JPWO2019111839A1 - Composition for volatile substance emission - Google Patents

Abstract

In the volatile substance-containing composition, a means for continuously releasing the volatile substance for a long period of time is provided. More specifically, it is volatile, containing (A) a polyalkylene oxide compound, a diol compound, and a polyalkylene oxide modified product obtained by reacting a diisocyanate compound, (B) a filler, and (C) a volatile substance. A composition for material dissipation is provided.

Description

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

Compositions containing useful volatile substances in resin gels are used for various purposes. For example, when the volatile substance is an aromatic substance, a good scent can be emitted into the room. Alternatively, if the volatile substance is a pest or vermin-inducing substance, the pest or vermin can be attracted, which makes it easy to exterminate.

In such a volatile substance-containing composition, it is required that the volatile substance is continuously released for a long period of time (that is, the release sustainability is high).

Japanese Unexamined Patent Publication No. 6-32863 Japanese Unexamined Patent Publication No. 6-140052 Japanese Unexamined Patent Publication No. 8-12871 Japanese Unexamined Patent Publication No. 6-98627 Japanese Unexamined Patent Publication No. 2001-172358 Japanese Unexamined Patent Publication No. 2002-265780 Japanese Unexamined Patent Publication No. 2002-331203 JP-A-2007-254363 Special Table 2017-517611 International Publication No. 2013/084983

An object of the present invention is to provide a volatile substance-containing composition having excellent sustainability of release of a volatile substance.

The present inventors have found that a composition containing a specific polyalkylene oxide modified product, a filler, and a volatile substance is excellent in the release sustainability of the volatile substance, and further improved the present invention to complete the present invention. I came to let you.

The present invention includes, for example, the subjects described in the following sections.
Item 1.
(A) A polyalkylene oxide modified product obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound.
A composition for releasing volatile substances, which contains (B) a filler and (C) a volatile substance.
Item 2.
The polyalkylene oxide compound is 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. Item 2. The composition for releasing volatile substances according to Item 1, which comprises at least one selected from the group consisting of copolymers.
Item 3.
The diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol. Item 2. The composition for releasing volatile substances according to Item 1 or 2, which comprises at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol.
Item 4.
The diisocyanate compounds are 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3, Includes at least one selected from the group consisting of 5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzol-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI). , Item 3. The composition for releasing volatile substances according to any one of Items 1 to 3.
Item 5.
(B) Any of Items 1 to 4, wherein the filler contains at least one selected from the group consisting of silica, magnesium carbonate, clay, talc, calcium carbonate, titanium oxide, diatomaceous earth, cyclodextrin, and modified cyclodextrin. The composition for releasing volatile substances according to.
Item 6.
(C) The composition for releasing volatile substances according to any one of Items 1 to 5, wherein the volatile substance is one or more selected from the group consisting of fragrances and pest or vermin pheromones and extermination agents. Stuff.
Item 7.
A composition containing the following components (A) and (B) for absorbing a volatile substance-containing liquid composition.
(A) Polyalkylene oxide modified product obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound (B) Filler item 8.
The volatile substance in the volatile substance-containing liquid composition, which comprises a step of causing the composition containing the following components (A) and (B) to absorb the volatile substance-containing liquid composition into the atmosphere. A method of increasing release sustainability.
(A) Polyalkylene oxide modified product (B) filler obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound.

According to the present invention, the sustainability of release of volatile substances can be enhanced. The composition for releasing volatile substances of the present invention has a long-lasting effect of the volatile substances (that is, it is also excellent in sustained release) by gradually releasing the contained volatile substances. Moreover, the volatile substance dissipating composition of the present invention can contain a much larger amount of volatile substances than a normal resin can contain. Therefore, for a certain period of time from the start of release (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, The amount of volatile substances that can be released by 21, 22, 23, or 24 hours, or after 1, 2, 3, 4, 5, 6, or 7 days) and the total amount of volatile substances that can be released are also ordinary resins. Many compared to.

Hereinafter, each embodiment of the present invention will be described in more detail.

The composition for releasing volatile substances included in the present invention contains (A) a specific polyalkylene oxide modified product, (B) a filler, and (C) a volatile substance. These components may be referred to as a component (A), a component (B), and a component (C), respectively. Further, the composition for diverging volatile substances may be referred to as the composition for diverging volatile substances of the present invention.

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

Examples of the polyalkylene oxide 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. An example includes an oxide copolymer and the like. The polyalkylene oxide compound may be used alone or in combination of two or more. In addition, "/" here is a symbol used to indicate that it is a copolymer of each oxide. For example, ethylene oxide / propylene oxide copolymer represents a copolymer of ethylene oxide and propylene oxide.

Although not particularly limited, a polyalkylene oxide compound having a number average molecular weight of 5,000 to 50,000 is preferable, and a polyalkylene oxide compound having a number average molecular weight of 1,000 to 30,000 is more preferable.

The value of the number average molecular weight here is a value obtained by the measurement method described below. Number average molecular weight measurement method: A dimethylformamide solution having a polyalkylene oxide modified product concentration of 1% by mass is prepared, and measurement is performed using a high performance liquid chromatograph. Then, a molecular weight marker (polyethylene oxide) having a known molecular weight is measured under the same conditions, a calibration curve is created, and the number average molecular weight (Mn) is calculated. The measurement conditions are as follows.

