JPS59124941A - Drug-containing resin composition and its molding - Google Patents

Abstract

PURPOSE:To provide the titled compsn. capable of retaining an invariable medicinal effect or fragrance over a long period of time, by melt-mixing a thermoplastic resin compsn. contg. a drug with a thermoplastic resin non-compatible with the drug. CONSTITUTION:A thermoplastic resin (a) e.g. ethylene/vinyl acetate copolymer) compatible with a drug (b), such as perfume, vaporizable rust inhibitor or insecticide, is impregnated with or melt-mixed with the reagent (b) to obtain a resin compsn. (A). Compsn. A is melt-mixed with other thermoplastic resin (B) (e.g. crystalline PP) compatible with component (a), but incompatible with component (b). EFFECT:The loss of the drug is reduced and the effect of the drug and its persistence can be controlled. USE:Food packaging, protection of fruit and clothing, packing material for machines, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides for
This invention relates to a drug-containing resin composition and a molded article thereof.

Conventionally, vaporizable chemicals such as fragrances, fungicides, rust preventives, insect repellents, etc., have been impregnated into thermoplastic resins such as polyethylene and polypropylene '9 that are not compatible with ordinary chemicals.
They are combined into films and other molded products by extrusion molding, injection molding, etc.

(-gashi), vaporizable agents are generally volatile and dissipative substances, so they are incompatible thermochemicals.
A resin composition in which an i-type resin is impregnated with a drug, or a resin composition in which a drug is mixed in a molten incompatible thermoplastic resin,
Since 1Ilk of the drug is severely lost during molding, not only is molding difficult, but the duration of the medicinal effect is also very short.

Thermoplastic resins that have compatibility with vaporizable drugs are relatively easy to impregnate or melt-mix with drugs, but they have poor processability, such as poor film-forming properties and difficulty in molding. I have a problem with this.

In order to solve the problems described in -, the uninvented invention has been thoroughly investigated.
This is the result of stacking 1.

That is, the present invention provides a resin composition in which a thermoplastic resin (A) that is compatible with a drug is impregnated with the drug, and/or a resin composition in which the drug is mixed in a molten thermoplastic resin (A). The present invention relates to a drug-containing resin composition obtained by melt-mixing a substance into the thermoplastic resin (other thermoplastic resin CB which is compatible with the habit resin (A) but incompatible with the drug) and a molded article thereof. It is something.

The present inventors have discovered that even if the thermoplastic resin (A) that is compatible with the above-mentioned drug is sufficiently impregnated with the drug, the drug is difficult to desorb and volatilize from the resin surface, and sufficient aroma or medicinal efficacy can be exerted. , film formation or molding is difficult, or when the drug-containing composition is melt-mixed with a thermoplastic resin (B) that is incompatible with the drug and compatible with the thermoplastic resin (A), the aromatic The present invention was completed based on the knowledge that it exhibits medicinal effects, can control the fragrance and persistence of its medicinal effects, and is easy to manufacture or mold. .

As the thermoplastic resin (A) used in the present invention,
Petroleum resin, unvulcanized rubber, polybutene, poly 1. I-vinyl resin, carboxyl group-containing ethylene polymer, but especially ethylene-vinyl acetate j1, intermediate polymer (EVA)
), 1,000 ethylene-acrylic ethyl resistant combination (EEA)
The carboxyl group-containing ethylene copolymer of No. 1 is preferable because it always has good compatibility with the drug and the thermoplastic resin CB described below.

Particularly preferred is ethylene-vinyl acetate copolymer.

