JP3433246B2 - Resin composition for sustained release of vaporizable components - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for gradually releasing a useful vaporizing component, which contains a fragrance, a deodorant, an antibacterial / mildewproofing agent and an anticorrosive / rustproofing agent. A single agent or a mixture of agents is used.

Products using the resin composition of the present invention include pellets, films, sheets, molded products, artificial flowers, aromatic materials, sanitary containers, sanitary appliances, agricultural materials, piping materials, food samples, fishery materials, and metal industry products. It has a wide range of uses as a storage material, a packaging material, and various kinds of daily goods made of Pustix, and its industrial application field is extremely wide and covers all products.

[0003]

2. Description of the Related Art There have been many documents and patents on aromatic plastic products containing a synthetic resin containing a fragrance. The present inventors have conducted research on this aromatic plastics product for many years, and one of the achievements during this period is "aromatic resin composition" (Japanese Patent Laid-Open No. 2-292).
369) "Perfume sheet having biological activity" (JP-A-3-258899) "Method for producing fragrant resin composition"
(JP-A-4-13615) and the like.

[0004] After that, the researches by the present inventors were further continued and had a wider range of application, and not only perfume but also other functional materials such as deodorant materials, antibacterial / mildewproofing materials and anticorrosion / anticorrosion materials. As a result of intensive efforts to develop a resin composition applicable to a rust preventive material, the present invention has been achieved.

Among the above research results of the present inventors,
Is mainly a polyolefin resin, which is economically advantageous, but it has low compatibility with the polarity of the base resin and high strength, and sometimes it is difficult to disassemble or discard it after use. Since it was found, the inventors have conducted a search for improving these various drawbacks together and expanding the application to each functional material, and finally arrived at the present invention to be conspicuous.

[0006]

The functional material contained in the synthetic resin has a thermal stability of 160 in a nitrogen atmosphere.
Many are below ℃, and many are colored and decomposed in the air at lower temperatures. A resin composition which is used at 0 to 100 ° C., particularly preferably at 20 to 80 ° C., and which can gradually vaporize and release a functional material as an active ingredient over a long period of time, has a
Care must be taken to prevent the specific components of the functional material from bleeding rapidly or even absorbing moisture during the period of use. This allows the selection of functional material types, the development of a method of adding them to resins, and the study of polar, compatibility, physical properties and chemical properties of resins, so that these properties can be played together. It was confirmed from the preliminary experiments of the present inventors that this must be done.

Subsequent to this, the present inventors conducted many experiments to establish the technology and performance required for the commercialization of the present invention, and found that they were fragrances, deodorants, antibacterial and antifungal agents. It has been discovered that volatile components such as anticorrosion and rust preventive agents have good affinity when combined with ester type plasticizers and ester type biodegradable synthetic resins, and have appropriate vaporizing properties with time, and finally the present invention It was successfully completed.

[0008]

Means for Solving the Problems The present inventors have made at least one vaporizable material selected from the group consisting of fragrances, deodorants, antibacterial and antifungal agents, and anticorrosive and antirust agents into waxes and oligomers . The melting or freezing point to which it belongs is above room temperature
1 to 30% by weight of a solid additive contained in at least one ester-type plasticizer selected from solids having a highly polar ester structure is mixed with an ester-type biodegradable synthetic resin and 40 to 150 ° C. It has been found that a resin composition having a very good quality and capable of gradually releasing a vaporizable component can be obtained when kneading and molding after kneading.

The structure and operation of the present invention will be described in detail below. First, the vaporizable material in the present invention is stable at 150 ° C. or lower and has a vapor pressure of 15
It is a liquid, semi-solid or solid with a temperature of 1 mmHg or more at 0 ° C.

The vaporizable material of the present invention and the ester type plastic material of the present invention are very different in properties. That is, the wax and oil used in the present invention
A pole with a melting point or freezing point above room temperature that belongs to Gomer
The ester type plastic material selected from solids having a highly active ester structure has a distillation temperature range of 180 ° C / 1 mmHg-2.
50 ° C / 30mmHg, particularly preferably 190 ° C / 1mm
The vapor pressure is from Hg to 220 ° C./10 mmHg, which is significantly smaller than the vapor pressure of the vaporizable material used in the present invention. The ester-type plasticizer is a hydroxy fatty acid condensate, an aliphatic dibasic acid-di (or poly) ol condensate, a higher fatty acid-higher alcohol condensate, a natural fat or oil or a hydrogenated product thereof, alone or in a mixture. Further, the ester type biodegradable synthetic resin is a material having a structure of a hydroxy fatty acid polycondensation product or an aliphatic dibasic acid-di (or poly) ol polycondensation product, and the ester type biodegradable synthetic resin is modified. If there is a part of the structure, ether bond, acid amide bond, carbonate bond,
It is a material that may contain a ketone bond, a urethane bond or an alicyclic bond.

Next, typical ones contained in the vaporizable material in the present invention will be described. The fragrance is selected from natural fragrances (vegetable fragrances, animal fragrances) and synthetic fragrances, and it may be a single fragrance (simple, isolated or single fragrance) or a mixed fragrance (formulation, blend or solution). It may be.

Among the plant-based flavors, the important ones are plant essential oils,
Balsam, oleoresin, resinoid, concrete,
Absolute, with many varieties and in liquid, semi-solid and solid forms.

