TWI841544B - Compositions for emitting volatile substances - Google Patents

Abstract

The present invention provides a means for a composition containing volatile substances to release the volatile substances continuously for a long time. More specifically, it provides a composition for emitting volatile substances, comprising: (A) a polyoxyalkylene modified substance obtained by reacting a polyoxyalkylene compound, a diol compound and a diisocyanate compound; (B) a filler; and (C) a volatile substance.

Description

Compositions for emitting volatile substances

The present invention relates to a composition for emitting volatile substances.

Background technology Compositions containing useful volatile substances in resin gels are used for various purposes. For example, when the volatile substances are aromatic substances, they can make the room emit a good fragrance. Alternatively, when the volatile substances are pest or animal attractants, they can attract pests or animals and can be easily expelled.

For compositions containing such volatile substances, it is required that the volatile substances can be released continuously for a long time (i.e., the release duration is high). Prior art literature Patent literature

[Patent Document 1] Japanese Patent Publication No. 6-32863 [Patent Document 2] Japanese Patent Publication No. 6-140052 [Patent Document 3] Japanese Patent Publication No. 8-12871 [Patent Document 4] Japanese Patent Publication No. 6-98627 [Patent Document 5] Japanese Patent Publication No. 2001-172358 [Patent Document 6] Japanese Patent Publication No. 2002-265780 [Patent Document 7] Japanese Patent Publication No. 2002-331023 [Patent Document 8] Japanese Patent Publication No. 2007-254363 [Patent Document 9] Japanese Patent Publication No. 2017-517611 [Patent Document 10] International Publication No. 2013/084983

Summary of the invention Problem to be solved by the invention The problem of the present invention is to provide a composition containing volatile substances with excellent volatile substance release sustainability. Means for solving the problem

The inventors of this case discovered that a composition containing a specific polyoxyalkylene modified product, a filler and a volatile substance has excellent release sustainability of the volatile substance, and they continued to improve and finally completed the present invention.

The present invention includes the following topics. Item 1 A composition for dispersing volatile substances, comprising: (A) a polyoxyalkylene modified substance obtained by reacting a polyoxyalkylene compound, a diol compound and a diisocyanate compound; (B) a filler; and (C) a volatile substance. Item 2 A composition for dispersing volatile substances as described in Item 1, wherein the polyoxyalkylene compound comprises: at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide/propylene oxide copolymer, ethylene oxide/butylene oxide copolymer, propylene oxide/butylene oxide copolymer and ethylene oxide/propylene oxide/butylene oxide copolymer. Item 3: A volatile substance dispersing composition as described in item 1 or 2, wherein the aforementioned diol compound comprises: at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,9-nonanediol. Item 4: A composition for emitting volatile substances as described in any one of items 1 to 3, wherein the aforementioned diisocyanate compound comprises: at least one selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-xylene-2,4-diisocyanate and 2,4-toluene diisocyanate (TDI). Item 5: A composition for dispersing volatile substances as described in any one of items 1 to 4, wherein (B) the filler comprises: at least one selected from the group consisting of silicon oxide, magnesium carbonate, clay, talc, calcium carbonate, titanium oxide, diatomaceous earth, cyclodextrin and modified cyclodextrin. Item 6: A composition for dispersing volatile substances as described in any one of items 1 to 5, wherein (C) the volatile substances are selected from one or more selected from the group consisting of fragrances and pheromones and repellents for pests or animals. Item 7 A composition for absorbing liquid from a liquid composition mixed with volatile substances, comprising the following (A) components and (B) components: (A) a polyoxyalkylene modified substance obtained by reacting a polyoxyalkylene compound, a diol compound and an isocyanate compound; and (B) a filler. Item 8 A method for increasing the sustainability of the release of volatile substances from a liquid composition into the atmosphere, the liquid composition being a liquid composition mixed with volatile substances, the method comprising: a step of absorbing liquid from a liquid composition mixed with volatile substances by a composition comprising the following (A) components and (B) components; (A) a polyoxyalkylene modified substance obtained by reacting a polyoxyalkylene compound, a diol compound and a diisocyanate compound; and (B) a filler. Invention Effect

According to the present invention, the release duration of volatile substances can be improved. The volatile substance dispersing composition of the present invention can make the volatile substances contained therein slowly diffuse, and the effect of the volatile substances can be maintained for a longer time (that is, it also has excellent sustained release). In addition, the volatile substance dispersing composition of the present invention can contain more volatile substances than the volatile substances that can be contained in general resins. Therefore, from the start of release to the time when a predetermined period of time (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 hours, or 1, 2, 3, 4, 5, 6 or 7 days) has passed, the amount of volatile substances that can be released and the total amount of volatile substances that can be released are greater than those of general resins.

The following is a detailed description of each embodiment of the present invention.

The volatile substance-releasing composition included in the present invention contains (A) a specific polyoxyalkylene modified substance, (B) a filler, and (C) a volatile substance. These components are sometimes referred to as component (A), component (B), and component (C), respectively. In addition, the volatile substance-releasing composition is sometimes referred to as the volatile substance-releasing composition of the present invention.

The specific polyoxyalkylene modified product (component (A)) is a compound obtained by reacting (polymerizing) a polyoxyalkylene compound, a diol compound and a diisocyanate compound.

The aforementioned polyoxyalkylene compound can be exemplified by polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide/propylene oxide copolymer, ethylene oxide/butylene oxide copolymer, propylene oxide/butylene oxide copolymer, and ethylene oxide/propylene oxide/butylene oxide copolymer. The polyoxyalkylene compound can be used alone or in combination of two or more. In addition, "/" is a symbol for indicating a copolymer of each oxide. For example, ethylene oxide/propylene oxide copolymer means a copolymer of ethylene oxide and propylene oxide.