Measuring machine: HLC-8220 (manufactured by Tosoh Corporation)
Column: Tosoh Corporation TSK GEL Multipore HXL-M Column temperature: 40 ° C
Eluate: Dimethylformamide Flow rate: 0.6 ml / min
Further, a polyalkylene oxide compound having an ethylene oxide group of 90% by mass or more is preferable, and a polyalkylene oxide 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, 2,3-butanediol, and 1,4-butanediol. , 1,5-Pentanediol, 1,6-hexanediol, 1,9-nonanediol and the like can be exemplified. These diol compounds can be used alone or in combination of two or more. The diol compound does not include the polyalkylene oxide compound. That is, the diol compound is a diol compound other than the polyalkylene oxide compound.

The ratio of the diol compound used is preferably 0.8 to 2.5 mol, more preferably 1.0 to 2.0 mol, based on 1 mol of the polyalkylene oxide compound. The number of moles of the polyalkylene oxide compound can be obtained by dividing its mass by the number average molecular weight.

The diisocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups (-NCO) in the same molecule, and is, for example, 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate ( HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI), 1,8-dimethylbenzol-2,4 − Diisocyanate, 2,4-tolylene diisocyanate (TDI) and the like. Among these diisocyanate compounds, dicyclohexylmethane-4,4'-diisosianate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are preferably used. Each of these diisocyanate compounds may be used alone, or two or more kinds may be used in combination.

The ratio of each of the polyalkylene oxide compound, the diol compound, and the diisocyanate compound used is the ratio of the number of moles of the isocyanate group of the diisocyanate compound to the total number of moles of the terminal hydroxyl group of the polyalkylene oxide 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.

As a method for reacting the polyalkylene oxide compound, the diol compound, and the diisocyanate compound, a known method can be used. For example, a method of dissolving or dispersing these in a reaction solvent such as toluene, xylene, or dimethylformamide to react; a method of uniformly mixing these in powder or solid form and then heating to a predetermined temperature for reaction; And so on. From the viewpoint of industrial implementation, a method in which each raw material is continuously supplied in a molten state and mixed and reacted in a multi-screw extruder is preferable. In this case, the temperature of the reaction is preferably 70 to 210 ° C.

Further, when producing the modified polyalkylene oxide, a catalyst may be added into the reaction system from the viewpoint of accelerating the reaction. For example, as a catalyst, an appropriate amount of triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, triethylenediamine and the like can be added.

By such a method, a modified polyalkylene oxide can be obtained. According to such a method, the modified polyalkylene oxide is usually obtained in the form of, for example, pellets, sheets, films and the like. These may be used as they are in the composition for releasing volatile substances of the present invention, or may be used in the composition for releasing volatile substances of the present invention after being pulverized by, for example, a crusher or the like. The pulverization method is not particularly limited, but it is preferable to freeze pulverize in order to prevent fusion due to shear heat generation during pulverization. For example, it can be frozen and pulverized using liquid nitrogen.

When producing the modified polyalkylene oxide, the filler (B) may be added to the reaction system. In this case, since the obtained polyalkylene oxide modified product-containing composition already contains the component (A) and the component (B), the present invention can be obtained by adding the component (C) to the composition. A composition for releasing volatile substances can be prepared. The polyalkylene oxide modified product-containing composition obtained by adding the filler (B) in the reaction system may also be used as it is in the composition for releasing volatile substances of the present invention, or may be used as it is by a pulverizer or the like. After being pulverized, it may be used in the composition for releasing volatile substances of the present invention. The pulverization method is not particularly limited, but it is preferable to freeze pulverize in order to prevent fusion due to shear heat generation during pulverization. For example, it can be frozen and pulverized using liquid nitrogen.

The polyalkylene oxide modified product is preferably water-absorbent (that is, has a water-absorbing ability). In particular, in preparing the composition for releasing volatile substances of the present invention, it is preferable to include (C) the volatile substance in the polyalkylene oxide modified product. In this case, for example, the volatile substance is added to water. A method is preferably used in which the volatile substance and water are layer-separated (two-layer separation) after being dissolved or dispersed, or the volatile substance-containing liquid is absorbed by the polyalkylene oxide modified product. be able to. Although not particularly limited, the water absorption capacity of the polyalkylene oxide modified product is preferably 10 to 40 g / g, more preferably 15 to 35 g / g. In the present invention, the water absorption capacity means that 1.0 g of a polyalkylene oxide modified product is weighed (A [g]) and then immersed in 100 mL of ion-exchanged water at room temperature (22 ° C.) for 24 hours. After gelling and filtering the gel with a wire mesh of 200 mesh (pore size: 75 μm), the mass (B [g]) of the gel, which is a filter (residue), is measured, and the value calculated by the following formula ( Since A is 1, it is B) after all.

Water absorption capacity (g / g) = B / A
Further, although not particularly limited, the water elution content of the polyalkylene oxide modified product is preferably 10 to 40% by mass, and more preferably 15 to 35%. The water elution component in the present invention is determined by the following formula after weighing the gel after measuring the water absorption capacity for 8 hours in a hot air dryer at 50 ° C. (C [g]). Is the value to be.