[0013] Typical plant flavors are those obtained from the following plants (only the main family names are shown) by a steam distillation method, a pressing method, an extraction method, a dry distillation method and the like. That is, yew, pine, cedar, cypress, koyamae, gramineae, lily family, hemp family, iris family, ginger family,
Orchidaceae, Pepperidae, Sandalaceae, Magnoliaceae, Lumbaceae, Anemoneaceae, Owlaceae, Lauraceae, Roses, Furoaceae, Rutaceae, Camellia, Anemoneaceae, Violetaceae, Ginkgoaceae, Fusariumaceae, Araliaceae , Essential oils, oleoresin, resinoids, concrete, absolute of plants belonging to Aceraceae, Astragalus, Lamiaceae, Rubiaceae, Ominaceae, Asteraceae, Legumes, Hawthorne, Brassicaceae, etc. and fragrances purified from them. It is a component substance.

Animal flavors include musk, civet,
There are catrium, ambergris, muskrat and shell incense. These may be in the form of powder, semi-solid, solid or liquid such as alcohol tincture. In addition to these purified products, solids and crystals, synthetic substances such as nitromusks, indane musks, tetralin musks, isochroman musks, indole compounds, quinoline compounds, mercaptans, thioethers, amines, and amides are also fragrances. May be used as. Typical examples of macrocyclic musk fragrances are muscone, civetone, cyclopentadecanone, cyclopentadecanolide, ambrettolide, cyclohexadecanolide, ethylene brushlate, and oxahexadecanolide. is there. Of course, these may be liquids, semi-solids, solids, or crystals. Of course, the above may be used alone or as a mixture.

In terms of chemical structure, synthetic fragrances are mainly composed of alcohols, aldehydes, ketones, acetals, ketals, acids, lactones, esters, terpene hydrocarbons and their derivatives. The components include thiols, thioethers, phenols, nitro compounds, amines, amides, isothiocyanates and the like, and these forms are liquid, semi-solid, solid or crystalline.

Examples of synthetic substances include hydrocarbons such as pinene, camphene, limonene, dipenter, terpinolene, myrcene, cymen and caryophyllene, aliphatic alcohols, terpene alcohols, sesquiterpene alcohols, aromatic alcohols, substituted phenols, aliphatics. Aldehydes, terpene-based aldehydes, aromatic aldehydes, aromatic lactones, phenylglycidates, various formal, various acetals, various ketones, various esters,
There are cyclic esters, cyclic ketones, and ionones. These may be liquids, solids, crystals or the like, and these may be used alone or as a mixture.

Incidentally, in the case of a usual mixed fragrance, a top note, a middle note and a base note are often used in combination in consideration of their volatility.

Although the use of deodorants is somewhat limited as compared with fragrances, they have been used since ancient times. The deodorizing method used in the present invention is a sensory method (masking method) and a chemical reaction method (neutralization method, condensation method, addition method,
It is selected from materials suitable for oxidation / reduction method, adsorption reaction method, digestion method).

The deodorants useful in the sensory method are:
Formaldehyde-containing material, glyoxal, glutaraldehyde, aromatic aldehydes or ketones or esters, maleic acid esters, menthol, vanillin, polybasic acids, unsaturated fatty acids, aromatic carboxylic acids, substituted phenols, catechins, isothiocyanates, α- Examples include pinene, borneol, and abietic acid.

In addition to the above, flavanols and their derivatives, flavonols and their derivatives, polyhydric phenols, gallic acid or extracts from plant bark, plant leaves, plant stems, etc. (including essential oils) are useful for the chemical reaction method. Toka wood vinegar component or the like is used. This plant (only the main family name is shown) includes Pinaceae, Cedar family, Cypress family, Ginkgo family, Myrtaceae family, Asteraceae family, Camellia family, Lauraceae family, Lamiaceae family, Rubiaceae family, Beech family, Sesameaceae family, Asteraceae family. Family, Asteraceae,
Rose family, pomegranate family, gramineae family, palm family, lily family, maki family,
It belongs to the family of Musaceae, Hego and so on.

Antibacterial and antifungal agents include alcohols, aromatic alcohols, aldehydes, ketones, phenols, unsaturated fatty acids, aromatic acids, oxyacids, heterocyclic compounds, organic sulfur compounds, Materials suitable for the present invention are selected from organic chlorine compounds, natural essential oils and the like.

Among the antibacterial / antifungal agents, typical chemical substances suitable for the present invention are as follows: isothiocyanates, undecylenic acid, 8-oxyquinoline, oxytetracycline, fatty acid monoglyceride, guaiacol, glutaraldehyde, cleo. Sort oil, cresol, chloracetamide, chlorcresol, chlornaphthalene, dichlorobenzene, chlorphenesin, chloropicrin, 2-
Chlor-N- (hydroxymethyl) acetamide, salicylic acid, salicylic acid ester, dichloro-4-bromophenol, diphenyl, dimethoxane, 2- (4-thiocyanomethylthio) benzothiazole, thymol, dehydroacetic acid, p-chloromethaxylenol, 3 -Hydroxy-5-methylisoxazole, camphor, hinokitiol, pyrogallol, phenylphenol, 2-phenylethanol, 2-phenoxyethanol, benzyl alcohol, brombenzyl alcohol, α-bromocinnamic aldehyde, benzisothiazoline, phenol, resorcin, catechol, Resorcin monoacetate, 2-
Benzyl-4-chlorophenol, 1,2-dibromo-
2,4-dicyanobutane, sulfonamide-based derivatives, carbamate-based derivatives, and the like, and composites containing these are also used.

Among the anticorrosion and antirust agents, the compounds suitable for the present invention belong to so-called vaporization inhibitors, and include organic acid amine salts, carbonate amine salts, amine nitrite salts,
Selected from benzotriazole and its derivatives, oxybenzotriazole and its derivatives, caffeine and its derivatives, hexamethylenetetramine and its derivatives, diisopropylamine salts, dicyclohexylamine salts, urea salts, aromatic acid salts and hydrazine compound salts .