Although not particularly limited, polyoxyalkylene compounds having a number average molecular weight of 5,000 to 50,000 are preferred, and polyoxyalkylene compounds having a number average molecular weight of 10,000 to 30,000 are more preferred.

In addition, the value of the number average molecular weight is obtained by the following determination method. Method for determining the number average molecular weight: Prepare a dimethylformamide solution of a polyoxyalkylene modified product with a concentration of 1 mass %, and determine it by high-performance liquid chromatography. Then, determine a molecular weight marker (polyethylene oxide) of known molecular weight under the same conditions, make a comparison curve, and calculate the number average molecular weight (Mn). In addition, the determination conditions are as follows.

Measuring machine: HLC-8220 (manufactured by Tosoh Corporation) Column: TSK GEL Multipore HXL-M manufactured by Tosoh Corporation Column temperature: 40°C Eluent: dimethylformamide Flow rate: 0.6 ml/min In addition, polyoxyalkylene compounds having 90% by mass or more of ethylene oxide groups are preferred, and polyoxyalkylene compounds having 95% by mass or more of ethylene oxide groups are more preferred.

Examples of the aforementioned diol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol. These diol compounds may be used alone or in combination of two or more. In addition, the aforementioned diol compound does not include the aforementioned polyoxyalkylene compound. That is, the aforementioned diol compound is a diol compound other than the aforementioned polyoxyalkylene compound.

The usage ratio of the diol compound is preferably 0.8 to 2.5 mol, more preferably 1.0 to 2.0 mol, relative to 1 mol of the polyoxyalkylene compound. The molar number of the polyoxyalkylene compound can be obtained by dividing its mass by the number average molecular weight.

The aforementioned diisocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups (-NCO) in the same molecule, and examples thereof include 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-xylene-2,4-diisocyanate, and 2,4-toluene diisocyanate (TDI). Among these diisocyanate compounds, dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are preferably used. These diisocyanate compounds may be used alone or in combination of two or more.

The aforementioned polyoxyalkylene compound, diol compound and diisocyanate compound are used in the following proportions: the molar ratio of the isocyanate group of the diisocyanate compound to the total molar number of the terminal hydroxyl group of the polyoxyalkylene compound and the hydroxyl group of the diol compound [R value = (-NCO group/-OH group)] is preferably about 0.7 to 1.2, more preferably about 0.8 to 1.05.

The method for reacting the polyoxyalkylene compound, the diol compound, and the diisocyanate compound can be a known method. For example, a method of dissolving or dispersing them in a reaction solvent such as toluene, xylene, or dimethylformamide and reacting them; and a method of uniformly mixing these substances in powder or solid form, heating them to a predetermined temperature, and reacting them. From the perspective of industrial-scale implementation, a method of continuously supplying each raw material in a molten state and mixing them in a multi-screw extruder to react them is preferred. At this time, the reaction temperature is preferably 70 to 210°C.

In addition, when producing polyoxyalkylene modified products, a catalyst may be added to the reaction system from the viewpoint of promoting the reaction. For example, appropriate amounts of triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin dilaurate, 2-ethylhexanoate tin, and triethylenediamine may be added as catalysts.

By this method, a polyoxyalkylene modified product can be obtained. If this method is used, the polyoxyalkylene modified product can generally be obtained in the form of pellets, sheets or films. These can be used directly in the volatile substance dispersing composition of the present invention, or they can be crushed by a crusher and then used in the volatile substance dispersing composition of the present invention. The crushing method is not particularly limited, but in order to prevent melting due to shear heat during crushing, it is preferable to perform cryogenic crushing. For example, liquid nitrogen can be used for cryogenic crushing.

In addition, when producing the polyoxyalkylene modified substance, a filler (B) may be added to the reaction system. At this time, the obtained composition containing the polyoxyalkylene modified substance already contains the components (A) and (B), and therefore, the volatile substance dispersing composition of the present invention may be prepared by adding the component (C) to the composition. In addition, the composition containing the polyoxyalkylene modified substance obtained by adding the filler (B) to the reaction system may be directly used in the volatile substance dispersing composition of the present invention, or may be used in the volatile substance dispersing composition of the present invention after being pulverized by a pulverizer or the like. The pulverization method is not particularly limited, but in order to prevent melting due to shear heat during pulverization, cryogenic pulverization is preferably performed. For example, cryogenic pulverization may be performed using liquid nitrogen.

The polyoxyalkylene modified substance is preferably water-absorbent (i.e., has water-absorbing capacity). In particular, it is preferable to make (C) the volatile substance contained in the polyoxyalkylene modified substance when preparing the volatile substance dispersing composition of the present invention. In this case, for example, the following method can be used: the volatile substance is added to water to dissolve or disperse it, or the volatile substance and water are separated into layers (two-layer separation), and then the polyoxyalkylene modified substance absorbs the liquid mixed with the volatile substance. Although not particularly limited, the water-absorbing capacity of the polyoxyalkylene modified substance is preferably 10-40 g/g, more preferably 15-35 g/g. In addition, the water absorption capacity referred to in the present invention means: 1.0 g of polyoxyalkylene modified product (A[g]) is weighed and immersed in 100 mL of ion exchange water at room temperature (22°C) for 24 hours to gel, and the gel is filtered through a 200 mesh (pore size: 75 μm) metal mesh, and the gel mass (B[g]) of the filtered product (residue) is measured and calculated according to the following formula (since A is 1, the value is B).