Water elution (mass%) = {(AC) / A} x 100

As the filler (component (B)), a filler known to be used for a resin can be appropriately selected and used as long as the effect of the present invention is not 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, diatomaceous earth and the like.

Silica, the specific surface area thereof is preferably more than ^{40m 2 / g, 50m 2 /} g or more, ^{60 m} 2 / g or more, ^70m 2 / g or more, ^{80 m} 2 / g or more, ^90m 2 / g or more, 100 m ² / g The above, or 110 m ² / g or more is more preferable. 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. Further, the silica preferably has an oil absorption amount of 100 mL / 100 g or more, more preferably 150 mL / 100 g or more, and further preferably 190 mL / 100 g 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. The oil absorption amount is a value measured by the method described in JIS K5101-13-2: 2004.

Specific examples of clay include bentonite, smectite and the like. As used herein, bentonite includes organic bentonite (trimethylstearylammonium bentonite, benzyldimethylstearylammonium bentonite, dimethyldistearylammonium bentonite, etc.). Further, in the present specification, smectite includes organic smectite (for example, dimethyl distearyl ammonium hectorite, lithium sodium magnesium trioctyl methyl ammonium silicate, lithium sodium silicate magnesium chloride dipolyoxyethylene palm alkyl (C8). ~ C18) Methylammonium, etc.)).

Examples of the organic filler include cyclodextrin (for example, α-, β-, or γ-cyclodextrin, etc.), modified cyclodextrin (for example, methyl-modified-cyclodextrin, hydroxypropyl-modified-cyclodextrin, etc.), and the like. .. Among them, silica, magnesium carbonate, clay, cyclodextrin, modified cyclodextrin and the like are preferable.

Further, the filler is preferably particles (powder).

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

The volatile substance (component (C)) is not particularly limited as long as it does not volatilize at normal temperature and pressure (25 ° C., 1 atm) when used together with the component (A). In particular, substances (fragrances) that are excellent in aromaticity by volatilizing, or substances that can attract and / or exterminate pests or vermin (for example, pheromones and extermination agents) are preferable. That is, one or more selected from the group consisting of fragrances, pest pheromones, vermin pheromones, pest control agents, and pest control agents is preferable. The pests are not particularly limited, but examples include sanitary pests and food pests, and more specifically, cockroaches, flies, abs, mosquitoes, fleas, fleas, termites, mites, bees, chemists, centipedes, millipedes, moths, etc. Examples include ants and termites. The vermin is not particularly limited, and examples thereof include small mammals (particularly small rodents), and examples include mice and rats.

Although not particularly limited, examples of the fragrance include aloosimene, allyl caproate, allyl heptate, amyl propionate, anesole, anisaldehyde, anisole, benzaldehyde, benzyl acetate, benzylacetone, benzyl alcohol, benzyl butyrate, and benzyl formate. Benzyl Isovalerate, benzyl propionate, β γ-hexenol, camphen, cypress, carbachlor, left-handed-carbeol, d-carboxylic, left-handed-carbonate, cinnamyl formate, citral (neral), citronellol, citronellyl acetate, isobutyric acid Citronellyl, citronellylnitrile, citronellyl propionate, cumin alcohol, cuminaldehyde, Cyclal C, cyclohexylethyl acetate, decylaldehyde, dihydromilsenol, dimethylbenzylcarbinol, dimethylbenzylcarbinate acetate, dimethyloctanol, diphenyloxide, ethyl acetate , Ethyl acetoacetate, ethyl amylketone, ethyl benzoate, ethyl butyrate, ethylhexyl ketone, ethylphenyl acetate, eucalyptor, eugenol, fenquil acetate, fenquil alcohol, flor acetate (tricyclodecenyl acetate), frutene ( Tricyclodecenyl propionate), γ-methylionone, γ-n-methylionone, γ-nonalactone, geraniol, geranyl acetate, geranyl formate, geranyl isobutyrate, geranylnitrile, hexenol, hexenyl acetate, cis-3-hexenyl acetate, Hexenyl isobutyrate, cis-3-hexenyl thioglycenate, hexyl acetate, hexyl formate, hexyl neopentanoate, hexyl thioglycate, hydroatropa alcohol, hydroxycitronellal, indol, isoamyl alcohol, α-ionone, β-ionone, γ -Ionone, α-iron, isobornyl acetate, isobutyl benzoate, isobutyl quinoline, isomenthol, isomentone, isononyl acetate, isononyl alcohol, p-isopropylphenylacetaldehyde, isopregol, isopregil acetate, isoquinolin, cis-jasmon, laurin aldehyde (dodecalal) ), Rigstral, limonene, linalol, linarool oxide, linaryl acetate, linaryl formate, mentone, menthyl acetate, methylacetophenone, methylamylketone, methylanthranylate, methyl benzoate , Methylbenzyl acetate, Methylcavicol, Methyleugenol, Methylheptenone, Methylheptin carbonate, Methylheptylketone, Methylhexylketone, α-iso (γ) methylionone, Methylnonylacetaldehyde, Methyloctylacetaldehyde, Methylphenylcarbinate acetate, Methyl salicylate, Milsen, Neral, Nerrol, Neryl acetate, Nonyl acetate, Nonylaldehyde, Octalactone, Octyl alcohol (octanol-2), Octylaldehyde, Orange terpines (d-limonene), p-cresol, p-cresylmethyl ether, p -Simen, p-methylacetophenone, phenoxyethanol, phenylacetaldehyde, phenylethyl acetate, phenylethyl alcohol, phenylethyldimethylcarbinol, pinene (α-pinene, β-pinene), prenyl acetate, propyl butyrate, pregon, rose oxide, saflor , Α-terpinen, γ-terpinen, terpineol (4-terpineol, α-terpineol), terpineol, terpinyl acetate, tetrahydrolinarool, tetrahydromilsenol, tonalide, undecenal, veratrol, verdox, vertenex, viridine, etc. Be done.