Typical chemical substances suitable for the present invention among the anticorrosive / rust inhibitors are benzoic acid amine salt, fatty acid amine salt, dicyclohexylamine carbonate, diisopropylamine carbonate, dicyclohexylamine nitrite and diisopropylamine nitrite. Nitrate, benzotriazole, alkylbenzotriazole, chlorobenzotriazole, oxybenzotriazole, oxybenzotriazole amine salt, oxybenzotriazole hydrazine salt, 1-
Examples include (3-chloroallyl) hexamine salt, caffeine and its derivatives, organic acid urea salts and their derivatives, and of course, composites containing them can also be used. Corrosion and rust preventive agents include those for iron, non-ferrous metals (for example, copper, silver, zinc, aluminum, solder) and other alloys depending on the type of compound contained.

The above-mentioned various vaporizable materials are generally polar molecules, which are different from nonpolar molecules having symmetrical charge distribution. Therefore, the vaporization property of the vaporizable component in the present invention is appropriately interpreted as follows from the results of many preliminary experiments conducted by the present inventors. That is, the vaporizable material in the present invention is a perfume solution that has been often used by the present inventors, as long as it is a material that is thermally stable at 150 ° C. or lower in an inert gas (in air in some cases). Not only that, it also contains various liquids, semisolids or solid low molecular weight compounds having a vapor pressure of 150 ° C./1 mmHg or more. The solid form may be a powder, a lump, or a crystal, and a vapor pressure of a sublimable substance should be understood as a sublimation pressure.

The above-mentioned various vaporizable materials are used alone or as a mixture depending on the purpose of use, and various combinations must be carried out when the functionality is to be comprehensively exhibited. However, it is excluded from the present invention in the case where the chemical reaction is caused by the mixing of the vaporizable materials and the function is lost, or the vapor pressure becomes 150 ° C./1 mmHg or less. In addition, even when a serious chemical reaction does not occur, it may be difficult to disperse or mix in the ester type plastic material due to rapid solidification or change to a hygroscopic compound, so preliminary experiments should be conducted. It is necessary to be careful not to cause an inconvenient composition.

Next, an ester-type plasticizer which are use in the present invention, hydroxy fatty acid condensates, aliphatic dibasic acid - di (or poly) ol condensates, higher fatty acid - higher alcohol condensates, natural fats and oils or a hydrogen melting point or freezing point is at room temperature or above I alone or a mixture wax or oligomers or mixtures thereof der additives
It is a solid having a highly polar ester structure. When a perfume, a deodorant, an antibacterial / mildewproof agent, or an anticorrosive / rust preventive agent is contained (dispersed or dissolved) in this plastic material, it must be solid. Why is it important to add this solid material to the base resin as an additive?
This is a finding from a preliminary experiment that the occurrence of significant bleeding on the surface of the molded product of the resin composition according to the present invention and the remarkable change in the morphology of the molded product are small.

Generally, the term "plasticizer" refers to a liquid having a high boiling point and a low melting point such as chlorinated paraffin and dialkyl phthalate. The plasticizer in the present invention has a melting point of room temperature or higher belonging to wax and oligomer. It is a solid having a highly polar ester structure, and if the technical expression of perfume is used, it can be said that the composition has a very large retention effect and a very low volatility.

Castor oil, which is known in the art, is therefore a good plasticizer, but it is excluded from the plasticizers of the present invention because it does not solidify at room temperature like waxes or oligomers.

Books selected from waxes and oligomers
The typical ester-type plastic materials used in the present invention are mostly high-boiling substances of wax-like or gum-like substances having melting points or freezing points of room temperature or higher (many of which have boiling points of 250 ° C. or higher). The typical ones are as follows. Cocoa butter, cashew butter, tallow butter, nutmeg fat, palm fat, palm kernel oil, palm oil, Yamaha zero, beef tallow, lard,
Horse fat, mutton fat, boar fat, bird fat, pine fat, capo kuro, candelilla wax, whale wax, jojoba wax, shellac wax, palm wax, beeswax, hardened oil wax, ivota wax, wood wax, rice bran wax, wool wax, cotton wax, laurin dodecyl, octadecyl laurate, palmitic acid propyl, butyl palmitate, amyl, octyl palmitate, decyl palmitate, propyl stearate, butyl stearate, amyl stearate, octyl stearate, decyl stearate, stearic acid Dodecyl,
Other higher fatty acid ester wax, waxy fatty acid di- or triglyceride, higher alkyl succinate, higher alkyl glutarate, higher alkyl adipate, higher alkyl pimelic acid, higher alkyl azelate, higher alkyl sebacate, 2-oxylauric acid Methyl (or ethyl), methyl 2-oxycaprate (or ethyl), methyl 2-oxymyristate (or ethyl), methyl 2-oxypalmitate (or ethyl), methyl 2-oxystearate (or ethyl)
Etc. are the basic ones. Of course, the above methyl (or ethyl) may be a higher alkyl or alkenyl.

The polyester-based plasticizer can be synthesized from a dibasic acid and glycol (in some cases, together with a chain reaction terminator). Wax-like or gum-like substances suitable for the present invention have a molecular weight of 5
It is an oligomer of about 00 to 10,000. For example, adipic acid ester, azelaic acid ester, and sebacic acid ester having a molecular weight of 1000 to 5000 are easy to use. As the polyester plasticizer, hydroxy fatty acid or lactone is used as a raw material. For example, glycolic acid, lactic acid, propiolactone, butyrolactone,
Alternatively there are oligomers from caprolactone. Also in this case, the wax-like or gum-like substance having the above-mentioned molecular weight is used. It should be noted that natural unsaturated fats, drying oils, and semi-drying oils that have been appropriately hydrogenated and processed so that their melting points or freezing points are higher than room temperature are also useful in the present invention.

