TW201927846A - Composition for emitting volatile substance - Google Patents

Abstract

Provided is a volatile-substance-containing composition from which the volatile substance is sustainedly released over a long period. More specifically, a composition for emitting a volatile substance is provided, the composition comprising (A) a poly(alkylene oxide) modification product obtained by reacting a poly(alkylene oxide) compound, a diol compound, and a diisocyanate compound, (B) a filler, and (C) the volatile substance.

Description

Composition for volatile substance emission

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

BACKGROUND ART A composition in which a useful volatile substance is contained in a resin gel is used for various purposes. For example, when the volatile substance is an aromatic substance, a good aroma can be emitted indoors. Alternatively, when the volatile substance is a pest or beast inducement substance, the pest or beast can be attracted, and it can be easily expelled by this.

As for a composition containing such a volatile substance, it is required that the volatile substance can be continuously released for a long period of time (that is, the sustained release is high).
Prior technical literature Patent literature

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

SUMMARY OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a volatile substance-containing composition having excellent sustained release of volatile substances.
Means to solve the problem

The inventors of the present case found that a composition containing a specific polyoxyalkylene modified substance, a filler, and a volatile substance has excellent sustained release of the volatile substance, and then continues to improve until the present invention is completed.

The invention includes subject matter such as those set out below.
Item 1 A composition for emitting volatile substances, containing:
(A) a polyoxyalkylene modified product obtained by reacting a polyoxyalkylene compound, a diol compound, and a diisocyanate compound;
(B) fillers; and
(C) Volatile substances.
Item 2. The volatile substance emitting composition according to item 1, wherein the polyoxyalkylene compound includes: selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and ethylene oxide. Group consisting of alkylene / propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene oxide copolymer At least one of them.
Item 3 The volatile substance emitting composition according to item 1 or 2, wherein the diol compound comprises: selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, Dipropylene glycol, trimethyl glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,9 -At least one member of the group consisting of nonanediol.
Item 4. The composition for emitting a volatile substance according to any one of Items 1 to 3, wherein the diisocyanate compound includes: 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-diisocyanate (TDI).
Item 5. The composition for emitting a volatile substance according to any one of Items 1 to 4, wherein (B) the filler comprises: selected from the group consisting of silicon oxide, magnesium carbonate, clay, talc, calcium carbonate, titanium oxide, and silicon. At least one of the groups consisting of diatomaceous earth, cyclodextrin and modified cyclodextrin.
Item 6. The volatile substance dispersing composition according to any one of Items 1 to 5, wherein (C) the volatile substance is selected from the group consisting of a perfume, a pest or a animal pheromone, and a repellent. One or more of them.
Item 7: A composition for absorbing liquid with a volatile substance-doped liquid composition, containing the following components (A) and (B):
(A) a polyoxyalkylene modified product obtained by reacting a polyoxyalkylene compound, a diol compound, and an isocyanate compound; and
(B) Filler.
Item 8: A method for continuously improving the release of volatile substances in a liquid composition to the atmosphere. The liquid composition is a liquid composition in which a volatile substance is blended. The method includes the following: (A) The step of absorbing the liquid composition in which the volatile substance is mixed with the composition of the component and the component (B);
(A) a polyoxyalkylene modified product obtained by reacting a polyoxyalkylene compound, a diol compound, and a diisocyanate compound; and
(B) Filler.
Invention effect

According to the present invention, the sustained release of volatile substances can be improved. The composition for volatile substance emission of the present invention can slowly disperse the contained volatile substance, and the effect of the volatile substance can be maintained for a long time (that is, it also has excellent sustained-release property). In addition, the composition for volatile substance emission of the present invention may contain a larger amount of volatile substance than the mass of volatile substance that a general resin may contain. Therefore, from the start of the release to a predetermined 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), the amount of volatile matter that can be released and the total amount of volatile substances that can be released are all higher than those of ordinary resins. many.

Embodiments for Carrying Out the Invention Hereinafter, each embodiment of the present invention will be described in detail.

The composition for emitting a volatile substance contained in the present invention contains (A) a specific polyoxyalkylene modified substance, (B) a filler, and (C) a volatile substance. These components may be referred to as (A) component, (B) component, and (C) component, respectively. In addition, this volatile substance emission composition may be referred to as the volatile substance emission composition of the present invention.

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

Examples of the aforementioned polyoxyalkylene compound include 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 compounds can be used singly or in combination of two or more kinds. In addition, "/" is a symbol used here to indicate the copolymer of each oxide. For example, ethylene oxide / propylene oxide copolymer means a copolymer of ethylene oxide and propylene oxide.

Although not particularly limited, a polyoxyalkylene compound having a number average molecular weight of 5,000 to 50,000 is preferable, and a polyoxyalkylene compound having a number average molecular weight of 10,000 to 30,000 is more preferable.