Water absorption capacity (g/g) = B/A Also, although not particularly limited, the water solubility of the polyoxyalkylene modified product is preferably 10-40% by mass, and more preferably 15-35%. In addition, the water solubility in the present invention means: after drying the gel after the water absorption capacity measurement in a hot air dryer at 50°C for 8 hours, weigh its mass (C[g]) and calculate the value according to the following formula.

Water soluble content (mass %) = {(A-C)/A} × 100

The filler (component (B)) can be appropriately selected from known fillers that can be used in resins without impairing the effects of the present invention. The filler can be an inorganic filler or an organic filler.

Examples of the inorganic filler include silicon oxide, magnesium carbonate, clay, talc, calcium carbonate, titanium oxide and diatomaceous earth.

The silicon oxide preferably has a specific surface area of 40 m ² /g or more, more preferably 50 m ² /g or more, 60 m ² /g or more, 70 m ² /g or more, 80 m ² /g or more, 90 m ² /g or more, 100 m ² /g or more, or 110 m ² /g or more. The upper limit of the specific surface area is not particularly limited, and examples thereof include 400 m ² /g or less, 380 m ² /g or less, 350 m ² /g or less, or 300 m ² /g or less. In addition, the silicon oxide preferably has an oil absorption of 100 mL/100 g or more, preferably 150 mL/100 g or more, and more preferably 190 mL/100 g or more. The upper limit of the oil absorption is not particularly limited, and examples thereof include 400 mL/100 g or less, 380 mL/100 g or less, 350 mL/100 g or less, or 300 mL/100 g or less. The oil absorption is a value measured by the method described in JIS K5101-13-2:2004.

Clay can be specifically exemplified by bentonite and bentonite. In this specification, bentonite includes organized bentonite (such as trimethyl stearammonium bentonite, benzyl dimethyl stearammonium bentonite and dimethyl distearammonium bentonite). In addition, bentonite in this specification includes organized bentonite (such as dimethyl distearammonium lithium bentonite, lithium silicate, sodium, magnesium trioctyl ammonium methide, lithium silicate, sodium, magnesium chloride diethylene glycol coconut alkyl (C8~C18) ammonium methide, etc.).

In addition, organic fillers include, for example, cyclodextrin (e.g., α-, β-, or γ-cyclodextrin, etc.) and modified cyclodextrin (e.g., methyl-modified cyclodextrin, hydroxypropyl-modified cyclodextrin, etc.), etc. Among them, silicon oxide, magnesium carbonate, clay, cyclodextrin, and modified cyclodextrin are particularly preferred.

In addition, the filler is preferably in the form of particles (powder).

The filler may be used alone or in combination of two or more.

The aforementioned volatile substance (component (C)) is not particularly limited as long as it does not completely evaporate at normal temperature and pressure (25°C, 1 atmosphere) when used together with component (A). It is particularly preferred to use a substance (fragrance) that can volatilize to have an excellent aroma or a substance that can attract and/or repel pests or animals (such as pheromones and repellents). That is, it is preferably a fragrance and one or more selected from pest pheromones, pest pheromones, pest repellents, and pest repellents. Pests are not particularly limited, and examples include sanitary pests and food pests, and more specifically include cockroaches, flies, horseflies, mosquitoes, centipedes, fleas, lice, mites, bees, caterpillars, centipedes, millipedes, moths, ants, and termites. In addition, although pests are not particularly limited, examples include small mammals (especially small rodents), such as mice and rats.

Although not particularly limited, the fragrance may include, for example, alloocimene, allyl caproate, allyl heptanoate, amyl propionate, anisole, anisaldehyde, anisole, benzaldehyde, benzyl acetate, benzylacetone, benzyl alcohol, benzyl butyrate, benzyl formate, benzyl isovalerate, benzyl propionate, βγ-hexenol, camphene, camphor, carvacrol, levocarvacrol, d-carvacrol, levocarvacrol, cinnamyl formate, neral, citronellol, citronellyl acetate, citronellyl isobutyrate, citronellyl nitrile, citronellyl propionate, anisol, anisaldehyde, Cyclal C, cyclohexyl ethyl acetate, decanal, dihydrogeranyl alcohol, dimethylbenzyl carbinol, dimethylbenzyl carbinol acetate, dimethyloctanol, diphenyl oxide, ethyl acetate, ethyl acetylacetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexanone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl acetate, fenchol, Flor acetate (tricyclodecenyl acetate), frutene (tricyclodecenyl propionate), γ-methylionone, γ-n-methylionone, γ-nonalactone, geranyl alcohol, geranyl acetate, geranyl formate, geranyl isobutyrate, geranyl nitrile, hexenol, hexenyl acetate, cis-3-hexenyl acetate, hexenyl isobutyrate, cis-3-hexenyl chamomile acid, hexyl acetate, hexyl formate, hexyl pentanoate Ester, Hexyl Chamomide, Hydrogenated Globulol, Hydroxycitronellal, Indole, Isoamyl Alcohol, α-ionone, β-ionone, γ-ionone, α-iridium ketone, Isoborneol Acetate, Isobutyl Benzoate, Isobutylquinoline, Isomenthol, Isomenthone, Isononyl Acetate, Isononyl Alcohol, Isopropylphenylacetaldehyde, Isomenthol, Isomenthyl Acetate, Isoquinoline, Cis-Jasmone, Lauraldehyde (Dodecanal), Ligustral ), limonene, linalool, linalool oxide, linalool acetate, linalool formate, menthone, menthyl acetate, methyl acetophenone, methyl amyl ketone, methyl amine benzyl ester, methyl benzoate, methyl benzyl acetate, methyl eugenol, methyl heptenone, methyl heptylene carbonate, methyl heptanone, methyl hexanone, α-iso(γ)methyl ionone, methyl nonyl acetaldehyde, methyl octyl acetaldehyde, methyl phenyl acetate, methyl salicylate, moon Cinnamylene, neral, nerol, neryl acetate, nonyl acetate, nonanal, octalactone, octanol (octanol-2), octanal, citrus terpenes (d-limonene), p-cresol, p-cresol methyl ether, p-carmelane, p-methylacetophenone, phenoxyethanol, phenylacetaldehyde, phenylethyl acetate, phenylethanol, phenethyl dimethyl carbinol, pinene (α-pinene, β-pinene), isoprenyl acetate, propyl butyrate, menthol, rose oxide, safrole, α-terpinene, γ-terpinene, terpineol (4-terpineol, α-terpineol), terpinolene, terpineol acetate, tetrahydrolinalool, tetrahydrogeranyl alcohol, tonalide, undecenal, veratrol, Verdox, Vertenex and pyridine, etc.