The most suitable base resin of the present invention is an ester type biodegradable synthetic resin, the structure of which is a hydroxy fatty acid polycondensation product or an aliphatic dibasic acid-di (or poly) ol polycondensation product. A polymer or a polycondensation product having a mixture of these is basically used. However, in the structure, a part of ether bond (-O-), acid amide bond (-CONH- or -CONR-), carbonic acid ester bond (-O-CO-O-), ketone bond (-CO-), urethane A bond (-NHCOO- or -NRCOO-) or an alicyclic bond may be contained. This alicyclic bond is a structure in which cycloalkylene group, oxacycloalkylene group, azacycloalkylene group, oxaazacycloalkylene group and some methylene groups of these alkylene groups are substituted with carbonyl group or carboxyl group. Yes, and may contain a bond such as lactone, lactide, lactam, or urea in some cases.

One of the representative ester-type biodegradable synthetic resins in the present invention is a polycondensation product of hydroxy fatty acid, and well known ones are polyglycolic acid (or polyglycolide) and polylactic acid. (Or polylactide), a polycondensation product of glycolic acid and lactic acid (or polyglycolide lactide). Further, a ring-opening polymerization product of a lactone such as polypropiolactone, polybutyrolactone, polyvalerolactone, poly β-methyl-δ-valerolactone, polycaprolactone, or a ring-opening copolymerization of a mixture of these monomer lactones is used. Mixed lactones are also useful. Other biodegradable polyesters include copolycondensates of cyclic acid anhydrides and oxiranes. In addition, glycolide, lactide, phosgene, carbonic acid ester, caprolactone, ketene, ketene acetal, alkylene oxide, glycidyl compound may be present in the reaction system and modified in the above-mentioned cocondensation and copolymerization.

The compounds as the raw material of the aliphatic dibasic acid are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Maleic acid, fumaric acid, itaconic acid, malic acid, tartaric acid, cyclohexanedicarboxylic acid, dibasic acid having an ether group or a ketone group, and lower esters, acid anhydrides and acid chlorides thereof are useful. The di (or poly) ol raw material is alkylene glycol, alkylene carbonate, alkylene oxide, lower fatty acid ester of alkylene glycol, glycol having ether group or ketone group, and in order to improve the viscosity and crosslinkability of the polycondensation product. A small amount of a polyol such as glycerin, trimethylolpropane, or pentaerythritol may be mixed.

On the other hand, recently, there is biopolyester biosynthesized by microorganisms as a biodegradable synthetic resin. A typical example of the polyester is ICI Polyester (main component is hydroxybutyrate and its trade name is Biopol), and such a biosynthetic product is also included in the ester-type biodegradable synthetic resin of the present invention.

As the ester-type biodegradable synthetic resin, a resin that can be generally used for extrusion molding and injection molding and that can be used at a temperature as low as possible is suitable, and a resin having a molding temperature of 200 ° C. or higher is unnecessary. Is. Cellulose acetate butyrate (melting point to 140 ° C, molding temperature 120 to 190 ° C) is an ester type semi-synthetic resin that has been known for a long time.
However, it has the drawback of poor biodegradability. On the other hand, polyglycolic acid, modified polyglycolic acid, polylactic acid, modified polylactic acid, poly-ε-caprolactone, polyethylene succinate, poly-β-hydroxyalkanoate,
Cocondensation products of lactide (or glycolide) and caprolactone, copolymers of cyclic ethers and cyclic esters, etc. are relatively new.

Particularly, polyglycolide and polylactide having a molecular weight of up to 10,000 and copolymers containing them as a main component are synthesized by thermal (ring-opening) polymerization, enzymatic polymerization, and metal compound catalyst (ring-opening) polymerization. If these oligomers are obtained, a method of introducing an ether bond, an acid amide bond, a carbonic acid ester bond, a ketone bond, a urethane bond or an alicyclic bond by a secondary chemical condensation method, that is, modification is carried out. It can be polymerized into an ester-type biodegradable synthetic resin.

Aliphatic dibasic acid HOCO (CH ₂ ) _n CO
Polyester obtained from OH and various glycols means n ≧ 4 in the case of ethylene glycol and n ≧ 3,1,6-hexanediol in the case of 1,4-butanediol. For n ≧
In the case of 2, diethylene glycol, when n ≧ 8, the polycondensation product shows a moldable melting point. However, there are cases where it is still not sufficient, so at that time, a mixed type polyester of other components, a small amount of tribasic acid or polyol is added to the raw material to increase the crosslinkability, or a biochemical method is used. For example, polyester in which poly (hydroxybutyric acid / hydroxyvaleric acid) is incorporated can be used.

When an optically active hydroxy fatty acid is used as the raw material of polyester, R- is used as the monomer.
The crystallinity of polyester varies depending on whether the polymer, S-form or racemate is used, and whether those polymers are in regular arrangement or in the form of block copolymer. . Since the thermophysical properties of the polyester change depending on this, it is advantageous for the base resin used in the present invention to know the glass transition point, melting point, thermal decomposition temperature, etc. of the resin by preliminary experiments. is there. The ester-type biodegradable synthetic resin referred to in the present invention tends to undergo thermal decomposition in the air faster than ordinary general-purpose plastics, and therefore temperature and time during kneading and molding should be as mild as possible. It is preferable that the operation is performed within a short time by selecting.

