chamber).

In addition, if liquid drugs adhere to the inner surface of the tubular film even after being left for a long time, the maximum drug content that the film can contain has been exceeded, so increase the pinch pressure during manufacturing. , reduce the amount of liquid drug adhering to the inner surface of the tubular film, or
Alternatively, the problem may be dealt with by increasing the content of polar groups in the flexible resin or by increasing the content of the flexible resin in the composition.

The tubular film in the method of the present invention may be either a single layer or a multilayer, but in the case of a multilayer structure, the tubular film may contain a soft resin A that is compatible with a liquid drug, or at least 1% by weight of the soft resin A. ,
It is also important that the composition of thermoplastic resin B, which is incompatible with the drug, be used as the innermost layer.

For example, if it is acceptable for the drug to ooze out from both the inner and outer surfaces of the tubular film, the annular single-layer film is constructed from a composition of soft resin A or thermoplastic resin B containing resin A. When it is desired to mainly exude the drug only on the inner surface, the inner layer is made of soft resin A or thermoplastic resin B containing resin A.
It is preferable that the composition be a laminated film having at least two layers, the outer layer of which is a barrier film.

Such barrier resins include acrylonitrile-rich copolymers, saponified ethylene-vinyl acetate copolymers, polyvinylidene chloride resins, polyether resins such as polyethylene terephthalate, polyamide resins, polycarbonate resins, and other heat-resistant resins. There is plastic resin.

Further, in the present invention, commonly used additives such as fillers, pigments, ultraviolet absorbers, antioxidants, and plasticizers may be added.

E. Effects As described above, according to the method of the present invention, there is no step of heating and kneading the drug, so the drug does not volatilize or deteriorate in quality. Furthermore, since a soft resin that is compatible with the drug is used, it is possible to mix the drug at a high concentration and adjust the sustainability of the drug's efficacy.

Furthermore, a method of introducing a liquid drug into the inside of the tubular film to wet the inner surface of the tubular film, flattening the tubular film, and allowing the drug to penetrate into the film prevents volatilization of the drug during the manufacturing process and also speeds up the process. It can be simplified. Furthermore, since the drug is permeated from the inner surface of the film, clear printing can be applied to the outer surface of the film before the drug penetrates to the outer surface.

F. Examples The method of the present invention will be explained in more detail with reference to Examples below.

Example 1 Ethylene-vinyl acetate copolymer (EVA, manufactured by Toyo Soda Kogyo Co., Ltd., trade name: Ultracene UE632)
After mixing 50% by weight of pellets with 50% by weight of low-density polyethylene (LDPE, manufactured by Nippon Petrochemical Co., Ltd., product name: Nisseki Lexron F311EE), the mixture was fed into an extruder and subjected to bottom blow inflation. A tubular film with a thickness of about 50 μm and a folded diameter of about 80 cm was produced. When manufacturing the tubular film, a white rose-based blended fragrance was collected to a height of about 10 cm in the inner space of the tubular film at the pinch point just before Nitzprol, so that the inner surface of the film was wetted with the fragrance in an amount of about 1.2 g/ ^m2 . Adjusted the pinch pressure. Incidentally,
The pinch pressure at this time was approximately 0.5 kg/cm. Further, during film formation, no fragrance was felt during the indoor period.

When this tubular film was rolled up and left indoors for about 2 days and then opened, it was found that not only the outside surface of the film but also the inside surface was not wet, and no adhering liquid with a content of about 2.4% by weight was visible. Despite this, the film emitted a fragrance from the inside and outside, and it lasted for about 6 months.

Comparative Example 1 EVA and LDPE used in Example 1 impregnated with about 4.8% by weight of a white rose-based blended fragrance were subjected to two-layer coextrusion inflation with a layer ratio of 50:50 and EVA as the inner layer. A tubular film with a thickness of about 50 μm was obtained. Even though the inner layer was EVA containing fragrance, the air was filled with a strong fragrance during film formation.

Comparative Example 2 Using only the LDPE used in Example 1, white rose-based blended fragrance was collected to a height of about 10 cm in the inner space of the pinch part of the tubular film just before Nitzprol during bottom blow inflation, and the pinch was applied. Adjust the pressure to approximately 0.5Kg/cm, and the inner surface of the film will be approximately 1.2kg/cm.
A tubular film with a thickness of about 50 μm and a folded diameter of 80 cm was obtained by making it wet with a fragrance of g/m ² . No aroma was felt in the air during film formation.

When this tubular film was wound up and left indoors for about two days and then opened, the inner surface of the film was very sticky, and the outer surface also felt slightly sticky. As a result of analyzing the film after removing the liquid adhering to the surface by wiping it with a cloth, it was found that out of the fragrance equivalent to about 2.4% by weight, only about 1.5% by weight penetrated into the LDPE, and about 0.9% by weight was absorbed into the LDPE. It was found that it remained attached to the surface. Further, after the liquid adhering to the surface was removed, the film had a fragrance from the inside and outside, but when it was left indoors, it lost most of the fragrance after about 3 weeks.

Example 2 90% by weight of the LDPE pellets used in Example 1,
After mixing with 10% by weight of EVA pellets, it is put into an extruder, and during bottom blow inflation, an antistatic agent solution (manufactured by Dainippon Ink Chemical Co., Ltd., product given name:
Saiastat SN) to a height of about 5 cm,
The pinch pressure was adjusted to about 2 kg/cm so that the inner surface of the film was wetted with about 0.2 g/m ² of the antistatic agent solution to obtain a tubular film with a thickness of about 100 μm and a folded diameter of about 25 cm.

When this tubular film was left indoors for about a week and then opened, both the inner and outer surfaces of the film were exposed, and even though no liquid with a content of about 0.2% by weight could be observed, the outer surface was exposed. It was possible to apply corona treatment, sufficient antistatic effect was observed on both the inner and outer surfaces, and the heat sealability was good.

Comparative Example 3 The LDPE pellets and EVA pellets used in Example 1 and the antistatic agent liquid of Example 2 were mixed in a ratio of 90 parts: 10
When the pellets were mixed at a weight ratio of 20 parts and then put into an extruder, the existing liquid caused the pellets to slip and the extruder to cause a surging phenomenon, making it impossible to obtain a good film.

After the resulting defective film was left indoors for about a week, it was no longer subjected to corona treatment.

Example 3 Nylon 6 (PA manufactured by Toray Industries, Inc., trade name: Amilan)
1021), adhesive resin (manufactured by Nippon Petrochemical Co., Ltd., product name: N Polymer R1100), and EVA in a layer ratio
35:15:50, and during three-layer coextrusion inflation with EVA as the inner layer, in the inner space of the pinch part of the tubular film just before the Nippuro roll,
A 20% by weight ethyl acetate solution of a vaporizable fungicide (BCA, α-bromocinnamic aldehyde) was poured into a container about 10 cm long.
The pinch pressure was adjusted to about 0.5 kg/cm so that the inner surface of the film was wetted with about 2 g/m ² of the solution to obtain a tubular film with a thickness of about 50 μm and a folded diameter of about 60 cm. There was no sense of BCA odor in the indoor air during film formation.

When this tubular film was left indoors for about 2 days and then opened, it was found that both the inner and outer surfaces of the film were smooth, and even though no adhering liquid equivalent to about 4% by weight could be observed, it weighed about 0.8%. % BCA odor was felt only from the inside and not from the outside.

Comparative Example 4 Nylon 6, adhesive resin, and EVA mixed with about 0.8% by weight of a volatile fungicide were mixed in a layer ratio of 35:15:
50, and three-layer coextrusion inflation was performed using EVA as an inner layer to obtain a tubular film with a thickness of about 50 μm. Because the outer layer was made of nylon 6, a BCA odor was emitted from the inflation tube during film formation, and there was a strong BCA odor coming from the extruder's raw material input port (hopper).

G. Effects of the Invention As can be seen from the above explanation, the method for producing the film containing the present invention is simple and can be carried out easily. In addition, since the chemical is not heated and kneaded and molded, the chemical will not volatilize and pollute the air, or the chemical will not deteriorate and lose its effectiveness. Furthermore, it is possible to obtain a drug-containing film containing a drug at a high concentration and having a long-lasting drug effect.

Furthermore, a liquid drug is introduced into the tubular film to wet the inner surface of the tubular film, and the tubular film is flattened to allow the drug to penetrate into the film, thereby preventing volatilization of the drug and simplifying the manufacturing process. be able to. In addition, since the drug penetrates from the inner surface of the film, printing can be done before it oozes out to the outer surface, and the corona discharge treatment effect is fully demonstrated within that period, resulting in clearer printing than conventional drug-containing films. This makes it possible to overcome the poor printability common to drug-containing films.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of the process of the present invention using the top blowing inflation method, and FIG. 2 is a process explanatory diagram of the method of the present invention using the bottom blowing inflation method. 1, 11... circular die, 2, 2', 12...
Tubular film, 3... Guide plate, 4, 6, 8, 14
...Nitsprol, 5,9...Guide roll,
7,13...Liquid drug.

Claims (1)

[Scope of Claims] 1. The inside of a tubular film, at least the inside of which is made of a composition of a soft resin A that is compatible with a drug, or a thermoplastic resin B that contains the soft resin A and is incompatible with a drug. A method for producing a drug-containing film, which comprises: introducing a liquid drug to wet the inner surface of the tubular film, flattening the tubular film, and allowing the drug to penetrate into the film. 2. The method according to claim 1, characterized in that the inner surface of the tubular film is wetted by introducing and retaining a liquid chemical into the inner space of the pinched portion of the tubular film during inflation molding. Method for producing drug-containing film. 3. Claim 1 or 2, wherein the soft resin A is an ethylene-vinyl acetate copolymer, and the content of the soft resin A in the thermoplastic resin B composition is at least 1% by weight. A method for producing a drug-containing film. 4. The innermost layer of the tubular film is made of a composition of thermoplastic resin B containing at least 1% by weight of ethylene-vinyl acetate copolymer or ethylene-vinyl acetate copolymer, and the whole is a laminated film of at least two layers. A method for producing a drug-containing film according to claim 1 or 2, which comprises: 5. Claim 1, wherein the liquid drug is selected from the group of fragrances, fungicides, rust preventives, antistatic agents, insect repellents, preservatives, or solutions thereof.
5. A method for producing a drug-containing film according to any one of Items 4 to 4.