The value of the number-average molecular weight is a value obtained by the measurement method set forth below. Number average molecular weight measurement method: A dimethylformamide solution having a concentration of 1% by mass of a polyoxyalkylene modified product is prepared and measured by high-speed liquid chromatography. Next, a molecular weight marker (polyethylene oxide) having a known molecular weight was measured under the same conditions, a calibration curve was prepared, and a number average molecular weight (Mn) was calculated. The measurement 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 ℃
Dissolution: Dimethylformamide Flow rate: 0.6ml / min
In addition, a polyoxyalkylene compound having an ethylene oxide group of 90% by mass or more is preferable, and a polyoxyalkylene compound having an ethylene oxide group of 95% by mass or more is more preferable.

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

Relative to 1 mole of the aforementioned polyoxyalkylene compound, the use ratio of the aforementioned diol compound is preferably 0.8 to 2.5 moles, and more preferably 1.0 to 2.0 moles. The molar number of the polyoxyalkylene compound can be determined by dividing the 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. For example, 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexa Methylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-xylene-2,4-diisocyanate and 2,4-diisocyanate toluene (TDI). Among these diisocyanate compounds, dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are suitably used. These diisocyanate compounds may be used alone or in combination of two or more.

The respective usage ratios of the aforementioned polyoxyalkylene compounds, diol compounds, and diisocyanate compounds are as follows: relative to the total number of moles of the terminal hydroxyl group of the polyoxyalkylene compound and the hydroxyl group of the diol compound, the isocyanate of the diisocyanate compound The molar number ratio of the group [R value = (-NCO group / -OH group)] is preferably about 0.7 to 1.2, and more preferably about 0.8 to 1.05.

As a method for reacting the polyoxyalkylene compound, the diol compound, and the diisocyanate compound, a conventional method can be used. Examples thereof include a method of dissolving or dispersing them in a reaction solvent such as toluene, xylene, or dimethylformamide, and reacting them; and uniformly mixing these materials in a powder or solid state, and heating to A method of pre-determining the temperature and reacting it. From the standpoint of industrial-scale implementation, a method of continuously supplying each raw material in a molten state and mixing and reacting it in a multi-axis extruder is preferred. At this time, the aforementioned reaction temperature is preferably 70 to 210 ° C.

In addition, when producing a polyoxyalkylene modified product, a catalyst may be added to the reaction system from the viewpoint of promoting the reaction. For example, triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, and triethylenediamine can be added in a suitable amount as a catalyst.

A polyoxyalkylene modified product can be prepared by this method. According to this method, polyoxyalkylene modified materials can generally be obtained in the form of pellets, sheets or films. These can be used directly in the composition for volatile substance emission of the present invention, or they can be pulverized, such as a pulverizer, and then used in the composition for volatile substance emission of the present invention. The pulverization method is not particularly limited, but in order to prevent fusion due to shear heating during pulverization, freeze pulverization is preferable. For example, freeze pulverization can be performed using liquid nitrogen.

In addition, when producing a modified polyoxyalkylene, a filler (B) may be added to the reaction system. At this time, the obtained composition containing the polyoxyalkylene modified product already contains the (A) component and the (B) component. Therefore, the volatile substance emission of the present invention can be adjusted by adding the (C) component to the composition. Using composition. In addition, the composition containing the polyoxyalkylene modified product obtained by adding (B) filler to the reaction system can be directly used in the composition for volatile substance emission of the present invention, or can be used in the present invention after being pulverized by a pulverizer or the like. Composition for the emission of volatile substances. The pulverization method is not particularly limited, but in order to prevent fusion due to shear heating during pulverization, freeze pulverization is preferable. For example, freeze pulverization can be performed using liquid nitrogen.

The polyoxyalkylene modified product is preferably water-absorbing (that is, has water-absorbing ability). In particular, when preparing the composition for volatile substance emission of the present invention, the (C) volatile substance is preferably contained in the polyoxyalkylene modified substance. At this time, for example, the following method can be suitably used: Add the volatile substance to water to dissolve or disperse it, or make the volatile substance and water show a layer separation (two-layer separation) state, and then make the polyoxyalkylene modified product mixed with the liquid of the volatile substance To be aspirated. Although not particularly limited, the water absorption capacity of the polyoxyalkylene modified product is preferably 10 to 40 g / g, and more preferably 15 to 35 g / g. In addition, the so-called water absorption capacity in the present invention means that a polyoxyalkylene modified product (A [g]) having a weight of 1.0 g is weighed and immersed in 100 mL of ion-exchanged water at room temperature (22 ° C) for 24 hours to condense. After gelation, the gel was filtered through a 200 mesh (pore size: 75 μm) metal mesh, and then the gel mass (B [g]) of the filtrate (residue) was measured and the value calculated according to the following formula (since A is 1, the The value is B).

Water absorption capacity (g / g) = B / A
In addition, although not particularly limited, the water solubility of the polyoxyalkylene modified product is preferably 10 to 40% by mass, and more preferably 15 to 35%. In addition, the so-called water-soluble content in the present invention means that the gel after measuring the water absorption capacity is dried by a hot air dryer at 50 ° C for 8 hours, and then the mass (C [g]) is measured and calculated by the following formula .