Further, examples of the pheromone include sex pheromones, collective pheromones, alarm pheromones and the like. Specific examples include attractants (particularly insect attractants), and more specifically, for example, (Z) -9-tricosene, (Z) -11-beki-1nodecene-1-aldehyde, (Z). ) -5-Hexadecene, 1-chlor-3-methyl-bud-2-ene, 3-chlor-3-methyl-bud-1-ene, terpineol, farnesol, geraniol, acetic acid, iso Valerian acid, trimethylamine, indole, piperidine, phenylesterol, ammonium carbonate, scatol, formaldehyde, hexamethylenetetramine, ammonium carbamate, papaine, butyric acid, isobaraldehyde, ethylamine, chlorinated alkenepolio Examples thereof include aliphatic monoesters of formaldehyde, pancreatin and vanillin.

Examples of the exterminating agent include salicylic acid, benzoic acid, sorbic acid, p-chloro-m-xylenoyl, 2- (4'-thiazoyl) benzimidazole and the like.

Alternatively, as the insect pheromone, an aliphatic linear aldehyde having 12 to 20 carbon atoms, an aliphatic linear acetate having 12 to 20 carbon atoms having one or more saturated or double bonds, and 7 carbon atoms. ~ 20 Aliphatic Linear Alcohol, 7-15 Carbon Spiroacetal, 10-25 Carbon Aliphatic Linear Ketone, 10-10 30 Aliphatic Hydrocarbon, 10-20 Carbon Carbon Examples thereof include an aliphatic linear aldehyde having 12 to 20 carbon atoms, an aliphatic linear acetate having 12 to 20 carbon atoms having one or more saturated or double bonds, and 7 carbon atoms. Aliphatic linear alcohols of ~ 20 and spiroacetals having 7-15 carbon atoms are preferred. Specifically, Z7Z11-hexadecadienyl acetate, which is a sex pheromone substance of pink ball worm (Wataakamushi), Z7E11-hexadecadienyl acetate, and Z-8-d, which is a sex pheromone substance of Oriental fruit moss (Nashihimeshinkui). Decenyl acetate, E-5-decenyl acetate, which is a sex pheromone substance of peach twig bowler (Momokibaga), Z-9-dodecenyl acetate, which is a sex pheromone substance of Grapeberry Moss (Hosohimehamaki), European Grape E7Z9-dodecadienyl acetate, which is a sex pheromone substance of vine moss (grape hosohamaki), E-11-tetradecenyl acetate, which is a sex pheromone substance of light brown apple moss (Ringo uschairohamaki), codling moss (kodolinga) E8E10-dodecadienol, which is a sex pheromone substance, Z-11-tetradecenyl acetate, which is a sex pheromone substance of leaf roller (hamakiga), and Z3Z13-octadecaji, which is a sex pheromone substance of peach tree bowler (Kosukashiba). Enylacetate and E3Z13-octadecadienylacetate, Z-11-hexadecenal, which is a sex pheromone substance of American ball worm (Otobacco), Z-9-hexadecenal, which is a sex pheromone substance of Oriental tobacco bad worm (Tobacco moth), soybean pod E8E10-dodecadienyl acetate, which is a sex pheromone substance of Borer (Mameshiniga), Z-11-hexadeceenyl acetate and Z-11-hexadecenal, which are sex pheromone substances of diamond back moss (Konaga), and cabbage army worm (Yotoga). ) Sex pheromone substances Z-11-hexadecenyl acetate, Z-11-hexadecenor and n-hexadecyl acetate, beet army worm (Shiroichimojiyoto) sex pheromone substance Z9E12-tetradecadienyl acetate and Z -9-Tetradecenol, Z9E11-Tetradecadienyl acetate, which is a sex pheromone substance of common cut worm (Hasmonyoto), Z9E12-Tetradecadienyl acetate, Z-9-Tetradecenyl, which is a sex pheromone substance of fall army worm. Acetate, E-4-tridecenyl acetate, which is a sex pheromone substance of tomato pin worm, Rice stem bowler (Nikameiga) ) Sex pheromone substances Z-11-hexadecenal and Z-13-octadecenal, coffee leaf minor sex pheromone substances 5,9-dimethylpentadecane and 5,9-dimethylhexadecan, peach leaf minor (peach hamogriga) sex 14-Methyl-1-octadecene, which is a pheromone substance, Z-13-icosen-10-one, which is a sex pheromone substance of peach fruit moss (Momoshiniga), and 7,8-epoxy, which is a sex pheromone substance of gypsy moss (Maimaiga). -2-Methyloctadecane, Z-13-hexadecene-11-inyl acetate, which is a sex pheromone substance of pine processionary moss, 2-butanol, which is a sex pheromone substance of Kebukaakachakogane, Yellow Wish Erongate Chafer ( Z-7,15-hexadecadien-4-olid, which is a sex pheromone substance of Nagachakogane), n-dodecyl acetate, which is a sex pheromone substance of sugar cane wire worm (Okinawakanshakushikometsuki), sugar cane wireworm (saximakanshak) E-9,11-dodecadienyl butyrate, which is a sex pheromone substance of Shikometsuki), E-9,11-dodecadienyl hexanate, and a sex pheromone substance of capreaschafer (Douganebuibui) (R)- Z-5- (Octo-1-enyl) -oxacyclopentan-2-one, hexylhexanoate, E-2-hexenylhexanoate and octyl, which are sex pheromone substances of rice leaf bug (Akahigehisomidorikasumikame) Butyrate, sex pheromone of sorghum plant bug (Akasujikasumikame), hexylbutyrate, E-2-hexenylbutyrate and E-4-oxo-2-hexenal, sex pheromone of white peach scale (Kuwashirokaigaramushi) The substances (6R) -Z-3,9-dimethyl-6-isopropenyl-3,9-decadienyl propionate and (6R) -Z-3,9-dimethyl-6-isopropenyl-3, 9-Decadienol, a sex pheromone substance of Vine Milliebug (Grape beetle) (S) -5-methyl-2- (1-propen-2-yl) -4-hexenyl 3-methyl-2-butenoate, house Z-9-tricosen, a sex pheromone substance of fry (ye flies), a sex pheromone substance of German cockroach (chabanegokiburi) Examples include gentisilquinone isovalerate, which is a quality, and 1,7-dioxaspiro [5.5] undecane, which is a sex pheromone substance of olive fruit fly (olive fruit fly).