The operation of incorporating the various vaporizable materials used in the present invention into the ester type plastic material selected from wax and oligomer is carried out as follows. A vaporizable material or a liquid, a semisolid, or a solid (for example, a solution, an adsorption powder, an inclusion powder or a mixture thereof) containing the vaporizable material is put into a wax or an oligomer which has been heated to a softening point to a melting point in advance and vigorously stirred. The mixing ratio of both is not particularly limited, but in many cases, 0.3 to 3.0 parts of the volatile material is mixed with 1 part of the ester-type plastic material. On this occasion,
Be careful not to ignite the mixture and make it as uniform as possible. And, when this mixture is cooled to room temperature, it must be solidified, which is important for facilitating the subsequent operation.

The solid additive thus obtained must normally be crushed or crushed, and the crushed powder can be stored at room temperature or below for a considerable period of time. Therefore, when mixing the above, a small amount of UV absorber, antioxidant,
It is also good to add stabilizers, lubricants, pigments, fillers, etc. These operations are preferably performed in an inert gas, but in some cases, they can be performed in air. This solid additive is then mixed with the ester type biodegradable synthetic resin in an amount of 1 to 30% by weight, particularly preferably 2 to 28% by weight, and then kneaded. This kneading temperature is 40-150 ° C
In order to ensure product performance and work safety, the addition amount of the solid additive should be maintained at 1 to 30% by weight. If it is 30% by weight or more, the vaporization or evaporation of the vaporizable material becomes vigorous, and the work is likely to be dangerous, and the performance of the resin composition as a product is deteriorated with time. Further, if the addition amount is 1% by weight or less, it is uneconomical in the case of the present invention, and the method already applied to the perfume by the present inventors (JP-A-2-292369 and JP-A-4-13615) is used. Is more advantageous.

The resin composition of the present invention for gradually releasing a vaporizable component is vaporizable depending on the type of the vaporizable component, the environment in which it is used, and the combination of the ester type plasticizer and the ester type biodegradable synthetic resin. The sustained release effect of the ingredients changes considerably.

First, the sustained release period will be described. When the relative humidity is around 50% at room temperature and atmospheric pressure, the product sample piece of the present invention (10 cm × 10 cm, thickness 1 mm) is hung in the center of a glass box of 1 cubic rice to release the vaporizable component. As a result of examining the period, vaporization started after the start of the experiment, the earliest was about 20 days, and the latest was about 500 days. When the change with time of the vaporizable component was examined, as long as the combination material of the ester type plasticizer-ester type biodegradable synthetic resin in the present invention was used, no remarkable imbalance occurred in the vaporization evaporation of the active component. The amount of vaporized components tended to decrease at almost the same rate during the period of use. This phenomenon was very different from the case of ordinary plastic materials such as ABS resin, acrylic resin, polyethylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate, polystyrene, polybutadiene and polypropylene.

In the case of ordinary plastics through the above comparative experiment, after the test period, the sample piece is deformed,
Although cracks and discoloration were observed in some cases, only slight shrinkage and change in transparency due to sustained release of the vaporizable material were observed in the product sample piece of the present invention.

In the case of ordinary plastics, if the amount of the vaporizable material mixed in was large, bleeding of the liquid was seriously caused for several days after the start of the experiment, and the sample was observed for distortion and cloudiness. And in such a case, the analysis result of the head space gas in the box was far from the sustained release of the vaporizable material. The product of the present invention does not cause such inconvenience as long as the conditions specified in the present invention are maintained.

General technical operations for carrying out the present invention will be described with reference to laboratory methods. First, a porcelain dish or stainless steel container is filled with a predetermined amount of an ester-type plastic material selected from waxes or oligomers, and this is heated and liquefied at the lowest possible temperature. Then, a predetermined amount of vaporizable material (which may be liquid or solid) is charged and stirred and cooled. Cooling is generally below 40 ° C. If the cooling product is not solidified (it may not be solidified due to the melting point lowering), some solid powder (eg Aerosil silica, talc, kaolin, clay, activated alumina, natural or synthetic zeolite, zirconium silicate phosphate) , Urea resin, phenol resin, urethane resin, etc.) are added and mixed to solidify at about 40 ° C or less. Then, the solidified product is pulverized into a uniform powder or crushed granules. If a small amount of liquid bleeds during this crushing,
It is possible to add a small amount of the above solid powder, but in such a case, it is generally not appropriate to mix the vaporizable material and the ester plasticizer, so it is recommended to re-prepare. To be done.

The solid additive thus obtained is often in the form of a white to light brown powder or powder, but if necessary, a small amount of a dye or a stabilizer may be added in advance. You may keep it. Then, the solid additive is mixed with powder or granules of the ester-type biodegradable synthetic resin at 1 to 30% by weight at room temperature. Some ester-type biodegradable synthetic resins have a low glass transition point but a high melting point (some have a melting point close to or higher than 200 ° C.). It is preferable to mix the base resin and subject it to a pelletizer so that the molding temperature falls within the range of 40 to 150 ° C. After the required ingredients have been mixed, put the whole mixture on a pelletizer, 40-150 ° C.
Knead in. This kneading is preferably carried out at a temperature as low as possible and in a short time. In some cases, the kneading may be directly carried out in a molding machine without using a pelletizer. In the case of direct molding, it is better to confirm in a preliminary experiment that a homogeneous molded product can be obtained by kneading in a molding machine.

[0048]

EXAMPLES The present inventors have conducted a number of experiments on the resin composition of the present invention for gradually releasing a vaporizable component, and have clarified the superiority of the present invention. In order to explain the contents, some representative examples will be extracted and shown below as examples. Therefore, the method of the present invention should not be construed as being limited to only the examples shown below, and the embodiments may be arbitrarily modified and implemented without departing from the spirit and spirit of the present invention. Is natural.