Water solubility (% by mass) = ((A-C) / A) × 100

The filler ((B) component) can be appropriately selected and used as a filler that is known to be used in a resin before the effects of the present invention are impaired. The filler may be an inorganic filler or an organic filler.

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

Silicon oxide specific surface area at 40m ² / g or more is preferred, 50m ² / g or more, 60m ² / g or more, 70m ² / g or more, 80m ² / g or more, 90m ² / g or more, 100m ² / g or more Or more preferably 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, it is preferable that the amount of oil absorption of silica is 100mL / 100g or more, and more preferably 150mL / 100g or more, and more preferably 190mL / 100g or more. The upper limit of the oil absorption amount 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. In addition, the oil absorption is a value measured in accordance with the method set out in JIS K5101-13-2: 2004.

Specific examples of the clay include bentonite and bentonite. In the present specification, the bentonite includes organic bentonite (trimethylstearyl ammonium bentonite, benzyldimethylstearyl ammonium bentonite, dimethyldistearylammonium bentonite, etc.). In addition, in this specification, bentonite includes organic bentonite (e.g. lithium dimethyl distearate, bentonite, lithium silicate, sodium, magnesium trioctylmethyl ammonium, lithium silicate, sodium, and magnesium chloride dimer ring. Oxyethane coconut alkyl (C8 ~ C18) methylammonium, etc.).

In addition, the organic filler may be, for example, cyclodextrin (such as α-, β-, or γ-cyclodextrin) and modified cyclodextrin (such as methyl modified cyclodextrin, hydroxypropyl modified cyclodextrin, etc.) )Wait. Among them, silica, magnesium carbonate, clay, cyclodextrin and modified cyclodextrin are preferred.

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

The filler can 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 volatilize at room temperature and pressure (25 ° C, 1 atmosphere) when used with the component (A). Particularly preferred are substances (fragrances) that have excellent aroma properties by volatilization or substances 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 the group consisting of pest pheromone, pest pheromone, pest repellent, and pest repellent. Pests are not particularly limited, and examples thereof include hygiene pests and food pests, and more specifically, cockroaches, flies, maggots, mosquitoes, pupae, fleas, lice, mites, bees, caterpillars, pupae, horses, moths, ants and termites Wait. In addition, although the mammal is not particularly limited, examples thereof include small mammals (especially small rodents) and mice and rats.

Although not particularly limited, the flavor may be, for example, Alloocimene, allyl hexanoate, allyl heptanoate, amyl propionate, fennel brain, anisaldehyde, anisyl ether, benzaldehyde , Benzyl acetate, benzyl acetone, benzyl alcohol, benzyl butyrate, benzyl formate, benzyl isovalerate, benzyl propionate, β γ-hexenol, pinene, camphor, eugenol, levulinol Erigerol, d-Carrageenone, L-carrageenone, cinnamyl formate, neral, citronellol, citronellyl acetate, citronellyl isobutyrate, citronellonitrile, propionic acid Citronellol, Anisyl Alcohol, Anisaldehyde, Cyclal C, Cyclohexyl Ethyl Acetate, Decyl Aldehyde, Dihydrogeraniol, Dimethyl Benzyl Methanol, Dimethyl Benzyl Methanol Acetate, Dimethyl Octanol, Oxidation Diphenyl, ethyl acetate, ethyl acetoacetate, ethylpentanone, ethyl benzoate, ethyl butyrate, ethylhexanone, ethylphenyl acetate, eucalyptol, eugenol, ethyl acetate , Methanol, Flor acetate (tricyclodecenyl acetate), frutene (tricyclodecenyl propionate), γ-methylionone, γ-n-methylionone, γ-nonon Lactone, geraniol Oxalol, geranyl acetate, geranyl formate, geranyl isobutyrate, geranonitrile, hexenyl alcohol, hexenyl acetate, cis-3-hexenyl acetate, hexenyl isobutyrate, Cis-3-hexenyl chamomile, hexyl acetate, hexyl formate, hexyl octopentanoate, hexyl chamomile, hydrolanthyl alcohol, hydroxycitronellal, indole, isoamyl alcohol, α -Ionone, β-ionone, γ-ionone, α-irisone, isoamyl acetate, isobutyl benzoate, isobutyl quinoline, isomenthol, isomentholone, isononyl acetate Ester, isononanol, p-isopropylphenylacetaldehyde, isomenthol, isomenthol, isoquinoline acetate, isoquinoline, cis jasmonone, lauraldehyde (dodecylaldehyde), ligustral (Ligustral), Limonene, agaric alcohol, agaric alcohol oxide, agaric acetate, agaric acid formate, menthol, menthol acetate, methylacetophenone, methylpentanone, methyl o-aminobenzate, methyl benzoate, methyl acetate Benzyl benzyl ester, methylacetophenone, methyl eugenol, methylheptenone, methylheptyne carbonate, methylheptanone, methylhexanone, α-iso (γ) methylionone, methyl Nonylacetaldehyde, methyloctyl Acetaldehyde, methylphenyl orthoacetate, methyl salicylate, laurene, neral, nerol, neryl acetate, nonyl acetate, nonanal, caprolactone, octanol (octanol- 2) Octanal, citrus terpenes (d-limonene), p-cresol, p-cresol methyl ether, p-dill hydrocarbon, p-methylacetophenone, phenoxyethanol, phenylacetaldehyde, phenethyl acetate , Phenethyl alcohol, phenethyl dimethyl methanol, limonene (α-pinene, β-pinene), isoprene acetate, propyl butyrate, menthol, rose oxide, yellow Camphor oil, α-terpinene, γ-terpinene, terpineol (4-terpineol, α-terpineol), terpineolene, terpineol acetate, tetrahydroalbergol, tetrahydro Geraniol, Tonalide, Undecenal, Veratrole, Verdox, Vertenex, and Pyridine.