Volatile substances can be used alone or in combination of two or more. A substance that is a fragrance and a substance that is a pest or a vermin pheromone or a pesticide can be used in combination, but in particular, a substance that is a fragrance is used alone or in combination of two or more, or a pest. It is preferable to use one or a combination of two or more selected from the group consisting of pheromones, pest pheromones, pest control agents, and pest control agents.

The composition for releasing volatile substances of the present invention may contain other components as long as the effects of the present invention are not impaired. As the other component, for example, a non-volatile component may be contained. As the other component, for example, an insecticidal component is preferably mentioned. Preferable examples of the insecticidal component include neonicotinoid dinotefuran and acetamiprid, pyrrole chlorfenapyr, phenylpyrazole fipronil, macrolide lactone emamectin benzoate, and organophosphorus triclophon. Of these, water-soluble insecticides are preferred, and dinotefuran is particularly preferred.

In the composition for dissipating volatile substances of the present invention, the mass ratio of the components (A) and (B) is preferably about 1: 0.0001 to 0.2, preferably 1: 0.001 to 0. It is more preferably about .15, and even more preferably about 1: 0.01 to 0.1. In these ranges, the lower limit of the component mass ratio (B) may be 0.0001, 0.0005, 0.001, 0.005, or 0.01. Further, in these ranges, the upper limit of the (B) component mass ratio is 0.2, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.10. It may be 12, 0.11, or 0.1.

The method for producing the composition for releasing volatile substances of the present invention is not particularly limited. For example, it can be produced by first preparing a composition containing the component (A) and the component (B) (composition containing (A) and (B)) and adding the component (C) to the composition (composition containing (A) and (B)). Further, when the other component is included, for example, when the component (C) is included, the other component can be included at the same time.

When preparing the compositions containing (A) and (B), the component (A) may be prepared first, and then the component (B) may be mixed thereto, or as described above, at the time of preparing the component (A). The component (B) may be added to the reaction system in advance (during the polymerization reaction). As a method of mixing the component (B) with the component (A) after preparing the component, a known method used when adding a filler to the resin can be used. More specifically, (A) and (B) are obtained by mixing the components (A) and (B) while heating as necessary using, for example, a roller, a kneader, an extruder, or the like. The containing composition can be prepared.

As a method of incorporating the component (C) into the compositions containing (A) and (B), for example, a liquid composition containing the component (C) is made to absorb the liquid composition containing (A) and (B). The method can be mentioned. Examples of the solvent of the liquid composition containing the component (C) include water, an organic solvent (for example, ethanol, etc.), and a mixed solution thereof, and water is particularly preferable. As the liquid composition containing the component (C), a composition containing the solvent and the component (C) is preferable, and a composition containing only the solvent and the component (C) is more preferable. In the liquid composition containing the component (C), the solvent is preferably contained in an amount of 80 to 99% by mass, 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% by mass. Further, the upper limit of the range may be about 99, 98, 97, or 96% by mass. Further, in the liquid composition containing the component (C), the component (C) is preferably contained in an amount of 1 to 20% by mass, more preferably 2 to 10% by mass, and more preferably 3 to 6% by mass. preferable. The lower limit of the range may be 1, 2, 3, or 4% by mass. Further, the upper limit of the range may be 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, or 6% by mass.