Example 1 A powder prepared by mixing 100 g of lemon oil and 50 g of Aerosil # 300 (manufactured by Nippon Aerosil Co., Ltd., silica) is mixed and dispersed in a melt of 200 g of hydrogenated jojoba oil kept at 50 ° C. The mixture was then cooled to 10 ° C. to a hard cheese-like solid which was ground to give 350 g of a solid additive of lemon oil. On the other hand, 1800 g of polycaprolactone (melting point, about 52 ° C.) is mixed with a small amount of yellow pigment, and 300 g of the solid additive is added while stirring at 53 ° C. and vigorously mixed. Then, this mixture is put into an extruder, kneaded, extruded into a linear shape having a diameter of 3 mm, cooled to 10 ° C., cut and pelletized. The pellets obtained here were able to gradually emit the scent of lemon for about half a year without impairing the properties of the resin composition.

When the pellets are heated to about 50 ° C., they are softened and can be freely deformed, so that a molded product can be obtained by placing the pellets in a lemon-shaped mold, press-molding and cooling.
This is a scented display fruit sample.

As a comparative example, when only the lemon oil was directly added to the polycaprolactone without using the above-mentioned solid additive and molding was performed, the volatilization of the lemon oil from the molded product was rapid and the surface of the molded product was Liquid bleed was seen in the product, and the change in the scent was also quite noticeable, so it was of poor commercial value as a display material for advertising.

Example 2 Zirconium silicate fine powder (Japanese Patent Publication No. 63-249)
(See No. 71) 45 g of cypress oil (Hinoki thiol 1.7
%) (Containing 50%) in a mortar under a nitrogen stream while thoroughly rubbing them together to prepare a light brown powder. Carosas' α-polyester (molecular weight, about 3500; melting point, about 60 ° C.) 100 g made from adipic acid and 1.6-hexanediol and Sabin pine citrus fruit fat (melting point, about 45 ° C.)
C.) 25 g at 60 to 65.degree. C. and the above light brown powder is added to the liquid oligomer wax and cooled to 10.degree. C. with vigorous stirring to form a solid additive (A). On the other hand, a supercooled liquid (B) prepared by adding a small amount of green dye to 200 g of polycaprolactone (melting point, 60 ° C.), heating and mixing at 60 to 70 ° C., and then cooling to about 50 ° C. or less is prepared. Then, (A) is put into (B) and vigorously stirred, and then temporarily heated to about 55 ° C. to form a uniform wax-like substance, which is then cooled to about 40 ° C. between the biaxial rollers. And extruded into a sheet with a thickness of 2 mm. This sheet is cut into small pieces (length 3 mm, width 3 mm) to form pellets. This pellet contains polycaprolactone, polylactic acid,
Cellulose butyrate acetate, vinyl acetate-ethylene copolymer,
Alternatively, it can be kneaded with a mixture of these and the like and heat-molded into a linear shape or a sheet shape. This molded product can be used as a hot melt type encapsulant for tile cracks in kitchens and baths, and other water leak areas. Since this encapsulating material has the aroma and bactericidal properties of cypress, it was useful for household use. This encapsulant retains the fragrance of cypress for several months.

Examples 3 to 15 In place of cypress oil in Example 2, 50 g of the plant component (synthetic product or formulation) shown in Table 1 was added and the same operation was carried out. The results shown in Table 1 were obtained. However, green pigment was not added to polycaprolactone, and the final product was made into a film sheet with a thickness of 200 microns (10 cm x 10 cm), which was hung in a room (20 ° C) for storage, and then the aroma retention period was calculated. The results are shown in Table 1.

[0054]

[Table 1] (Note: * 1 is the absolute obtained by extracting vanilla beans with acetone and diluting it with about half the volume of ethanol.)

Example 16 50g blended coffee flavor oil and Aerosil # 380
30 g (manufactured by Nippon Aerosil Co., Ltd., silica) was thoroughly mixed in a mortar and mixed with 10 g of hydrogenated jojoba oil, 10 g of cetyl palmitate and 10 g of refined cocoa butter.
It is poured into a heated liquid substance and mixed vigorously, then cooled and pulverized. The solid additive powder obtained here was sprinkled into a mixed melt of 1200 g of polycaprolactone (melting point, about 50 ° C.) and 400 g of polylactic acid (melting point, about 160 ° C.), vigorously mixed at about 120 ° C., and then cooled. And granulate. The granules are relatively easily pressed into a coffee bean-like shape. This molded product is placed at the store for advertising at coffee beans shops or coffee shops and continues to emit aroma for about one year. The used ones decomposed naturally if they were sprayed in the soil, and some effects of soil sterilization and soil insecticide were also observed during this period.

Examples 17 to 21 100 g of purified beef tallow, 80 g of purified beeswax and 60 g of ethyl 2-oxylaurate were heated and melted, and then about 6
The mixture is cooled to 0 ° C., and 200 g of the floral bouquet compounding fragrance shown in Table 2 is mixed with this, and then cooled to room temperature. 30 g of the crushed solid additive obtained here was mixed with 70 g of an equimolar copolycondensate of lactic acid-glycolic acid (melting point, about 72 ° C.) and kept at 75-80 ° C. in a closed container to mix. Then cool down. The cooled product was crushed into granules and enclosed in a small paper bag of 1 g each, which was useful as a deodorant and aromatic material for handbags and leather products. The change in the fragrance balance was slightly different depending on the type of fragrance, and some changes in the fragrance due to air oxidation were also observed. In order to prevent these changes, 0.1% of an antioxidant (“2,6-di-t-butylcresol, α-tocopherol or butylhydroxyanisole”) is added to the fragrance for practical use. It can be used for various purposes. Table 2 shows changes in scent, changes in color, and usage period.