In addition, pheromone can be exemplified by sexual pheromone, gathering pheromone and alert pheromone. The specific substance may be an inducer (especially an insect inducer), and more specifically, for example: (Z) -9-docosatriene, (Z) -11-hexadecene-1-aldehyde, ( Z) -5-hexadecene, 1-chloro-3-methyl-but-2-ene, 3-chloro-3-methyl-but-1-ene, terpineol, bacterol, geraniol Alcohol, acetic acid, isovaleric acid, trimethylamine, indole, piperidine, phenylethanol, ammonium carbonate, skatole, formaldehyde, hexamethylenetetramine, ammonium carbamate, papain, butyric acid, isovaleraldehyde, ethyl Amines, chlorinated olefin polyols, aliphatic monoesters, pancreatin and vanillin.

The repellent can be exemplified by salicylic acid, benzoic acid, sorbic acid, p-chlorosaccharol, and 2- (4'-thiazole) benzimidazole.

Alternatively, insect pheromone can be exemplified by aliphatic linear aldehydes having 12 to 20 carbon atoms, saturated linear acetic acid esters having 12 to 20 carbon atoms which are saturated or have one or two or more double bonds, Aliphatic linear alcohols with 7 to 20 carbons, spiral acetals with 7 to 15 carbons, aliphatic linear ketones with 10 to 25 carbons, aliphatic hydrocarbons with 10 to 30 carbons and 10 to 10 carbons 20 alkaloidic acid, etc., and aliphatic straight chain aldehydes having 12 to 20 carbon atoms, saturated straight chain acetic acid esters having 12 to 20 carbon atoms that are saturated or have 1 or 2 double bonds, Aliphatic linear alcohols having 7 to 20 carbon atoms and spiral acetals having 7 to 15 carbon atoms are particularly preferred. Specific examples are: Sexual pheromone substances of Pink ballworm, namely Z7Z11-hexadecadienyl acetate and Z7E11-hexadecadienylhexanoate; Oriental peach (Oriental fruit moth), which is Z-8-dodecenyl acetate; Peach twig borer, which is E-5-decenyl acetate; Sexual pheromone substance of Grape berry moth (Z-9-dodecenyl acetate); Sexual pheromone substance of Grape vine moth (E7Z9-Dodecane di) Alkenyl acetate; sex pheromone substance of Light brown apple moth, namely E-11-tetradecenyl acetate; Codling moth sex pheromone substance, E8E10-dodecadienol; sexual pheromone substance of Leaf roller moth, namely Z-11-tetradecenyl acetate; sexual pheromone of Peach tree borer Substances, namely Z3Z13-octadecadienyl acetate and E3Z13-octadecadienyl acetate; sexual pheromone substance of Amercian bollworm, namely Z-11-hexadecenal; Of Tobacco Moth (Oriental tobacco budworm) Pheromones, Z-9-hexadecenal; Sex pheromone of Soybean pod borer, E8E10-dodecadienyl acetate; Diamondback moth Pheromones, namely Z-11-hexadecenyl acetate and Z-11-hexadecenal; Sexual pheromones of Cabbage armyworm (Z-11-hexadecenyl) Acetate, Z-11-hexadecenol and n-hexadecyl acetate; sexual pheromone substances of the beet armyworm, namely Z9E12-tetradecanedienyl acetate and Z-9- Tetradecenol; sex pheromone substances of Common cutworm, namely Z9E11-tetradecanedienyl acetate and Z9E12-tetradecanedienyl acetate; Fall March bug (Fall Army worm's sex pheromone substance, namely Z-9-tetradecenyl acetate; Tomato pinworm's sex pheromone substance, namely E-4-tridecenyl acetate; two Sex pheromone of Rice Stem Borer, namely Z-11-hexadecenal and Z-13-octadecenal; Sex pheromone of Coffee leaf miner, that is, 5,9-dimethylpentadecane and 5,9-dimethylhexadecane; Peach leaf Miner) sex pheromone substance, namely 14-methyl-1-octadecene; Peach fruit moth (Peach fruit moth) sex pheromone substance, namely Z-13-eicosene-10-one; Sexual pheromone substance of Gypsy moth, namely 7,8-epoxy-2-methyloctadecane; Sexual pheromone substance of Pine processionary moth, namely Z-13-ten Hexene -11-yl acetate; sex pheromone substance of Dasylepida ishigakiensis , namely 2-butanol; sex pheromone substance of yellowish long chafer, namely Z-7,15-hexadecane Diene-4-lactone; sex pheromone substance of Sugarcane wireworm ( Manocanus okinawensis ), namely n-dodecyl acetate; sugarcane wireworm; Melanotus okinawensis, M. sakishimensis Pheromones, namely E-9,11-dodecadienyl butyrate and E-9,11-dodecadienylhexanoate; Sexual cost of Cupreus Chafer Lomon substance, namely (R) -Z-5- (oct-1-enyl) -hexacyclopentane-2-copper; sexual pheromone substance of Rice leaf bug, namely hexanoic acid Hexyl ester, E-2-hexenylhexanoate and octyl butyrate; orghum plant bug) sexual pheromone substances, namely hexyl butyrate, E-2-hexenyl butyrate and E-4- pendant oxygen 2-hexenal; White mulberry shell scale insect (White Peach scale), which is (6R) -Z-3,9-dimethyl-6-isopropenyl-3,9-decadienyl propionate and (6R) -Z-3 , 9-dimethyl-6-isopropenyl-3,9-decadienol; sexual pheromone substance of Vine mealybug, (S) -5-methyl-2- (1-propen-2-yl) -4-hexenyl 3-methyl-2-butenoate; a sexual pheromone substance of the house fly, namely Z-9-docosatriene; Sexual pheromone substance of German cockroach, namely reproductive quinone isovalerate; sexual pheromone substance of olive fruit fly, namely 1,7-II Spiro [5.5] undecane and the like.