In addition, pheromones include sex pheromones, collection pheromones and alarm pheromones, etc. Specific substances include attractants (especially insect attractants), and more specifically, (Z)-9-tricosene, (Z)-11-hexadecene-1-aldehyde, (Z)-5-hexadecene, 1-chloro-3-methyl-but-2-ene, 3-chloro-3-methyl-but-1-ene, terpineol, chlorobenzenol, geraniol, acetic acid, isovaleric acid, trimethylamine, indole, piperidine, phenylethyl alcohol, ammonium carbonate, skatin, formaldehyde, hexamethylenetetramine, ammonium formate, papain, butyric acid, isovaleraldehyde, ethylamine, chlorinated olefin polyol aliphatic monoesters, pancreatin and vanilla extract, etc.

Examples of the remover include salicylic acid, benzoic acid, sorbic acid, p-chlorobenzene and 2-(4'-thiazole)benzimidazole.

Alternatively, insect pheromones may include aliphatic straight-chain aldehydes having 12 to 20 carbon atoms, aliphatic straight-chain acetates having 12 to 20 carbon atoms which are saturated or have 1 or more double bonds, aliphatic straight-chain alcohols having 7 to 20 carbon atoms, spiroaldehydes having 7 to 15 carbon atoms, aliphatic straight-chain ketones having 10 to 25 carbon atoms, aliphatic hydrocarbons having 10 to 30 carbon atoms, and carvacrolic acid having 10 to 20 carbon atoms, and aliphatic straight-chain aldehydes having 12 to 20 carbon atoms, aliphatic straight-chain acetates having 12 to 20 carbon atoms which are saturated or have 1 or more double bonds, aliphatic straight-chain alcohols having 7 to 20 carbon atoms, and spiroaldehydes having 7 to 15 carbon atoms are particularly preferred. Specific examples include: the sex pheromone substances of pink ballworm, namely Z7Z11-hexadecadienyl acetate and Z7E11-hexadecadienyl hexanoate; the sex pheromone substances of oriental fruit moth, namely Z-8-dodecenyl acetate; the sex pheromone substances of peach twig borer, namely E-5-decenyl acetate; the sex pheromone substances of grape berry moth, namely Z-9-dodecenyl acetate; the sex pheromone substances of grape vine moth, namely E7Z9-dodecadienyl acetate; the sex pheromone substances of light brown apple moth, namely E-11-tetradecenyl acetate; the sex pheromone substances of codling moth, namely The pheromone substances of leaf roller moth are E8E10-dodecadienol; the pheromone substances of leaf roller moth are Z-11-tetradecadienyl acetate; the pheromone substances of peach tree borer are Z3Z13-octadecadienyl acetate and E3Z13-octadecadienyl acetate; the pheromone substances of Amercian bollworm are Z-11-hexadecenal; the pheromone substances of Oriental tobacco budworm are Z-9-hexadecenal; the pheromone substances of soybean pod borer are E8E10-dodecadienyl acetate; the pheromone substances of diamondback moth are The pheromone substances of cabbage armyworm are Z-11-hexadecenyl acetate and Z-11-hexadecenal; the pheromone substances of cabbage armyworm are Z-11-hexadecenyl acetate, Z-11-hexadecenol and hexadecyl acetate; the pheromone substances of beet armyworm are Z9E12-tetradecadienyl acetate and Z-9-tetradecadienol; the pheromone substances of common cutworm are Z9E11-tetradecadienyl acetate and Z9E12-tetradecadienyl acetate; the pheromone substances of fall armyworm are Z-9-tetradecadienyl acetate; the pheromone substances of tomato pinworm are E-4-tridecenyl acetate; the pheromone substances of rice stem borer are Borer) sex pheromone substances, namely Z-11-hexadecenal and Z-13-octadecene aldehyde; Coffee leaf miner sex pheromone substances, namely 5,9-dimethylpentadecane and 5,9-dimethylhexadecane; Peach leaf miner sex pheromone substances, namely 14-methyl-1-octadecene; Peach fruit moth sex pheromone substances, namely Z-13-eicosene-10-one; Gypsy moth sex pheromone substances, namely 7,8-epoxy-2-methyloctadecane; Pine processionary moth sex pheromone substances, namely Z-13-hexadecene-11-yl acetate; Dasylepida ishigakiensis sex pheromone substances, namely 2-butanol; Yellowish elongate chafer), namely Z-7,15-hexadecadiene-4-lactone; Sugarcane wireworm ( Melanotus okinawensis ), namely n-dodecyl acetate; Sugarcane wireworm ( Melanotus okinawensis, M. sakishimensis ), namely E-9,11-dodecadienyl butyrate and E-9,11-dodecadienyl hexanoate; Cupreus chafer, namely (R)-Z-5-(oct-1-enyl)-hexacyclopentane-2-copper; Rice leaf bug (Rice leaf bug) The pheromones of the plant bug are hexyl hexanoate, E-2-hexenyl hexanoate and octyl butyrate; the pheromones of the Sorghum plant bug are hexyl butyrate, E-2-hexenyl butyrate and E-4-hydroxy-2-hexenal; the pheromones of the White Peach scale are (6R)-Z-3,9-dimethyl-6-isopropenyl-3,9-decadienyl propionate and (6R)-Z-3,9-dimethyl-6-isopropenyl-3,9-decadienol; the pheromones of the Vine mealybug are (S)-5-methyl-2-(1-propen-2-yl)-4-hexenyl 3-methyl-2-butenoate; the pheromones of the House fly are (S)-5-methyl-2-(1-propen-2-yl)-4-hexenyl 3-methyl-2-butenoate. fly), namely Z-9-tricosene; the German cockroach, namely reproductive quinone isovalerate; the olive fruit fly, namely 1,7-dihydroquinone. Spiro[5.5]undecane, etc.