[0057]

[Table 2]

Examples 22 to 30 20 g of purified cashew butter, 10 g of purified carnauba wax and 8 g of purified shellac wax were heated and melted and kept at 60 ° C., and 35 g of the synthetic fragrance shown in Table 3 was melted and cooled. Solidify and crush. The solid additive thus obtained was mixed with 200 g of polycaprolactone (melting point, about 55 ° C.), gently heated and melted, immediately extruded into a wire having a diameter of 2 to 3 mm while cooling, and then cut into pellets. Table 3 shows the results of measuring the effective period until the odor of the synthetic fragrance disappears by keeping the pellet thinly spread on a watch glass and keeping it at room temperature.

[0059]

[Table 3]

When the synthetic fragrances shown in Table 3 were directly mixed with polycaprolactone to form pellets, bleeding of the synthetic fragrances occurred, and at first, a strong odor was exhibited, but the odor gradually weakened. The odor of the pellets disappeared.

Example 31 0.2 g of maleic anhydride, 0.5 g of itaconic anhydride, 3.5 g of benzoic acid and 5.2 g of abietic acid were thoroughly rubbed in a mortar, and then 10.0 g of dried green tea powder was added.
Add and mix well again to leave a green powder. On the other hand, p
-Refined wooden wax melt 1 mixed with 5% dichlorobenzene
If 50 g is prepared, and the above green powder is added thereto and vigorously kneaded and cooled, a solid additive is obtained. The crushed product of this solid additive is polycaprolactone (melting point, about 52 ° C)
After adding to a mixed melt of 150 g and 40 g of polylactic acid (melting point, about 140 ° C.) and kneading at about 100 ° C., a diameter of 1
Extrude into a linear shape of mm. This molded product is appropriately cut and filled in a Tetoron net bag. This filling bag was extremely useful as a cartridge for a device for deodorizing amines such as ammonia, trimethylamine, butylamine and nicotine.

Example 32 Equal volume mixture of glutaraldehyde, undecylene aldehyde, lauryl aldehyde and cinnamic aldehyde 100
50 g of zirconium silicate fine powder and 20 g of Aerosil # 380 (manufactured by Nippon Aerosil Co., Ltd., silica) are mixed while being sprinkled, and then sufficiently pulverized in a ball mill. This powder is sprinkled into 400 g of hydrogenated jojoba oil and 300 g of refined wooden wax, which is kept at a temperature of 65 ° C. or lower, mixed vigorously and then cooled to give a hard cheese-like solid. White powder. Biopol (manufactured by ICI, biosynthetic polyester, melting point, about 140 ° C.) 600 g and the above white powder 15
0 g was thoroughly mixed at room temperature with a ball mill, put in a pressure molding die and pressed at about 110 ° C. to a thickness of 2 mm.
Molded into a plate. This plate-like material was effective in deodorizing amines and mercaptans, and was used for removing the malodor in the freezer compartment.

Example 33 40 g of butyl p-oxybenzoate, 5 g of salicylic acid, o
A mixed fine powder of 55 g of phenylphenol was added to 350 g of purified carnauba wax, kneaded at about 80 ° C., cooled, and then ground. 200 g of the powder of the solid additive obtained here was mixed with 500 g of Biopol (manufactured by ICI, biosynthetic polyester, melting point, about 143 ° C.), placed in a pressure molding die and pressurized at about 120 ° C., Mold into a plate with a thickness of 2 mm. In addition to its strong bactericidal activity, this plate-like material has some acaricidal action, and its effect lasts for more than 30 months. This product is used as a packaging material for processed foods, fruits, paper products, and leather products in addition to molded products, such as films and sheets. As a container, it was suitable for long-term storage of sizing agents and emulsions.

Example 34 The solid additive obtained in Example 33 was replaced with polyethylene succinate (melting point, about 100 ° C.) 5 instead of biopol.
1 g of the granular material obtained by mixing with 00 g and pressure molding is enclosed in a small paper bag. This pouch shows an excellent antifungal effect for a long period of time when it is placed in a packaging box for leather products (bags, shoes, clothes, furs, bags, etc.) one by one. In this example, instead of polyethylene succinate, ε
Almost similar results can be obtained by using a ring-opening polymer of caprolactone and trimethylene oxide or trimethylene carbonate.

Examples 35 to 42 200 g of hydrogenated jojoba oil and 100 g of refined rice bran wax
The mixture was melted while being kept at 60 to 70 ° C., 140 g of an anticorrosive / rust preventive agent (vaporization inhibitor, hereinafter abbreviated as VPI) shown in Table 4 was added thereto, and the mixture was vigorously stirred in a nitrogen stream. Cool and crush the cake-like solid additive obtained. On the other hand, polycaprolactone (melting point, about 52 ° C) 40
0 g is melted, 100 g of the crushed product is added to this, and the mixture is kneaded in a nitrogen stream at a low temperature for as short a time as possible and then allowed to cool. The cooled product is extruded into a sheet by a biaxial roller heated to 45 to 50 ° C. Table 4 shows the results of the anticorrosion and anticorrosion tests performed on this sheet.

[0066]

[Table 4]

The results shown in Table 4 are obtained by sandwiching a business-card-sized thin metal piece with a sheet corresponding to that of the present example, and placing it in a non-woven bag.
This bag was hung in a room of a hot spring bath where the temperature was kept at 20 to 25 ° C., and the surface of the metal flakes was observed every month.
In other words, the one with the first corrosion spots after 2 months was ○, and the one with the first corrosion spots after 4 months was ○.
○, after 6 months, the first one with the appearance of corrosion spots ○ ○
Displayed as ○. When the type of VPI and the combination of applied metals shown in Table 4 were changed, rusting was observed after 1-2 months. If the sheet preparation operation and conditions of this example are not maintained, rusting is recognized within 3 months in most cases, and metal other than the anticorrosion and rust preventive agents shown in the present invention is used. The entire surface of the thin piece was rapidly rusted or discolored.
In the case of Examples 35, 36, and 38, it was effective for up to 12 months.