・Force, heat (What is plastic resin (B)? High, medium, and low density ethylene tj paper type amalgamation, warts, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene Polymers with α-olefins containing ethylene as a main component, such as -1 copolymers, ethyl-4-methylene-1 copolymers, and ethylene-on-7r copolymers; or polypropylene; Copolymer of propylene with other α-olefins, polybutene-1,
Poly-4-methylpentene-14N, +7) polyolefin resins and maleated products thereof, boria l-based resins such as nylon-6, nylon-8, 13, and nylon-12, polyhinyl alcohol-based resins, polyesters resins, saponified products of ethylene-vinyl acetate copolymers, and mixtures thereof.Resins that have relatively high crystallinity and good processability such as ease of manufacture are used.

Among these resins, polyolefin resins are preferred because they are versatile, inexpensive, and have good processability.

The drugs that are components of the resin composition and molded products of the present invention include fragrances, rust preventives, preventatives (powders, preservatives, insect repellents, rodent repellents,
These include deodorants, foresticides, pest repellents, and antifouling agents.

Typical examples of drugs listed below are listed below.

Fragrances include natural fragrances and artificial fragrances, and natural fragrances include animal fragrances such as jacola, shihet (raybyou incense), kasdol (kairi incense), and ambergris (ambergris), lavender oil, mustard oil, There are botanical fragrances made from plant essential oils such as lemon oil, orange oil, rose oil, camphor oil, sandalwood oil, and cypress oil.

In addition, artificial fragrances include synthetic fragrances made of terpene compounds or aromatic compounds, isolated fragrances whose components are separated by fractional distillation from essential oils, and various other types of single N+ incense and synthetic fragrances. It includes mixed fragrances prepared by combining four natural fragrances and other natural fragrances to make them suitable for practical use.

As a vaporized rust preventive agent, dicyclo-xylammorum-'ll! 4r m salts, inorganic and organic salts of organic amines such as cyclohexylammonium carbonate J4, isopropylammonium benzoate, diisopropylammonium succinate, etc., benzoic acid and oak I.
- Aromatic acids such as alcoholic acid, caprylic acid, pelargonic acid,
Capric acid has 6 to 10 carbon atoms, heterocyclic amines such as benzotriazole, methylbenzotriazole, nitro-substituted compounds such as m-dinitrobenzene, nitronaphthalene, Examples include methylenetetramine and its derivatives, and 47 compounds of one or more of these are used.

Further, specific examples of the other drugs mentioned above include food preservatives such as nruvic acid, tehi) to oral acetic acid, and Ui such as thiabendasole, /\inacin, and α-solomucinnamaldehyde (BCA). ijl agent, DDT agent, BHC agent, Dol) 7 agent, parathion agent, DIlV
Insect repellents such as P agents and PGP agents, insecticides, formalin, salicylic acid, freon-1, phenol, nitrofurasono,
Disinfectants such as nitrofuryl acrylic amine F, phenylmercury acetate, phenylmercury oleate, antifouling agents such as naphthene rust-resistant, copper oleate, or naramycin (trade name,
Tanabe Pharmaceutical Co., Ltd.), Ramtalin (trade name, Matsushita Electric Works Co., Ltd.)
, cotomycin (trade name, manufactured by Osaka Kasei Co., Ltd.) and other rodent repellents.
You may use a combination of 2 and 4 types.

The composition of the present invention combines the drug with a compatible thermoplastic resin (
Heat that is incompatible with the drug after pre-impregnating with A) or mixing with the molten thermoplastic resin (A)? If the composition is blended with plastic resin (B) and melt-mixed, but if the drug is a liquid such as perfume, thermoplastic resin (A
), or in the case of solids such as mackerel repellents, insect repellents, mold repellents, etc., they may be dissolved in a suitable solvent and impregnated; and the drug are preferably melt-mixed in a kneader or extruder, such as 11f1.