The volatile substances may be used alone or in combination of two or more. Although the substances belonging to the fragrance may be used in combination with the substances belonging to the pest or animal pheromones or repellents, it is still preferred to use the substances belonging to the fragrance alone or in combination of two or more, or to use one or more selected from the group consisting of pest pheromones, pest animal pheromones, pest repellents and pest repellents in combination.

In addition, the volatile substance dispersing composition of the present invention may contain other ingredients within the scope that does not hinder the effect of the present invention. The other ingredients may also include non-volatile ingredients. Other ingredients are preferably insecticides. Examples of insecticides include: neonicotinoid-based dinotefuran and acetamiprid; pyrrole-based chlorfenapyr; phenylpyrazole-based fipronil; macrolide-based emamectin benzoate; and organophosphorus-based trichlorfon. Among these, water-soluble insecticides are preferred, and dinotefuran is particularly preferred.

In the volatile substance emitting composition of the present invention, the mass ratio of component (A) to component (B) is preferably about 1:0.0001 to 0.2, preferably about 1:0.001 to 0.15, and more preferably about 1:0.01 to 0.1. Within these ranges, the lower limit of the mass ratio of component (B) may be 0.0001, 0.0005, 0.001, 0.005 or 0.01. In addition, within these ranges, the upper limit of the mass ratio of component (B) may be 0.2, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11 or 0.1.

The method for producing the volatile substance emitting composition of the present invention is not particularly limited. For example, it can be produced by first preparing a composition containing component (A) and component (B) (composition containing (A) and (B)) and then adding component (C). In addition, when adding other components, for example, when adding component (C), other components can be added together.

When preparing the composition containing (A) and (B), the component (A) may be prepared first and then mixed with the component (B), or the component (B) may be added to the reaction system in advance when preparing the component (A) (during the polymerization reaction) as described above. As for the method of preparing the component (A) and then mixing the component (B), the known method used when adding fillers to resins can be used. More specifically, for example, the composition containing (A) and (B) may be prepared by mixing the components (A) and (B) using a roll, a kneader, or an extruder, while heating as necessary.

The method of making the composition containing (A) and (B) contain the component (C) can be exemplified by: a method of making the composition containing (A) and (B) absorb the liquid composition mixed with the component (C). The solvent of the liquid composition mixed with the component (C) can be exemplified by water, an organic solvent (such as ethanol, etc.) and a mixture thereof, and water is particularly preferred. The liquid composition mixed with the component (C) is preferably a composition containing a solvent and the component (C), and more preferably a composition consisting only of a solvent and the component (C). In the liquid composition mixed with the component (C), the solvent is preferably contained in an amount of 80 to 99% by mass, and more preferably 90 to 98% by mass. The lower limit of the range may be about 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93 or 94 mass %. In addition, the upper limit of the range may be about 99, 98, 97 or 96 mass %. In addition, in the liquid composition mixed with component (C), component (C) preferably contains 1 to 20 mass %, and preferably contains 2 to 10 mass %, and more preferably contains 3 to 6 mass %. The lower limit of the range may be 1, 2, 3 or 4 mass %. In addition, the upper limit of the range may be 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7 or 6 mass %.

The liquid composition mixed with component (C) may contain a solvent and components other than component (C). Such components may be, for example, a surfactant, and preferably a nonionic surfactant. More specifically, a nonylphenol-based surfactant may be used. In the liquid composition mixed with component (C), the content of the surfactant may be, for example, 0.05-0.5% by mass, and may be about 0.06-0.4% by mass, 0.07-0.3% by mass, 0.08-0.2% by mass, or 0.09-0.15% by mass.