Volatile substances can be used alone or in combination of two or more. Although a substance that is a spice can be used in combination with a substance that is a pest or pest pheromone or a repellent, it can be used alone or in combination of two or more substances. Pest pheromone, pest pheromone, pest repellent and pest repellent are used in combination of one or two or more kinds.

In addition, the composition for emitting a volatile substance of the present invention may contain other components within a range not hindering the effects of the present invention. The other ingredients may also include, for example, non-volatile ingredients. Other ingredients include, for example, insecticidal ingredients. The insecticidal component may be suitable, for example: dinotefuran and Acetamiprid of the neonicotinoid system; Chlorfenapyr of the pyrrole system; Fipronil); macrolides of emamectin benzoate; and organophosphorus-based trichlorfon. Among these, water-soluble insecticides are preferred, and dinotefuran is particularly preferred.

In the composition for emitting a volatile substance of the present invention, the mass ratio of the component (A) to the component (B) is preferably about 1: 0.0001 to 0.2, more preferably about 1: 0.001 to 0.15, and about 1: 0.01 to 0.1. Better. In these ranges, the lower limit of the mass ratio of the component (B) may be 0.0001, 0.0005, 0.001, 0.005, or 0.01. In addition, in these ranges, the upper limit of the mass ratio of the (B) component 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 composition for emitting a volatile substance of the present invention is not particularly limited. For example, a composition containing the component (A) and the component (B) (a composition containing the components (A) and (B)) can be prepared before the component (C) is prepared. In addition, when it contains other components, when it contains (C) component, it may contain other components together.

When preparing a composition containing (A) and (B), the component (A) may be prepared first, and then the component (B) may be mixed therein, or the component (A) may be prepared in advance as described above (during the polymerization reaction). Component (B) is added to the reaction system. As a method for mixing the component (B) after the component (A) is prepared, a conventional method used when adding a filler to the resin can be used. More specifically, for example, a composition containing (A) and (B) can be prepared by mixing a component (A) and a component (B) while heating, if necessary, using a roll, a kneader, or an extruder.

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

The liquid composition containing the component (C) may contain a solvent and components other than the component (C). Examples of such ingredients include surfactants, and non-ionic surfactants are preferred. More specifically, for example, a nonanol-based surfactant may be mentioned. In the liquid composition containing the (C) component, the content of the surfactant may be, for example, 0.05 to 0.5% by mass, and may be 0.06 to 0.4% by mass, 0.07 to 0.3% by mass, 0.08 to 0.2% by mass, or 0.09 to 0.15. Mass%.