The liquid composition containing the component (C) may contain a solvent and components other than the component (C). Examples of such a component include a surfactant, and a nonionic surfactant is preferable. More specifically, for example, a nonylphenol-based surfactant can be mentioned. Examples of the content of the surfactant in the liquid composition containing the component (C) include 0.05 to 0.5% by mass, 0.06 to 0.4% by mass, and 0.07 to 0.3. It may be about 0.08 to 0.2% by mass, or 0.09 to 0.15% by mass.

When the liquid composition containing the component (C) is absorbed by the compositions containing (A) and (B), the compositions containing (A) and (B), and the compositions containing (A) and (B) are contained. The mass ratio of the liquid composition containing the component (C) to be absorbed by the composition is preferably about 1: 1 to 30, more preferably about 1: 1 to 25, and 1: 1 to 20. More preferably. The upper limit of the mass is 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 about 30.

The present invention also includes embodiments in which the compositions containing (A) and (B) are used in particular for absorbing a volatile substance-containing liquid composition. That is, a composition containing a component (A) and a component (B) for absorbing a volatile substance-containing liquid composition is also included in the present invention. The present invention also comprises releasing the volatile substance in the volatile substance-containing liquid composition into the atmosphere, which comprises a step of causing the (A) and (B) -containing compositions to absorb the volatile substance-containing liquid composition. It also includes ways to increase sustainability. Various conditions for these embodiments are the same as those described above.

In addition, in this specification, "including" also includes "consisting essentially" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of."). In addition, the various properties (property, structure, function, etc.) described for each embodiment of the present invention described above may be combined in any way in specifying the subject matter included in the present invention. That is, the present invention includes all subjects consisting of any combination of each of the combinable properties described herein.

Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the following examples.

[Evaluation method]
The water absorption capacity, water elution component, and median diameter (when further pulverized after production) were measured for the polyalkylene oxide modified product described in the following production example according to the following method.
(1) Water absorption capacity The water absorption capacity of the modified polyalkylene oxide was measured by the following method.

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

Water absorption capacity (g / g) = B / A
(2) Water elution content The gel after measuring the water absorption capacity was dried in a hot air dryer at 50 ° C. for 8 hours, and then the mass was weighed (C [g]) to determine the water elution content by the following formula. ..

Water elution (mass%) = {(AC) / A} x 100
(3) Median diameter The median diameter was determined by the dry sieving method (JIS Z8815). Specifically, 50 g of the obtained sample is weighed, sieved using a JIS standard sieve (JIS Z8801), and then weighed for each sieve, and the integrated mass becomes 50% based on the result. The position diameter was calculated.

Production Example I: Production of Polyalkylene Oxide Modified Product 100 parts by mass of fully dehydrated polyethylene oxide having a number average molecular weight of 20000 and 0.9,4-butanediol in a storage tank A equipped with a stirrer kept at 80 ° C. The mixture was charged in a proportion of 0.1 parts by mass and 0.1 part by mass of dioctyltindilaurate, and stirred in a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4'-diisocyanate was charged into a storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.

Using a metering pump, set the mixture in storage tank A 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 at 110-140 ° C. It is continuously supplied to the twin-screw extruder (R value = 1.00), mixed in the extruder to carry out the reaction, strands are taken out from the extruder outlet, pelletized by a pelletizer, and a polyalkylene oxide modified product. Got The polyalkylene oxide modified product pellet obtained in Production Example I was used as a polyalkylene oxide modified product in the following examples.

The water absorption capacity of the obtained polyalkylene oxide modified product was 25 g / g, and the water elution content was 19% by mass.

Production Example II: Production number of modified polyalkylene oxide products Ethylene glycol obtained by heating an ethylene oxide / propylene oxide (mass ratio: 90/10) copolymer having an average molecular weight of 15,000 at a rate of 250 g / min and at 40 ° C. At a rate of 2.1 g / min, each was supplied to a 40 mmφ single-screw extruder (L / D = 40, set temperature: 90 ° C.) to melt and mix the two. Note that φ means the diameter of the screw.

The mixture obtained from the discharge port (discharged in a uniform molten state and analyzed by HPLC to confirm that the mixture was mixed at the charging ratio) was subjected to a 30 mmφ twin-screw extruder (L / D = 41. It was continuously supplied to the hopper port (set temperature: 80 ° C.) of 5). At the same time, dioctyl tindilaurate was supplied to the hopper mouth of the twin-screw extruder at a rate of 0.5 g / min.

Further, dicyclohexylmethane-4,4'-diisocyanate adjusted to 30 ° C. is also supplied at a rate of 12.4 g / min to the screw barrel portion located on the downstream side of the hopper mouth of the twin-screw extruder (R). Value = 0.95), the reaction was carried out continuously under a nitrogen atmosphere (set temperature: 180 ° C.). The strands obtained from the outlet of the twin-screw extruder were cooled and then pelletized with a pelletizer to obtain a modified polyalkylene oxide.

The water absorption capacity of the obtained polyalkylene oxide modified product was 20 g / g, and the water elution content was 15% by mass.