When the composition containing (A) and (B) absorbs the liquid composition mixed with the component (C), the mass ratio of the composition containing (A) and (B) to the liquid composition mixed with the component (C) absorbed by the composition containing (A) and (B) is preferably about 1:1-30, more preferably about 1:1-25, and more preferably about 1:1-20. The upper limit of the mass ratio may be about 1:2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

The present invention also includes the following embodiments, namely, the use of a composition containing (A) and (B) for absorbing liquid compositions (especially liquid compositions mixed with volatile substances). That is, a composition containing components (A) and (B) for absorbing liquid compositions mixed with volatile substances is also included in the present invention. In addition, the present invention also includes a method for improving the sustainability of the release of volatile substances in a liquid composition into the atmosphere, the method comprising the step of allowing a composition containing (A) and (B) to absorb a liquid composition mixed with volatile substances. The various conditions related to these embodiments are the same as those described above.

In addition, the term "comprising" in this specification also includes "consisting essentially of" and "consisting of.". In addition, when specifying the subject matter included in the present invention, the various characteristics (properties, structures, functions, etc.) described above for each embodiment of the present invention can be combined arbitrarily. That is, the present invention includes all the following subjects, namely: various subjects consisting of all combinations of various characteristics that may be combined in this specification. Examples

The present invention is described in more detail as follows, but the present invention is not limited to the following examples.

[Evaluation method] For the polyoxyalkylene modified product listed in the following production example, the water absorption capacity, water solubility and median particle size (when crushed after production) were evaluated according to the following method. (1) Water absorption capacity The water absorption capacity of the polyoxyalkylene modified product was measured according to the following method.

Weigh 1.0 g of polyoxyalkylene modified product (A[g]) and soak it in 100 mL of ion exchange water in a 200 mL beaker at room temperature (22°C) for 24 hours to gel. Then, filter the gel with a 200 mesh (pore size: 75 μm) metal mesh, measure its mass (B[g]) and calculate the water absorption capacity according to the following formula.

Water absorption capacity (g/g) = B/A (2) Water soluble content Dry the gel after the water absorption capacity test in a hot air dryer at 50°C for 8 hours, then weigh its mass (C[g]) and calculate the water soluble content according to the following formula.

Water soluble content (mass %) = {(A-C)/A} × 100 (3) Median particle size The median particle size is calculated using the dry sieving method (JIS Z8815). Specifically, 50 g of the sample is weighed and sieved using the JIS standard sieve (JIS Z8801). The sample is weighed after each sieve and the median particle size at which the cumulative mass is 50% is calculated based on the result.

Production Example I: Production of polyoxyalkylene modified products In a storage tank A which is kept at 80°C and equipped with a stirrer, 100 parts by mass of polyethylene oxide with a number average molecular weight of 20,000, 0.9 parts by mass of 1,4-butanediol, and 0.1 parts by mass of dioctyltin dilaurate are added in a ratio and stirred in a nitrogen atmosphere to prepare a uniform mixture. In addition, dicyclohexylmethane-4,4'-diisocyanate is added to a storage tank B which is kept at 30°C and stored in a nitrogen atmosphere.

The mixture in storage tank A was continuously supplied to a two-axis extruder (R value = 1.00) set at 110-140°C using a metering pump at a rate of 500 g/min and the dicyclohexylmethane-4,4'-diisocyanate in storage tank B at a rate of 19.4 g/min. The mixture was mixed and reacted in the extruder. Strands were released from the extruder outlet and pelletized by a pelletizer to obtain polyoxyalkylene modified products. The polyoxyalkylene modified products in the following examples used the polyoxyalkylene modified product pellets obtained in the Production Example I.

The water absorption capacity of the obtained polyoxyalkylene modified product was 25 g/g, and the water solubility was 19% by mass.

Production Example II: Production of polyoxyalkylene modified products Ethylene oxide/propylene oxide (mass ratio: 90/10) copolymer with a number average molecular weight of 15,000 was fed at a rate of 250 g/min and ethylene glycol heated to 40°C was fed at a rate of 2.1 g/min to a 40 mm φ single-axis extruder (L/D=40, set temperature: 90°C) and the two were melt-mixed. In addition, φ means the screw diameter.

The mixture obtained from the discharge port (discharged in a uniform molten state, and confirmed by HPLC analysis that it was mixed according to the feed ratio) was continuously fed to the feed hopper port (set temperature: 80°C) of a 30mmφ two-axis extruder (L/D=41.5). At the same time, dioctyltin dilaurate was fed to the feed port of the two-axis extruder at a rate of 0.5g/min.

Dicyclohexylmethane-4,4'-diisocyanate adjusted to 30°C was also supplied (R value = 0.95) to the screw sleeve located at the downstream side of the feed hopper of the aforementioned two-axis extruder at a speed of 12.4 g/min, and it was continuously reacted in a nitrogen environment (set temperature: 180°C). The strands obtained from the outlet of the two-axis extruder were cooled and pelletized by a pelletizer to obtain a polyoxyalkylene modified product.

The water absorption capacity of the obtained polyoxyalkylene modified product was 20 g/g, and the water solubility was 15% by mass.

Production Examples 1 to 16 A composition obtained by mixing 0.5 g (1 part by weight: Table 1), 1.5 g (3 parts by weight: Table 2), 2.5 g (5 parts by weight: Table 3) or 5 g (10 parts by weight: Table 4) of various fillers with 50 g of polyoxyalkylene modified product (Production Example I preparation) was melted and kneaded by a 4-inch roll (manufactured by Yasuda Seiki Co., Ltd. (Type: No.191-TM TEST MIXING ROLL)) at a roll temperature of 45 to 55°C. The composition was pressed for ³ minutes by a 68 t hot press (manufactured by Tokai Machinery Co., Ltd. (TYPE: VH6-5A-120B)) at a hot plate temperature of 150°C and a hot plate pressure of 30 kgf/cm2 to produce a sheet having a thickness of 2 mm. The various fillers used are shown in Tables 1 to 4. In addition, the polyoxyalkylene modified products are also listed as "resins" in the following tables.