When the composition containing (A) and (B) is used to absorb the liquid composition containing the component (C), the composition containing (A) and (B) and the composition containing (A) and (B) The mass ratio of the liquid composition mixed with the component (C) absorbed by the composition is preferably about 1: 1 to 30, more preferably about 1: 1 to 25, and more preferably about 1: 1 to 20. The quality limit can be 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 an embodiment in which the composition containing (A) and (B) is used for absorbing liquid by using a liquid composition (especially a liquid composition containing a volatile substance). That is, a composition for absorbing a liquid composition containing a volatile substance and containing the component (A) and the component (B) is also included in the present invention. In addition, the present invention also includes a method for continuously improving the release of volatile substances in a liquid composition into the atmosphere, the method comprising: mixing a composition containing (A) and (B) with a volatile substance The liquid composition is a step of aspirating liquid. The conditions for these embodiments are the same as those described above.

In addition, the term "comprising" in this specification also includes "the term" comprising "includes" consisting essentially of "and" consisting of. "). In addition, in specifying the subject matter of the present invention, various characteristics (property, structure, function, etc.) described above with respect to each embodiment of the present invention can be arbitrarily combined. That is, the present invention encompasses all the subject matter, that is, various subjects constituted by all combinations of various characteristics contained in this specification, which are possible combinations.
Examples

The present invention is more specifically described below, but the present invention is not limited by the following examples.

[Evaluation method]
For the polyoxyalkylene modified product carried in the following production examples, the water absorption energy, water content, and median particle size were determined as follows (when crushed after production).
(1) Water absorption capacity The water absorption capacity of the polyoxyalkylene modified product was measured by the following method.

After weighing 1.0 g of the polyoxyalkylene modified product (A [g]), it was immersed in 100 mL of ion-exchanged water in a 200 mL volume beaker at room temperature (22 ° C) for 24 hours to gelate. . Then, the gel was filtered through a 200 mesh (pore size: 75 μm) metal mesh, and the mass (B [g]) was measured, and the water absorption capacity was calculated by the following formula.

Water absorption capacity (g / g) = B / A
(2) Water-soluble content: The gel after the water absorption capacity measurement was dried for 8 hours with a hot air dryer at 50 ° C, and the mass (C [g]) was measured, and the water-soluble content was determined by the following formula.

Water solubility (mass%) = ((AC) / A) × 100
(3) Median diameter The median diameter was determined by a dry sieving method (JIS Z8815). Specifically, 50 g of the sample obtained was weighed and sieved using a JIS standard sieve (JIS Z8801). After each sieving, the sample was weighed, and a 50% median particle size was calculated based on the result.

Production Example I: Production of a polyoxyalkylene modified product was stored in a storage tank A maintained at 80 ° C. and equipped with a stirrer, so that 100 parts by mass of polyethylene oxide, 1,4- 0.9 parts by mass of butanediol and 0.1 parts by mass of dioctyltin dilaurate were added thereto and stirred under a nitrogen environment to prepare a homogeneous mixture. In addition, dicyclohexylmethane-4,4'-diisocyanate was put into storage tank B which had been kept at 30 ° C, and stored under a nitrogen atmosphere.

Using a metering pump, continuously feed the mixture in storage tank A at a rate of 500 g / min and the dicyclohexyl methane-4,4'-diisocyanate in storage tank B at a rate of 19.4 g / min. 140 ° C 2-axis extruder (R value = 1.00), mixed in the extruder for reaction, the strands were released from the extruder outlet, pelletized by a pelletizer, and a polyoxyalkylene modified Quality. In the following examples, the polyoxyalkylene modified particles obtained by using Production Example I were used as the polyoxyalkylene modified particles.

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 Product The ethylene oxide / propylene oxide (mass ratio: 90/10) copolymer having a number average molecular weight of 15,000 was heated at a rate of 250 g / minute and heated to 40 ° C. The ethylene glycol was fed to a 40 mmφ uniaxial extruder (L / D = 40, set temperature: 90 ° C.) at a rate of 2.1 g / minute, and the two were melt-mixed. In addition, φ means the diameter of the screw.

The mixture obtained from the discharge port (discharged in a uniform molten state, and confirmed to be mixed according to the feed ratio by HPLC analysis) was continuously supplied to the feeding hopper mouth (set temperature: 30 mmφ of a 2-axis extruder (L / D = 41.5) 80 ° C). At the same time, dioctyl dilaurate was supplied to the feed port of the 2-axis extruder at a rate of 0.5 g / minute.

At a speed of 12.4 g / min, the dicyclohexyl methane-4,4'-diisocyanate adjusted to 30 ° C was further supplied (R value = 0.95) to the downstream side of the hopper mouth of the aforementioned 2-axis extruder. The screw sleeve was continuously reacted in a nitrogen atmosphere (setting temperature: 180 ° C). The strands obtained from the exit of the biaxial extruder were cooled, and then pelletized with 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.