Example 43 50 g of γ-alumina fine powder (average particle size 1 to 2 μm, specific surface area 230 m ² / g) produced by hydrolysis of aluminum isopropoxide was added to this while stirring in a nitrogen stream. Sprinkle 100 g of lavender oil. The γ-alumina powder having absorbed the lavender oil is kneaded with 150 g of semi-solid hexaplus (manufactured by ICI, polyester oligomer, molecular weight about 5000) at 60 ° C. or lower in a nitrogen stream. When this kneaded product was cooled, a solid additive was obtained, which is crushed. 100 g of this crushed material was mixed with 200 g of polycaprolactone (melting point, about 50 ° C.) and 50 g of polylactic acid (melting point, about 160 ° C.) (70-80).
(° C) and kneaded in a nitrogen stream. At this time, if the purple dye is added and the color tone becomes uniform, put it in a wide-mouthed container and cool immediately to obtain a product. This product has a scent of lavender and is used as an aromatic material in the interior of a room or in an automobile.

Example 44 A mixture of 70 g of α-bromocinnamic aldehyde, 10 g of caffeine and 100 g of octadecyl stearate was heated and melted in a hot water bath, and a fine powder of urea resin (having a primary particle diameter of 0.1 to 0.1) was added thereto. 0.3 micron, secondary particle size 1 to 7 micron, moisture 0.2% or less, specific surface area 20 m ² / g) 90 g
Is added and cooled with mixing to form a powder of a solid additive. Carosas' α-polyester made from succinic acid and 1,4-butanediol (molecular weight, about 500
0, melting point, approx. 110 ° C) 200 g and polyglycolic acid 2
100 g of the above powder is added to a mixed melt with 0 g, and the mixture is kneaded, and the paste-like material is cooled and ground. The white powder obtained here is molded into a sheet and punched into a size of a 500-yen coin. This product exhibits its effect for 3 to 4 years by enclosing it as a mildewproof material and foodproof material when packaging products such as small-sized optical equipment, electric equipment, precision equipment, and instruments. This product is also effective for preserving lenses such as telescopes and cameras, and metals, ceramics, wood, leather, plastics, and textiles related to these devices. If it is in a dry state, it can be used for storing sports equipment, footwear and the like. When α-amyl cinnamic aldehyde or α-hexyl cinnamic aldehyde was used instead of α-bromocinnamic aldehyde in this example, a product having a jasmine odor was obtained, which was used as an aromatic and had an ammonia odor. Despite having an amine odor removing effect, it was not effective as a fungicide / mold inhibitor.

Example 45 The white powder obtained in Example 44 is reheated and the paste obtained is applied to a paper or nonwoven fabric with a heating roller to a thickness of about 1 mm. Apply this coating to a square (3
The cut pieces (cm × 3 cm) were used for the same purpose as in Example 44, and the results similar to the results in Table 4 were obtained. In addition, the above white powder is added to a long oily alkyd resin coating, unsaturated polyester resin coating or cellulose ester lacquer.
About 6 wt% was added and dispersed, and no spots or spots were observed on the surface of the coating film for about 10 months, and this coating film was also used as an antibacterial / antifungal agent.

Example 46 50 g of the white powder obtained in Example 44, 200 g of vinyl acetate-ethylene copolymer (melting point, about 120 ° C.),
Aliphatic petroleum resin (softening point, about 100 ° C.) 100 g is mixed and extruded from a heating roller to form a sheet. This sheet material was cut into a tape shape and used as an adhesive for hot melt such as plywood, fire board, and particle board. This hot-melt adhesive has a strong antifungal property and prevented the occurrence of mildew on the surface of plywood and various boards for about 1 year.

[0072]

EFFECTS OF THE INVENTION The products of the present invention are pellets, sheets, molded products,
It is used for various purposes such as paint. That is, the present invention makes a great contribution to many fields from industrial products to daily necessities, and the effect of the present invention is great.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 67/00-67/02 C08L 67/04

Claims (5)

(57) [Claims] 1. A fragrance, a deodorant, an antibacterial / antifungal agent and an anticorrosion agent.
At least one volatile material selected from the group consisting of rust preventive agents is used as a wax or an oligomer having a melting point or
Has a highly polar ester structure with a freezing point above room temperature
The solid additive 1 to 30 wt% which contains at least one ester-type plasticizer selected from solids, formed by molding were kneaded at 40 to 150 ° C. by mixing the ester biodegradable synthetic resin A resin composition for gradually releasing a vaporizable component. 2. The vaporizable material according to claim 1, which is a liquid, a semisolid or a solid which is stable at 150 ° C. or lower and has a vapor pressure of 1 mmHg or more at 150 ° C. Resin composition. 3. The ester type plasticizer is a hydroxy fatty acid condensate, an aliphatic dibasic acid-di (or poly) ol condensate, a higher fatty acid-higher alcohol condensate, a natural fat or oil or a hydrogenated product thereof, alone or in a mixture. The resin composition for sustained release of the vaporizable component according to claim 1. 4. The vaporizable component according to claim 1, wherein the ester-type biodegradable synthetic resin is a material having a structure of a polycondensation product of hydroxy fatty acid or a polycondensation product of aliphatic dibasic acid-di (or poly) ol. A resin composition for sustained release. 5. An ester-type biodegradable synthetic resin is modified, and its structure partially contains an ether bond, an acid amide bond, a carbonic acid ester bond, a ketone bond, a urethane bond or an alicyclic bond. A resin composition for gradually releasing the vaporizable component according to claim 1 or 4.