[Table 1]

[Table 2]

[table 3]

[Table 4]

In addition, various fillers were purchased from the market. The details of various fillers are as follows. In addition, the specific surface area of silicon oxide was measured by nitrogen adsorption method, and the oil absorption was measured by the method specified in JIS K5101-13-2:2004. Filler (1): Organized bentonite SUMECTON SAN [manufactured by Kunimine Industries Co., Ltd.] Filler (2): Organized bentonite SUMECTON STN [manufactured by Kunimine Industries Co., Ltd.] Filler (3): Silica beads Nipsil EL [manufactured by Tosoh Silicone Corporation] (specific surface area: 48 ^m2 /g, oil absorption: 180 mL/100 g) Filler (4): Silica Carplex 80 [manufactured by Evonik Japan Co., Ltd.] (specific surface area: 200 ^m2 /g, oil absorption: 245 mL/100 g) Filler (5): α-Cyclodextrin CAVAMAX W6 Food [manufactured by CycloChem Co., Ltd.] Filler (6): β-Cyclodextrin CAVAMAX W7 Food [manufactured by CycloChem Co., Ltd.] Ltd.] Filler (7): γ-cyclodextrin CAVAMAX W8 Food [CycloChem Co., Ltd.] Filler (8): Methyl-modified cyclodextrin CAVASOL W7M [CycloChem Co., Ltd.] Filler (9): Hydroxypropyl-modified cyclodextrin CAVASOL W7HP [CycloChem Co., Ltd.] Filler (10): Alkaline magnesium carbonate (lightweight) [Lin Jun Chemical Co., Ltd.]

Examples 1 to 17 The compositions obtained in Examples 1 to 16 were formed into square particles with a length and width of 4 mm using a Super straight Cutter (manufactured by DUMBBELL CO., LTD. (model: SSK-1000S-D, punching size (L): 100 mm)) to obtain particles of various compositions (length, width, thickness: 4 mm, 4 mm, 2 mm). These particles were used in Examples 1 to 16, respectively. In addition, among these particles, the particles obtained from the composition obtained in Example 16 were immersed in liquid nitrogen and crushed to a median particle size of 60 μm to obtain a powder of the composition. The powder was used in Example 17.

1 g of the particles or powders of the various compositions obtained (the number of particles: about 20) was immersed in 10 g of liquid A, B or C mixed with volatile substances, and allowed to absorb the liquid for 24 hours. Only the remaining liquid mixed with volatile substances that was not absorbed by the particles or powders of the composition was separated to obtain a granular or powdery liquid-absorbing composition (i.e., a composition for emitting volatile substances) (Examples 1 to 17). The various liquid-absorbing compositions obtained are collectively shown in Table 5.

[table 5]

The compositions of the liquids A, B or C mixed with volatile substances used in the examples are shown in Table 6. In addition, in Examples 1 to 16, the examples using the liquid A mixed with volatile substances are Examples 1a to 16a, the examples using the liquid B mixed with volatile substances are Examples 1b to 16b, and the examples using the liquid C mixed with volatile substances are Examples 1c to 16c. In addition, in Example 17, the example using the liquid A mixed with volatile substances is Example 17a.

[Table 6]

Three particles of the composition prepared by absorbing the liquid A mixed with volatile substances from the absorbent compositions obtained in Examples 1 to 16 were taken into a 25 mL vial and maintained in a headspace oven at 40° C. for 17 minutes. The gas phase in the 25 mL vial was then quantitatively analyzed by GC analysis (headspace method) to analyze the amount of volatile components released from the absorbent composition. In addition, 0.1 g of the composition prepared by absorbing the liquid A mixed with volatile substances from the absorbent composition obtained in Example 17 was taken into a vial and the amount of volatile components released from the absorbent composition was similarly analyzed.

(GC conditions, device body: GC-2014 (manufactured by Shimadzu Corporation), automatic sampler device: HT-2800T (manufactured by Alpha M.O.S. Japan K.K.), column: G-250, carrier: He (flow rate: 50 mL/min), detector: FID, INJ temperature: 230°C, detector temperature: 250°C)

By the GC analysis, the area value (peak area value) of limonene was detected from the absorption composition of the liquid A in which the volatile substances had been absorbed, as shown in Table 7.

In the composition prepared by absorbing the liquid A mixed with volatile substances, in the evaluation of the change in the amount of release over time of the liquid component mixed with volatile substances, since the release amount of almost all volatile components showed the same dynamics (release amount change) as limonene, limonene was selected as a representative component from the existing various volatile components for evaluation. In addition, the actual weight was confirmed by completely drying the three granules at the end, and the regional value was made the corrected regional value ("regional value/actual weight of three granules" or "regional value/actual weight of the powder used (0.1g)", that is, the regional value of limonene released per 1g of granules or powder). Hereinafter, the range value of limonene released per 1 g of granules or powder is sometimes referred to as the limonene supplement range value.

In addition, in the absorbent composition obtained in Examples 1 to 17, the liquid A mixed with volatile substances was absorbed and the prepared composition particles or powders were placed in a ventilated dryer set at 40°C and left to stand for 6 hours or 12 hours to evaporate the volatile components of the absorbed liquid. Thereafter, three particles of the absorbent composition were taken into a 25 mL vial and maintained in a headspace furnace at 40°C for 17 minutes. The gas phase in the 25 mL vial was quantitatively analyzed by GC analysis (headspace method) to analyze the amount of volatile components that have evaporated. The limonene correction region value detected by the GC analysis is shown in Table 7.

[Table 7]

Among the liquid absorbing compositions obtained in Examples 1 to 16, the composition particles prepared by absorbing the liquid B mixed with volatile substances were detected by GC analysis in the same manner as above to obtain the limonene correction region value. The results are shown in Table 8. In addition, for the composition prepared by absorbing the liquid B mixed with volatile substances, similar to the composition prepared by absorbing the liquid A mixed with volatile substances, in the evaluation of the change in the amount of release over time of the liquid components mixed with volatile substances, since the release amounts of almost all volatile components showed the same dynamics (release amount change) as limonene, limonene was selected as a representative component from the existing various volatile components for evaluation.

In addition, among the liquid absorption compositions obtained in Examples 1 to 16, the composition particles prepared by absorbing the liquid C mixed with volatile substances were subjected to GC analysis in the same manner as described above. In addition, in the evaluation of the change in the amount of release over time of the liquid component mixed with volatile substances, since the release amounts of almost all volatile components showed the same dynamics (release amount change) as Z-9-tricosene, Z-9-tricosene was selected from the various existing volatile components as a representative component for evaluation. Similar to the evaluation of the composition prepared by absorbing the liquid A mixed with volatile substances, the regional value of Z-9-tricosene released per 1g of particles (Z-9-tricosene supplementation regional value) was calculated for the composition prepared by absorbing the liquid C mixed with volatile substances. The results are shown in Table 9.

[Table 8]

[Table 9]

Comparative Examples 1-3 1 g (number of particles: about 20) of particles (length, width, thickness: 4 mm, 4 mm, 2 mm) prepared without adding fillers to the polyoxyalkylene modified product was immersed in 10 g of liquid A, B or C mixed with volatile substances and allowed to absorb the liquid for 24 hours. Only the remaining liquid mixed with volatile substances that was not absorbed by the particles of the composition was separated to obtain a granular polyoxyalkylene modified product that absorbed liquid. Three particles of the liquid-absorbed polyoxyalkylene modified product were taken into a 25 mL vial and maintained in a headspace furnace at 40° C. for 17 minutes. The gas phase in the 25 mL vial was then quantitatively analyzed by GC analysis (headspace method) under the same conditions as above to analyze the amount of volatile components evaporated by the liquid-absorbed polyoxyalkylene modified product.

In addition, the particles of the polyoxyalkylene modified product with liquid absorption were placed in a forced air dryer set at 40°C and left for 6 hours or 12 hours to evaporate the volatile components of the absorbed liquid. Afterwards, three particles of the polyoxyalkylene modified product were taken into a 25 mL vial and maintained in a headspace furnace at 40°C for 17 minutes. The gas phase in the 25 mL vial was quantitatively analyzed by GC analysis (headspace method) to analyze the amount of volatile components that had evaporated.

By GC analysis, the correction region values of limonene were detected from the polyoxyalkylene modified products of liquids A and B which had been adsorbed with volatile substances, as shown in Table 10.

[Table 10]

In addition, by GC analysis, the correction region value of Z-9-tricosene was detected from the polyoxyalkylene modified product of the liquid C which had been adsorbed with volatile substances, as shown in Table 11.

[Table 11]

(without)

Claims (7)

A composition for emitting volatile substances, comprising: (A) a polyoxyalkylene modified substance obtained by reacting a polyoxyalkylene compound having a number average molecular weight of 5000 to 50000, a diol compound and a diisocyanate compound; (B) a filler; and (C) a volatile substance, wherein the diol compound comprises: at least one selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol and 1,4-butanediol. As claimed in claim 1, the volatile substance emitting composition, wherein the aforementioned polyoxyalkylene compound comprises: at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide/propylene oxide copolymer, ethylene oxide/butylene oxide copolymer, propylene oxide/butylene oxide copolymer and ethylene oxide/propylene oxide/butylene oxide copolymer. The volatile substance emitting composition of claim 1 or 2, wherein the aforementioned diisocyanate compound comprises: at least one selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-xylene-2,4-diisocyanate and 2,4-toluene diisocyanate (TDI). The composition for emitting volatile substances as claimed in claim 1 or 2, wherein the filler (B) comprises: at least one selected from the group consisting of silicon oxide, magnesium carbonate, clay, talc, calcium carbonate, titanium oxide, diatomaceous earth, cyclodextrin and modified cyclodextrin. For example, the composition for dispersing volatile substances of claim 1 or 2, wherein (C) the volatile substances are selected from one or more of the group consisting of fragrances and pheromones and repellents for insects or animals. A composition for absorbing a liquid composition mixed with volatile substances, comprising the following (A) components and (B) components: (A) a polyoxyalkylene modified substance obtained by reacting a polyoxyalkylene compound with a number average molecular weight of 5000 to 50000, a diol compound and an isocyanate compound; and (B) a filler, wherein the diol compound comprises: at least one selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol and 1,4-butanediol. A method for increasing the sustainability of releasing volatile substances from a liquid composition into the atmosphere, wherein the liquid composition is a liquid composition mixed with volatile substances, and the method comprises: a step of allowing a composition containing the following (A) components and (B) components to absorb the liquid composition mixed with volatile substances; (A) a polyoxyalkylene modified substance obtained by reacting a polyoxyalkylene compound having a number average molecular weight of 5000 to 50000, a diol compound and a diisocyanate compound; and (B) a filler, wherein the aforementioned diol compound comprises: at least one selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol and 1,4-butanediol.