Manufacturing Examples 1 to 16
By using a 4-inch roll ((share) manufactured by Yasuda Seiki Co., Ltd. (type: No. 191-TM TEST MIXING ROLL)) and setting the roll temperature at 45 to 55 ° C, the polyoxyalkylene modified product (prepared in Preparation Example I 50g of various fillers are blended with 0.5g (1 part by weight: Table 1), 1.5g (3 parts by weight: Table 2), 2.5g (5 parts by weight: Table 3) or 5g (10 parts by weight: Table 4) The obtained composition is prepared by melting and kneading. The composition was pressurized for 3 minutes using a 68t hot press (type: VH6-5A-120B) manufactured by a 68t hot press at a setting of a hot plate temperature of 150 ° C and a hot plate pressure of 30 kgf / cm ² . A 2 mm thick sheet was produced.
The various fillers used are shown in Tables 1 to 4. In the following table, the modified polyoxyalkylene is also referred to as "resin".

[Table 1]

[Table 2]

[table 3]

[Table 4]

In addition, various fillers were purchased for commercial use. The detailed information of various fillers is as follows. The specific surface area of the silicon oxide is a value measured by a nitrogen adsorption method, and the oil absorption amount is measured by a method described in JIS K5101-13-2: 2004.
Filler (1): Organic bentonite SUMECTON SAN [KUNIMINE INDUSTRIES CO., LTD.]
Filler (2): Organic bentonite SUMECTON STN [KUNIMINE INDUSTRIES CO., LTD.]
Filler (3): Silica beads Nipsil EL [manufactured by TOSOH SILICA CORPORATION] (specific surface area: 48m ² / g, oil absorption: 180mL / 100g)
Filler (4): Silicon oxide Carplex 80 [manufactured by Evonik Japan Co., Ltd.] (specific surface area: 200m ² / g, oil absorption: 245mL / 100g)
Filler (5): α-cyclodextrin CAVAMAX W6 Food [manufactured by CycloChem Co., Ltd.]
Filler (6): β-cyclodextrin CAVAMAX W7 Food [manufactured by CycloChem Co., Ltd.]
Filler (7): γ-cyclodextrin CAVAMAX W8 Food [manufactured by CycloChem Co., Ltd.]
Filler (8): methyl modified cyclodextrin CAVASOL W7M [manufactured by CycloChem Co., Ltd.]
Filler (9): hydroxypropyl modified cyclodextrin CAVASOL W7HP [manufactured by CycloChem Co., Ltd.]
Filler (10): basic magnesium carbonate (light weight) [made by Lin Chung Pharmaceutical]

Examples 1 to 17
The composition obtained in Manufacturing Examples 1 to 16 was formed into a square granular shape with a length and a width of 4 mm by Super straight Cutter (DUMBBELL CO., LTD. (Type: SSK-1000S-D, punch size (L): 100 mm)). And granules (length, width, thickness: 4mm, 4mm, 2mm) of various compositions were prepared. These were used in Examples 1-16, respectively. In addition, among the particles, the particles obtained from the composition obtained in Production Example 16 were immersed in liquid nitrogen, and then pulverized to a median particle diameter of 60 μm to obtain a powder of the composition. This powder was used in Example 17.

1 g of the obtained granules or powders of various compositions (number of granules: about 20) were immersed in 10 g of liquid A, B, or C mixed with a volatile substance and allowed to absorb liquid for 24 hours. Separation of the liquid containing the volatile substances remaining in the particles or powders of the composition, to obtain a granular or powdery liquid absorbing composition (that is, a composition for emitting volatile substances) (Examples 1 to 17) ). The obtained various liquid-absorbent compositions are shown in Table 5.

[table 5]

Table 6 shows the composition of each of liquids A, B, or C doped with volatile substances used in Examples and the like. In addition, in Examples 1 to 16, the examples using liquid A doped with volatile substances are Examples 1a to 16a, and the examples using liquid B doped with volatile substances are Examples 1b to 16b. Examples of liquid C incorporating volatile substances are Examples 1c to 16c. In addition, in Example 17, the example using the liquid A with which the volatile substance was mixed is made into Example 17a.

[TABLE 6]

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

(GC conditions, device body: GC-2014 (made by Shimadzu Corporation), automatic sampler device: HT-2800T (made by Alpha MOS Japan KK), column: G-250, carrier: He (flow rate: 50 mL / min), Detector: FID, INJ temperature: 230 ° C, detector temperature: 250 ° C)

By this GC analysis, the regional value (peak area value) of limonene was detected from the liquid absorbing composition of liquid A in which the volatile substance was mixed with the volatile substance, as shown in Table 7.

For a composition prepared by absorbing liquid A mixed with a volatile substance, in the evaluation of the change in the amount of the released amount of the liquid component mixed with the volatile substance over time, due to the release of almost all volatile components The amount showed the same dynamics (change in release amount) as limonene, and limonene was selected as a representative component from various existing volatile components for evaluation. In addition, confirm the actual weight by completely drying the 3 granules at the end, so that the area value is the corrected area value ("area value / substantial weight of 3 parts of granules" or "area value / substantial weight of powder used" (0.1g) ", which is the regional value of limonene released per 1g of particles or powder). Hereinafter, the regional value of limonene released per 1 g of particles or powder may be referred to as a limonene correction regional value.