Production Examples 1 to 16
0.5 g (1 part by weight: Table 1) of various fillers in 50 g of the modified polyalkylene oxide (prepared in Production Example I), 1.5 g (3 parts by weight: Table 2), 2.5 g (5 parts by weight) : Table 3) or a composition containing 5 g (10 parts by weight: Table 4) is set by a 4-inch roll (manufactured by Yasuda Seiki Seisakusho Co., Ltd. (model: No. 191-TM TEST MIXING ROLL)) to set the roller temperature 45. It was prepared by melting and kneading at ~ 55 ° C. The composition is pressurized by a 68t hot press (manufactured by Tokai Kikai Seisakusho Co., Ltd. (TYPE: VH6-5A-120B)) for 3 minutes under the conditions of hot plate temperature setting 150 ° C. and hot plate pressure setting 30 kgf / cm ^2. As a result, a sheet having a thickness of 2 mm was produced.
The various fillers used are shown in Tables 1 to 4. In the table below, the modified polyalkylene oxide is also referred to as "resin".

As for various fillers, commercially available products were purchased and used. Detailed information on various fillers is as follows. The specific surface area of silica is a value measured by a nitrogen gas adsorption method, and the oil absorption amount is a value measured by the method described in JIS K5101-13-2: 2004.
Filler (1): Organic smectite smecton SAN [manufactured by Kunimine Industries, Ltd.]
Filler (2): Organic smectite smecton STN [manufactured by Kunimine Industries, Ltd.]
Filler (3): Silica beads Nip seal EL [manufactured by Toso Silica Co., Ltd.] (Specific surface area: 48 m ² / g, Oil absorption: 180 mL / 100 g)
Filler (4): Silica Carplex 80 [manufactured by Evonik Japan Co., Ltd.] (Specific surface area: 200 m ² / 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.]
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) [Made by Hayashi Junyaku]

Examples 1-17
The compositions obtained in Production Examples 1 to 16 are made into pellets of 4 mm square in length and width by a super straight cutter (manufactured by Dumbbell Co., Ltd. (model: SSK-1000S-D punching size (L): 100 mm)). Molding was performed to obtain pellets of various compositions (length, width, thickness: 4 mm, 4 mm, 2 mm). These were used in Examples 1 to 16, respectively. Further, among these pellets, the pellets obtained from the composition obtained in Production Example 16 were immersed in liquid nitrogen and then pulverized so as to have a medium diameter of 60 μm to obtain a powder of the composition. This powder was used in Example 17.

1 g of pellets or powders of the obtained various compositions (in the case of pellets, the number: about 20) is immersed in 10 g of a volatile substance-containing liquid A, B, or C, allowed to absorb the liquid for 24 hours, and then the composition. Only the excess liquid containing volatile substances that was not absorbed by the pellets or powder of the substance was separated to obtain a pellet-like or powder-like liquid-absorbing composition (that is, a composition for releasing volatile substances). (Examples 1 to 17). The various liquid absorbing compositions obtained are summarized in Table 5.

Table 6 shows the compositions of the volatile substance-containing liquids A, B, and C used in Examples and the like. In Examples 1 to 16, Examples 1a to 16a using the volatile substance-containing liquid A, Examples 1b to 16b using the volatile substance-containing liquid B, and the volatile substance-containing liquid C were used. Examples 1c to 16c used are used. Further, in Example 17, an example in which the volatile substance-containing liquid A is used is referred to as Example 17a.

Of the liquid absorbing compositions obtained in Examples 1 to 16, three pellets of the composition prepared by absorbing the volatile substance-containing liquid A were collected in a 25 mL vial and then headspaced at 40 ° C. The amount of volatile components released from the liquid absorbing composition is analyzed by quantitatively analyzing the gas in the gas phase part in the 25 mL vial by GC analysis (headspace method) while maintaining it in the oven for 17 minutes. did. Further, among the liquid absorbing compositions obtained in Example 17, 0.1 g of the composition prepared by absorbing the volatile substance-containing liquid A was collected in a vial, and the liquid absorbing composition was similarly collected. The amount of volatile components released from the material was analyzed.

(GC conditions ・ Equipment body: GC-2014 (manufactured by Shimadzu Corporation), ・ Autosampler equipment: HT-2800T (manufactured by Alpha Moss Japan Co., Ltd.), ・ Column: G-250, ・ Carrier: He (flow rate: He) 50 mL / min), ・ Detector: FID, ・ INJ temperature: 230 ° C, ・ Detector temperature: 250 ° C)

Table 7 shows the area values (peak area values) of limonene detected from the liquid absorbing composition obtained by absorbing the volatile substance-containing liquid A by the GC analysis.

In the composition prepared by absorbing the volatile substance-containing liquid A, in the evaluation of the change in the amount of the volatile substance-containing liquid component released over time, among various volatile components, almost all of the volatile components Since the amount of release showed the same behavior as limonene (change in amount of release), limonene was selected and evaluated as a typical component. In addition, the area value is corrected by finally confirming the real weight of 3 pellets by completely drying them (“area value / real weight of 3 pellets” or “area value / powder used”. The real weight of the body (0.1 g) ”, that is, the area value of limonene released per 1 g of pellet or powder). Hereinafter, the area value of limonene released per 1 g of pellet or powder may be referred to as a limonene correction area value.