The content of the drug may be determined according to Class A of the drug and Class 4 of the thermoplastic resins (A) and (B) depending on the purpose, use, etc. For example, using fragrance as a medicine1
7. When the resin (A) is an ethylene-vinyl acetate composite (hereinafter referred to as "EVA'"), the fragrance content is approximately proportional to the vinyl acetate (vA) content of EVA. However, if the VA content is 30% by weight, approximately 30% of fragrance can be impregnated. However, the strength of the fragrance increases with the amount of the fragrance-containing stone, but 0.01 to 1% by weight is sufficient in the final product, so the fragrance-impregnated EVA is diluted 10 to 100 times. If you do,
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 and the mixing ratio of the drug-containing resin (A) and the thermoplastic resin (B). For example, according to the experiments of the inventors of wood,
When EVA (VAI 5% by weight) impregnated with 10% by weight of the above-mentioned fragrance is diluted from ■ to 10 times the amount by using low-strength polyethylene as the thermoplastic resin (B), 0. Continues aroma for 5 to 1 year, from lO to 100
When diluted to double the amount, it maintains its fragrance for about 0.1 to 0.5 years. The durability of these substances also depends on the type of drug, resin (
It varies depending on the type of A), the content of carboxyl groups, the type of resin (B), etc., and the same tendency applies to other drugs, and it is selected as appropriate depending on the purpose, use, etc.

In the composition of the present invention, talc, calcium carbonate,
There is no problem in adding commonly used additives such as fillers such as clay, silica, alumina, wood powder, and paper chips, pigments, ultraviolet absorbers, oxidation inhibitors, and plasticizers. Further, a method of mixing the fragrance-containing thermoplastic resin (A') and another thermoplastic resin (B) containing a filler in advance is the thermoplastic resin (A).

Thermoplastic resin (B), filler and fragrance are directly combined with Hg,
J
The compounding machine or mixer used in the present invention may be any conventional one, such as a Henschel mixer, a Dalton mixer, a Nigu, a Banbury mixer, a hot roll mill, or an extruder. can be used.

Another invention included in the present application is a fragrance-containing molded article comprising a resin composition in which EVA is impregnated with a fragrance and/or a resin composition in which a fragrance is mixed in molten EVA, and a crystalline polyolefin resin. It is related to.

When directly impregnating fragrance into crystalline polyolefin resin,
Liquid fragrances do not impregnate the crystalline polyolefin resin and simply stick to the resin surface, and solid fragrances have a low melting point, so they melt and become liquid in the cylinder of the molding machine and mix. Because it is difficult to use, it contains fragrance, has low heat content, and not only has poor long-lasting efficacy, but also has large losses when mixed.

In comparison, the molded article of the present invention has the following characteristics. That is, (1) it is possible to make a film or molded product with a high concentration of fragrance; (2) it is possible to control the intensity and persistence of the fragrance; (3) the molding conditions are mild; There is almost no deterioration of the fragrance; (4) There is little volatilization and dissipation during processing, so there is almost no loss, and the fragrance is effectively contained, so it is very economical; (5) Processing such as film forming properties and (6) the fragrance-containing resin composition and the crystalline polyolefin resin can be kneaded and molded directly in an extruder.

The above-mentioned crystalline polyolefin resin is a polyolefin-based resin in the above-mentioned thermoplastic resin CB) and has crystallinity 5.
0% or more. If the crystallinity of the polyolefin resin is less than 50%, the blocking of the acid 1 film becomes significant, which is not preferable.

As mentioned above, the compositions and molded articles of the present invention have various advantages such as long-lasting medicinal effects, excellent moldability, and can be manufactured at low cost. It is applied to packaging materials and molded products such as films, sheets, pipes, artificial flowers, dolls, and containers by various forming methods such as molding.
When the molded article is a film, conventional methods such as an inflation method and a T-die method can be applied.

In addition, examples of scented films or scented products include food packaging, laminate materials for commuter passes, garbage bags for kitchens, restrooms, bathrooms, washrooms, storerooms, basements, cafeterias, ships, automobiles, etc. η1, used everywhere, including indoors of railway vehicles. On the other hand, products containing i.p. repellents, insect repellents, etc. are for fruit trees and fruits.

The composition of the present invention and its molded products have a wide range of uses, such as being useful for protecting grains, clothing, leather products, etc., and products containing rust inhibitors being used as packaging materials for steel pipes, machinery, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 When an ethylene-vinyl acetate copolymer (manufactured by Nichiki Petrochemical Co., Ltd., trade name: Nisseki Rexron V 270) was impregnated with rose-based fragrance blend 1, 17% by weight of the copolymer was impregnated. The above fragrance-containing ethylene-vinyl acetate copolymer 10
The weight part is low density polyethylene (hereinafter referred to as “LDPE”)
", manufactured by Nippon Petrochemical Co., Ltd., trade name: 1 stone Xuron F 22) was combined with 100 parts by weight of molten 41 kg to form a pellet, and the pellet was left in the atmosphere at room temperature. The fragrance had not been lost even after more than 6 months had passed.

Comparative Example 1 When the low-density polyethylene pellet of Example 1 was impregnated with the same rose-based blended fragrance as in Example 1, the amount was about 3% by weight.
Only impregnated. When these fragrance-containing pellets were left in the air at room temperature, most of the fragrance was lost in about 3 weeks.

Example 2 When the EVA used in Example 1 was impregnated with a commercially available Lyra-based perfume, 15% by weight was impregnated. After mixing 35 parts by weight of the above fragrance-containing EVA and 1 part of 5 tons of LDPE Ei of Example 1, a film was formed using an extruder, and a good blown film without blocking containing 5% by weight of fragrance was produced. We were able to.

Example 3 A test was carried out in the same manner as in Example 2, except that the lira-based blended fragrance used in Example 2 was replaced with a lemon-based fragrance, and the same good results were obtained.

Comparative Example 2 After mixing 35 parts by weight of the fragrance-containing EVA obtained in Example 2 and 85 parts by weight of the EVA of Example 1, a film was formed in the same manner as in Example 2, and blocking was observed. Remarkably, it did not result in a good blown film.

Comparative Example 3 When the LDPE used in Example 1 was directly impregnated with a commercially available □ Lila-based perfume, only about 0.5% by weight of the perfume could be contained.

When a 2-inflation film was formed in the same manner as in Example 2 using the above-mentioned LDPE containing perfume, only a film containing 0.3% by weight of perfume could be obtained.

Patent applicant: Japan Petrochemical Co., Ltd.

Claims (1)

[Claims] (]) A resin composition and/or a thermoplastic resin (A) that is compatible with a drug and impregnated with the drug. t yo melt 1
The composition "Resin M" in which the drug is mixed with the thermoplastic resin (A) containing the thermoplastic resin (A) is mixed with another thermoplastic resin (B) which is compatible with the thermoplastic resin (A) but incompatible with the drug. ) A drug-containing resin composition formed by melt-mixing. (2) The drug-containing resin composition according to claim 1, wherein the thermoplastic resin (A) is an ethylene copolymer having a carboxyl group. (3) The drug-containing resin composition according to claim 1 or 2, wherein the ethylene copolymer having a carboxyl group is an ethylene-vinyl acetate copolymer. (4) The drug-containing resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is a polyolefin resin. (5) The drug-containing resin composition according to any one of claims 1 to 4, wherein the polyolefin resin is polyethylene, polypropylene, or a mixture thereof. (6) The drug-containing resin composition according to any one of claims 1 to 5, wherein the drug is a vaporizable drug. (,7) The drug according to claim 6, wherein the vaporizable drug is at least one drug selected from the group of fragrances, preventive agents, rust preventives, insect repellents, and repellents. Containing resin composition. (8) By melt-mixing a crystalline polyolefin resin and a resin composition in which an ethylene-vinyl acetate copolymer is impregnated with a fragrance and/or a resin composition in which a fragrance is mixed into a molten ethylene-vinyl acetate copolymer. A fragrance-containing molded product characterized by: (9) The fragrance-containing molded article according to claim 8, wherein the molded article is a film.