In addition, in the liquid-absorbent composition obtained in Examples 1 to 17, the composition particles or powder prepared by absorbing liquid A mixed with a volatile substance into a liquid was placed in a blower dryer set at 40 ° C, Leave it for 6 hours or 12 hours to evaporate the volatile components of the absorbed liquid. After that, 3 particles of the liquid absorbing composition were taken into a 25 mL vial, and maintained in a headspace furnace at 40 ° C for 17 minutes, and then the gas phase partial gas in the 25 mL vial was quantitatively analyzed by GC analysis (headspace method). Analyze the amount of volatile components that have evaporated. Table 7 shows the limonene correction area values detected by this GC analysis.

[TABLE 7]

Among the liquid-absorbent compositions obtained in Examples 1 to 16, the composition particles prepared by absorbing liquid B mixed with a volatile substance were subjected to liquid-absorption, as described above, and analyzed by GC analysis to obtain a limonene correction region. value. The results are shown in Table 8. In addition, the composition prepared by absorbing liquid B mixed with volatile substances and absorbing liquid is the same as the composition prepared by absorbing liquid A mixed with volatile substances and absorbing liquid. In the evaluation of changes in the amount of volatile liquid components over time, since almost all volatile components show the same dynamics as limonene (change in the amount of release), limonene is selected from the existing various volatile components. It was evaluated as a representative component.

In addition, among the liquid-absorbent compositions obtained in Examples 1 to 16, GC analysis was performed on the composition particles prepared by absorbing liquid C mixed with a volatile substance by liquid-absorption.
In addition, for a composition prepared by absorbing liquid C mixed with a volatile substance and absorbing liquid, in the evaluation of changes in the amount of time-released of the liquid component blended with a volatile substance, almost all volatile constituents The released amount showed the same dynamics (change in the amount of release) as Z-9-docosatriene, and Z-9-docosatriene was selected as a representative component from the existing various volatile components for evaluation. The evaluation is the same as the composition prepared by absorbing liquid A mixed with volatile substances, and the composition prepared by absorbing liquid C mixed with volatile substances is absorbed. The regional value of Z-9-triosene (Z-9-tricosene corrected regional value). The results are shown in Table 9.

[TABLE 8]

[TABLE 9]

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

In addition, the granules of the liquid-absorbing polyoxyalkylene modified product were put into a blower dryer set at 40 ° C., and left to stand for 6 hours or 12 hours to evaporate the volatile components of the absorbed liquid. After that, 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, and then the gas phase in the 25mL vial was quantitatively analyzed by GC analysis (headspace method). For some gases, analyze the amount of volatile components that have been evaporated.

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

[TABLE 10]

In addition, by GC analysis, the value of the correction region of Z-9-ticostriene was detected from the liquid-absorbing polyoxyalkylene modified product of liquid C mixed with the volatile substance, as shown in Table 11.

[TABLE 11]

Claims (8)

A volatile substance emission composition containing: (A) a polyoxyalkylene modified product obtained by reacting a polyoxyalkylene compound, a diol compound, and a diisocyanate compound; (B) fillers; and (C) Volatile substances. The composition for emitting volatile substances according to claim 1, wherein the aforementioned polyoxyalkylene compound comprises: selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and ethylene oxide / ring At least at least one of the groups consisting of propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene oxide copolymer. 1 species. The composition for emitting a volatile substance according to claim 1 or 2, wherein the aforementioned diol compound comprises: 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-nonane At least one member of the group consisting of alcohol. The volatile substance emitting composition according to any one of claims 1 to 3, wherein the aforementioned diisocyanate compound comprises: selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), Methyl diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1 At least one of the group consisting of 2,8-xylene-2,4-diisocyanate and 2,4-diisocyanate (TDI). The volatile substance emitting composition according to any one of claims 1 to 4, wherein (B) the filler comprises: selected from the group consisting of silicon oxide, magnesium carbonate, clay, talc, calcium carbonate, titanium oxide, diatomaceous earth, At least one of the groups consisting of cyclodextrin and modified cyclodextrin. The volatile substance dispersing composition according to any one of claims 1 to 5, wherein (C) the volatile substance is selected from one of the group consisting of perfumes, pests or pest pheromones, and repellents Or 2 or more. A composition for absorbing liquid by mixing a liquid composition mixed with a volatile substance, containing the following components (A) and (B): (A) a polyoxyalkylene modified product obtained by reacting a polyoxyalkylene compound, a diol compound, and an isocyanate compound; and (B) Filler. A method for continuously improving the release of volatile substances in a liquid composition to the atmosphere. The liquid composition is a liquid composition in which a volatile substance is blended. The method includes: containing the following (A) component and ( B) the step of absorbing the liquid composition in which the volatile substance is mixed; (A) a polyoxyalkylene modified product obtained by reacting a polyoxyalkylene compound, a diol compound, and a diisocyanate compound; and (B) Filler.