Further, among the liquid absorbing compositions obtained in Examples 1 to 17, pellets or powders of the composition prepared by absorbing the volatile substance-blended liquid A are placed in a blower dryer set at 40 ° C. 6 The mixture was allowed to stand for an hour or 12 hours to evaporate the absorbed volatile components. Then, three pellets of the liquid absorbing composition were collected in a 25 mL vial, maintained in a headspace oven at 40 ° C. for 17 minutes, and the gas in the gas phase in the 25 mL vial was analyzed by GC (head). The amount of vaporized volatile components was analyzed by quantitative analysis using the space method). Table 7 shows the limonene correction area values detected by the GC analysis.

Among the liquid absorbing compositions obtained in Examples 1 to 16, the pellets of the composition prepared by absorbing the volatile substance-containing liquid B are subjected to limonene correction detected by GC analysis in the same manner as described above. The area value was calculated. The results are shown in Table 8. In the composition prepared by absorbing the volatile substance-containing liquid B, the amount of the volatile substance-containing liquid component released over time is the same as in the composition prepared by absorbing the volatile substance-containing liquid A. In the evaluation of changes, limonene was selected as a representative component because the release amount of almost all volatile components showed the same behavior (change in release amount) as limonene among various volatile components. And evaluated.

Further, among the liquid absorbing compositions obtained in Examples 1 to 16, the pellets of the composition prepared by absorbing the volatile substance-containing liquid C were subjected to GC analysis in the same manner as described above.
In the composition prepared by absorbing the volatile substance-containing liquid C, almost all of the volatile components are volatile in the evaluation of the change in the amount of the volatile substance-containing liquid component released over time. Since the release amount of the component showed the same behavior (change in release amount) as that of Z-9-tricosene, Z-9-tricosene was selected and evaluated as a representative component. Similar to the evaluation of the composition prepared by absorbing the volatile substance-containing liquid A, the composition prepared by absorbing the volatile substance-containing liquid C was released as Z-9 per 1 g of pellets. -Trichothecene area value (Z-9-Trichothecene correction area value) was calculated. The results are shown in Table 9.

Comparative Examples 1-3
1 g of pellets (length, width, thickness: 4 mm, 4 mm, 2 mm) (number of pellets: about 20) prepared without adding a filler to the modified polyalkylene oxide, 10 g of liquid A, B, or C containing a volatile substance After immersing the liquid in the pellet for 24 hours, only the excess volatile substance-containing liquid that was not absorbed by the pellet was separated to obtain a pellet-shaped liquid-absorbing polyalkylene oxide modified product. Three pellets of the liquid-absorbing polyalkylene oxide modified product were collected in a 25 mL vial and then maintained in a headspace oven at 40 ° C. for 17 minutes, and the gas in the gas phase in the 25 mL vial was changed to the same as above. The amount of volatile components evaporated from the liquid-absorbing polyalkylene oxide modified product was analyzed by quantitative analysis by GC analysis (headspace method) under the conditions of.

Further, the pellets of the liquid-absorbing polyalkylene oxide-modified product were placed in a blower dryer set at 40 ° C., and the absorbed hydrophobic component was allowed to stand for 6 hours or 12 hours to evaporate the absorbed volatile component. Then, three pellets of the liquid-absorbing polyalkylene oxide modified product were collected in a 25 mL vial, and then maintained in a headspace oven at 40 ° C. for 17 minutes, and the gas in the gas phase part in the 25 mL vial was discharged to GC. The amount of vaporized volatile components was analyzed by quantitative analysis by analysis (headspace method).

Table 10 shows the limonene correction area values detected by GC analysis from the polyalkylene oxide modified products that have absorbed the volatile substance-containing liquids A and B.

Table 11 shows the Z-9-trichothecene correction area values detected by GC analysis from the polyalkylene oxide modified product that has absorbed the volatile substance-containing liquid C.

Claims (8)

(A) A polyalkylene oxide modified product obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound.
A composition for releasing volatile substances, which contains (B) a filler and (C) a volatile substance. The polyalkylene oxide compound is 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. The composition for releasing volatile substances according to claim 1, which comprises at least one selected from the group consisting of copolymers. The diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol. The composition for releasing volatile substances according to claim 1 or 2, which comprises at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol. The diisocyanate compounds are 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3, Includes at least one selected from the group consisting of 5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzol-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI). , The composition for releasing volatile substances according to any one of claims 1 to 3. (B) Any of claims 1 to 4, wherein the filler comprises at least one selected from the group consisting of silica, magnesium carbonate, clay, talc, calcium carbonate, titanium oxide, diatomaceous earth, cyclodextrin, and modified cyclodextrin. The composition for releasing volatile substances described in silica. (C) The volatile substance according to any one of claims 1 to 5, wherein the volatile substance is one or more selected from the group consisting of a fragrance and a pest or vermin pheromone and a repellent. Composition. A composition containing the following components (A) and (B) for absorbing a volatile substance-containing liquid composition.
(A) Polyalkylene oxide modified product (B) filler obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound. The volatile substance in the volatile substance-containing liquid composition, which comprises the step of causing the composition containing the following components (A) and (B) to absorb the volatile substance-containing liquid composition into the atmosphere. A method of increasing release sustainability.
(A) Polyalkylene oxide modified product (B) filler obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound.