JP7185641B2 - Composition for volatile material dissipation - Google Patents

Description

TECHNICAL FIELD The present invention relates to a volatile substance-dissipating composition and the like.

Compositions containing useful volatile substances in resin gels are used in various applications. For example, if the volatile substance is an aromatic substance, a pleasant fragrance can be diffused into the room. Alternatively, if the volatile substance is a pest or vermin attractant, it can attract pests or vermin, thereby facilitating their extermination.

Such a volatile substance-containing composition is required to release the volatile substance continuously for a long time (that is, to have high sustained release).

JP-A-6-32863 JP-A-6-140052 JP-A-8-12871 JP-A-6-98627 JP-A-2001-172358 JP-A-2002-265780 JP-A-2002-331023 JP 2007-254363 A Japanese Patent Publication No. 2017-517611 WO2013/084983

An object of the present invention is to provide a volatile substance-containing composition that is excellent in sustained release of volatile substances.

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

The invention includes, for example, the subject matter described in the following sections.
Section 1.
(A) a modified polyalkylene oxide obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound;
A volatile material-dissipating composition comprising (B) a filler and (C) a volatile material.
Section 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 volatile substance-dissipating composition according to Item 1, comprising at least one selected from the group consisting of copolymers.
Item 3.
The diol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, Item 3. The volatile substance-dissipating composition according to Item 1 or 2, comprising at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol.
Section 4.
The diisocyanate compound is 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3, 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) 3. The composition for volatile substance dissipation according to any one of Items 1 to 3.
Item 5.
(B) Any one 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 volatile substance dissipation according to .
Item 6.
(C) The volatile substance-diffusing composition 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 pesticides. thing.
Item 7.
A composition containing the following components (A) and (B) for absorbing a volatile substance-containing liquid composition.
(A) Modified polyalkylene oxide obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound (B) Filler Item 8.
including the step of allowing a composition containing the following components (A) and (B) to absorb the volatile substance-containing liquid composition into the atmosphere: Methods for increasing sustained release.
(A) polyalkylene oxide modified product obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound (B) filler

According to the present invention, it is possible to enhance the sustained release of volatile substances. The volatile substance-dissipating composition of the present invention gradually releases the contained volatile substances, so that the effect of the volatile substances lasts longer (that is, it is also excellent in sustained release). Moreover, the volatile material-dissipating compositions of the present invention can contain amounts of volatile materials that are even greater than the amount of volatile materials that conventional resins 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, 21, 22, 23, or 24 hours (or 1, 2, 3, 4, 5, 6, or 7 days). more than

Each embodiment of the present invention will be described in further detail below.

The volatile material-dissipating composition encompassed by the present invention contains (A) a specific modified polyalkylene oxide, (B) a filler, and (C) a volatile material. These components are sometimes referred to as component (A), component (B), and component (C), respectively. Further, the volatile substance-dissipating composition is sometimes referred to as the volatile substance-dissipating composition of the present invention.

The specific modified polyalkylene oxide (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 compounds 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 copolymers and the like can be exemplified. A polyalkylene oxide compound can be used individually by 1 type or in combination of 2 or more types. Here, "/" is a symbol used to indicate a copolymer of each oxide. For example, an ethylene oxide/propylene oxide copolymer refers to 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 preferred, and a polyalkylene oxide compound having a number average molecular weight of 10,000 to 30,000 is more preferred.

In addition, the value of the number average molecular weight here is a value calculated|required by the measuring method of the following description. Number-average molecular weight measurement method: A dimethylformamide solution containing a modified polyalkylene oxide at a concentration of 1% by mass is prepared and measured using a high-performance liquid chromatograph. Then, a molecular weight marker (polyethylene oxide) with 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: TSK GEL Multipore HXL-M manufactured by Tosoh Corporation Column temperature: 40 ° C.
Eluent: dimethylformamide Flow rate: 0.6 ml/min
A polyalkylene oxide compound having 90% by mass or more of ethylene oxide groups is preferable, and a polyalkylene oxide compound having 95% by mass or more of ethylene oxide groups 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, and 1,9-nonanediol. These diol compounds can be used singly 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, per 1 mol of the polyalkylene oxide compound. The number of moles of the polyalkylene oxide compound can be obtained by dividing the 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. Examples include 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate ( HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzol-2,4 -diisocyanate, and 2,4-tolylene diisocyanate (TDI). Among these diisocyanate compounds, dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are preferably used. These diisocyanate compounds may be used alone or in combination of two or more.

The use ratio of each of the polyalkylene oxide compound, the diol compound, and the diisocyanate compound 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.

A known method can be used as a method for reacting the polyalkylene oxide compound, the diol compound, and the diisocyanate compound. For example, a method of dissolving or dispersing these in a reaction solvent such as toluene, xylene, or dimethylformamide and reacting them; a method of uniformly mixing powdery or solid materials and then heating them to a predetermined temperature to react them; etc. From the standpoint of industrial implementation, a method of continuously supplying each raw material in a molten state and mixing and reacting them in a multi-screw extruder is preferable. In this case, the reaction temperature is preferably 70 to 210°C.

Moreover, when producing the polyalkylene oxide-modified product, a catalyst may be added to the reaction system from the viewpoint of promoting the reaction. For example, suitable amounts of catalysts such as triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, and triethylenediamine can be added.

A modified polyalkylene oxide can be obtained by such a method. According to such a method, the modified polyalkylene oxide is usually obtained in the form of pellets, sheets, films, or the like. These may be used as they are for the composition for volatile substance dissipation of the present invention, or may be used for the composition for volatile substance dissipation of the present invention after being pulverized, for example, by a pulverizer or the like. The pulverization method is not particularly limited, but freeze pulverization is preferable in order to prevent fusion due to heat generated by shearing during pulverization. For example, it can be freeze-pulverized using liquid nitrogen.

Note that (B) a filler may be added to the reaction system when producing the modified polyalkylene oxide. In this case, since the resulting polyalkylene oxide-modified product-containing composition already contains the components (A) and (B), adding the component (C) to the composition allows the of volatile material stripping compositions can be prepared. The polyalkylene oxide-modified product-containing composition obtained by adding (B) a filler to the reaction system may be used as it is for the volatile substance-dissipating composition of the present invention, or may be processed by a grinder or the like. After being pulverized, it may be used in the volatile substance-dissipating composition of the present invention. The pulverization method is not particularly limited, but freeze pulverization is preferable in order to prevent fusion due to heat generated by shearing during pulverization. For example, it can be freeze-pulverized using liquid nitrogen.

The modified polyalkylene oxide is preferably water-absorbent (that is, has water-absorbing ability). In particular, in preparing the volatile substance-dissipating composition of the present invention, it is preferable to include (C) a volatile substance in the polyalkylene oxide-modified product. In this case, for example, the volatile substance is added to water, A method of dissolving or dispersing the volatile substance and water in a state of layer separation (two-layer separation) and allowing the polyalkylene oxide modified product to absorb the volatile substance-containing liquid is preferably used. 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 is defined by weighing (A [g]) of 1.0 g of the modified polyalkylene oxide and immersing it in 100 mL of deionized water at room temperature (22° C.) for 24 hours. After gelling and filtering the gel through a wire mesh of 200 mesh (pore size: 75 μm), the mass (B [g]) of the gel, which is the filtered material (residue), is measured, and the value calculated by the following formula ( Since A is 1, it boils down to B).

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

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

As the filler (component (B)), fillers known to be used in resins can be appropriately selected and used as long as the effects of the present invention are not impaired. The filler may be an inorganic filler or an organic filler.

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

Silica preferably has a specific surface area of 40 m ² /g or more, 50 m ² /g or more, 60 m ² /g or more, 70 m ² /g or more, 80 m ² /g or more, 90 m ² /g or more, 100 ^{m 2} /g or more. or more, or more preferably 110 m ² /g or more. The upper limit of the specific surface area is not particularly limited, but is exemplified by 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. Silica preferably has an oil absorption of 100 mL/100 g or more, more preferably 150 mL/100 g or more, and even more preferably 190 mL/100 g or more. The upper limit of the oil absorption is not particularly limited, but is exemplified by 400 mL/100 g or less, 380 mL/100 g or less, 350 mL/100 g or less, or 300 mL/100 g or less. The oil absorption is a value measured by the method described in JIS K5101-13-2:2004.

Specific examples of clay include bentonite and smectite. As used herein, bentonite includes organized bentonite (trimethylstearylammonium bentonite, benzyldimethylstearylammonium bentonite, dimethyldistearylammonium bentonite, etc.). In addition, in the present specification, smectites include organic smectites (e.g., dimethyldistearylammonium hectorite, lithium-sodium-magnesium trioctylmethylammonium silicate, lithium-sodium-magnesium silicate dipolyoxyethylene coconut alkyl chloride (C8 to C18) methylammonium, etc.).

Examples of organic fillers include cyclodextrin (eg, α-, β-, or γ-cyclodextrin), modified cyclodextrin (eg, 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).

A filler can be used individually by 1 type or in combination of 2 or more types.

The volatile substance (component (C)) is not particularly limited as long as it does not volatilize at normal temperature and normal pressure (25° C., 1 atm) when used together with component (A). In particular, a substance (perfume) that has excellent fragrant properties by volatilization, or a substance that can attract and/or exterminate pests or pests (for example, pheromones and pesticides) is preferable. That is, one or more selected from the group consisting of fragrances, pest pheromones, pest pheromones, pest exterminators, and pest exterminators are preferred. Pests are not particularly limited, but include sanitary pests and food pests. Examples include ants and termites. Pests are not particularly limited, but examples include small mammals (especially small rodents) such as mice and rats.

Examples of perfumes include, but are not limited to, alloocimene, allyl caproate, allyl heptonate, amyl propionate, anesol, anisaldehyde, anisole, benzaldehyde, benzyl acetate, benzylacetone, benzyl alcohol, benzyl butyrate, benzyl formate, Benzyl isovalerate, benzyl propionate, β γ-hexenol, camphene, camphor, carvacrol, levorotatory carveol, d-carvone, levorotatory carvone, cinnamyl formate, citral (neral), citronellol, citronellyl acetate, isobutyric acid Citronellyl, citronellyl nitrile, citronellyl propionate, cumin alcohol, cumin aldehyde, Cyclal C, cyclohexylethyl acetate, decylaldehyde, dihydromyrcenol, dimethylbenzylcarbinol, dimethylbenzylcarbyl acetate, dimethyloctanol, diphenyloxide, ethyl acetate , ethyl acetoacetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethylhexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenky acetate, fenky alcohol, furol 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 tiglate, hexyl acetate, hexyl formate, hexyl neopentanoate, hexyl tiglate, hydroatropa alcohol, hydroxycitronellal, indole, isoamyl alcohol, α-ionone, β-ionone, γ - ionone, α-irone, isobornyl acetate, isobutyl benzoate, isobutylquinoline, isomenthol, isomenthone, isononyl acetate, isononyl alcohol, p-isopropylphenylacetaldehyde, isopulegol, isopulegyl acetate, isoquinoline, cis-jasmone, lauric aldehyde (dodecanal ), ligustral, limonene, linalool, linalool oxide, linalyl acetate, linalyl formate, menthone, menthyl acetate, methylacetophenone, methyl amyl ketone, methyl anthranilate, methyl benzoate , Methyl benzyl acetate, Methyl chavicol, Methyl eugenol, Methylheptenone, Methylheptyne carbonate, Methylheptylketone, Methylhexylketone, α-iso(γ)methylionone, Methylnonylacetaldehyde, Methyloctylacetaldehyde, Methylphenylcarbyl acetate, Methyl salicylate, myrcene, neral, nerol, neryl acetate, nonyl acetate, nonylaldehyde, octalactone, octyl alcohol (octanol-2), octylaldehyde, orange terpenes (d-limonene), p-cresol, p-cresyl methyl ether, p -cymene, p-methylacetophenone, phenoxyethanol, phenylacetaldehyde, phenylethyl acetate, phenylethyl alcohol, phenylethyldimethylcarbinol, pinene (α-pinene, β-pinene), prenyl acetate, propyl butyrate, pulegone, rose oxide, safrole , α-terpinene, γ-terpinene, terpineol (4-terpineol, α-terpineol), terpinolene, terpinyl acetate, tetrahydrolinalool, tetrahydromyrcenol, tonalide, undecenal, veratrol, verdox, vertenex, viridine, etc. be done.

Examples of pheromones include sex pheromones, aggregation pheromones, and alarm pheromones. Specific substances include attractants (especially insect attractants). )-5-hexadecene, 1-chloro-3-methyl-but-2-ene, 3-chloro-3-methyl-but-1-ene, terpineol, fulnesol, geraniol, acetic acid, iso Valerian acid, trimethylamine, indole, piperidine, phenylethanol, ammonium carbonate, skatole, formaldehyde, hexamethylenetetramine, ammonium carbamate, papain, butyric acid, isovaleraldehyde, ethylamine, chlorinated alkenes polyol aliphatic monoesters of mol, pancreatin, vanillin, and the like.

Pesticides include, for example, salicylic acid, benzoic acid, sorbic acid, p-chloro-m-xylenol, 2-(4'-thiazolyl)benzimidazole and the like.

Alternatively, insect pheromones include straight-chain aliphatic aldehydes having 12 to 20 carbon atoms, straight-chain aliphatic acetates having 12 to 20 carbon atoms and having one or more saturated or double bonds, and 7 carbon atoms. ~20 aliphatic linear alcohols, C7-15 spiroacetals, C10-25 aliphatic linear ketones, C10-30 aliphatic hydrocarbons, C10-20 carvone Acids and the like, in particular, aliphatic straight-chain aldehydes with 12 to 20 carbon atoms, saturated or straight-chain aliphatic acetates with 12 to 20 carbon atoms having one or more double bonds, and 7 carbon atoms. Aliphatic linear alcohols of -20 and spiroacetals of 7-15 carbon atoms are preferred. Specifically, Z7Z11-hexadecadienyl acetate and Z7E11-hexadecadienyl acetate, which are the sex pheromone substances of pink ballworm (Gossypium bollworm), and Z-8-d, which is the sex pheromone substance of oriental fruit moss (Nashihimeshinkai) Decenyl acetate, E-5-decenyl acetate which is a sex pheromone substance of peach twig borer (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 of vine moss (grape vine), E-11-tetradecenyl acetate, which is a sex pheromone of light brown apple moss (apple moss), codling moss (codling moth) E8E10-dodecadienol, which is the sex pheromone of leaf roller (Tomato moth), Z-11-tetradecenyl acetate, which is the sex pheromone of leaf roller (Tomato moth), Z3Z13-octadecadie, which is the sex pheromone of peach tree borer (Kosukashiba) Enyl acetate and E3Z13-octadecadienyl acetate, Z-11-hexadecenal, a sex pheromone of American bollworm (Helicopter moth), Z-9-hexadecenal, a sex pheromone of Oriental tobacco budworm (Tobacco moth), Soybean pod E8E10-dodecadienyl acetate, which is a sex pheromone substance of Borer (bean bug moth), Z-11-hexadecenyl acetate and Z-11-hexadecenal, which are sex pheromone substances of diamondback moth (diamond back moth), Cabbage army worm (spodworm moth) ) sex pheromone substances Z-11-hexadecenyl acetate, Z-11-hexadecenol and n-hexadecyl acetate, and beet armyworm sex pheromone substances Z9E12-tetradecadienyl acetate and Z -9-tetradecenol, Z9E11-tetradecadienyl acetate and Z9E12-tetradecadienyl acetate, which are sex pheromones of common cutworm (Spodoptera litura), Z-9-tetradecenyl, which is sex pheromone of fall armyworm Acetate, E-4-tridecenyl acetate which is a sex pheromone substance of tomato pinworm, rice stem borer ) sex pheromone substances Z-11-hexadecenal and Z-13-octadecenal, coffee leaf miner sex pheromone substances 5,9-dimethylpentadecane and 5,9-dimethylhexadecane, peach leaf minor 14-methyl-1-octadecene as a pheromone substance, Z-13-icosen-10-one as a sex pheromone substance for peach fruit moss (Peach moth), 7,8-epoxy as a sex pheromone substance for gypsy moss (gypsy moth) -2-methyloctadecane, Z-13-hexadecen-11-ynyl acetate, which is the sex pheromone substance of pine processionary moss, 2-butanol, which is the sex pheromone substance of the red scarab beetle, Yellow Wish Elongate Chafer ( Z-7,15-hexadecadiene-4-olide, which is a sex pheromone substance of Japanese scarab beetle, n-dodecyl acetate, which is a sex pheromone substance of sugar cane wireworm E-9,11-dodecadienyl butyrate and E-9,11-dodecadienyl hexanate, which are sex pheromone substances of Saccharomyces cerevisiae, and (R)-, which is a sex pheromone substance of Capreas Chafer Z-5-(oct-1-enyl)-oxacyclopentan-2-one, hexylhexanoate, E-2-hexenylhexanoate and octyl, which are sex pheromones of the rice leaf bug Butyrate, sex pheromone substances of sorghum plant bugs (Calpus thunbergii), hexyl butyrate, E-2-hexenyl butyrate and E-4-oxo-2-hexenal, sex pheromones of white peach scale (mulberry scale) the substances (6R)-Z-3,9-dimethyl-6-isopropenyl-3,9-decadienylpropionate and (6R)-Z-3,9-dimethyl-6-isopropenyl-3, 9-decadienol, (S)-5-methyl-2-(1-propen-2-yl)-4-hexenyl 3-methyl-2-butenoate, a sex pheromone of vine millie bug (grape mealybug), house Z-9-tricosene, sex pheromone of fly (housefly), sex pheromone of German cockroach (German cockroach) gentisyl quinone isovalerate, which is a protein, and 1,7-dioxaspiro[5.5]undecane, which is a sex pheromone substance of olive fruit fly (olive fruit fly).

A volatile substance can be used individually by 1 type or in combination of 2 or more types. It is also possible to use a substance that is a fragrance in combination with a pest or vermin pheromone or a substance that is a pesticide, but in particular, one type of substance that is a perfume is used alone or in combination of two or more, or a substance that is a pest is used. It is preferable to use one or a combination of two or more selected from the group consisting of pheromones, pest pheromones, pesticides, and pesticides.

The volatile substance-dissipating composition 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 included. Other components are preferably insecticidal components, for example. Suitable insecticidal components include, for example, neonicotinoid dinotefuran and acetamiprid, pyrrole chlorfenapyr, phenylpyrazole fipronil, macrolide lactone emamectin benzoate, and organophosphorus triclofone. Among these, water-soluble insecticides are preferred, and dinotefuran is particularly preferred.

In the volatile substance-dissipating composition of the present invention, the mass ratio of component (A) and component (B) is preferably about 1:0.0001 to 0.2, and 1:0.001 to 0.2. It is more preferably about 0.15, and more preferably about 1:0.01 to 0.1. Within these ranges, the (B) component mass ratio lower limit may be 0.0001, 0.0005, 0.001, 0.005, or 0.01. Within these ranges, the upper limits of the component (B) mass ratio are 0.2, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0. It may be 12, 0.11, or 0.1.

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

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

As a method for including component (C) in the composition containing (A) and (B), for example, a liquid composition containing component (C) is absorbed into the composition containing (A) and (B). method. Examples of the solvent for the component (C)-containing liquid composition include water, organic solvents (such as ethanol), and mixtures thereof, with water being particularly preferred. The liquid composition containing component (C) is preferably a composition containing a solvent and component (C), more preferably a composition containing only a solvent and component (C). In the liquid composition containing component (C), the solvent content is preferably 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. Moreover, the upper limit of the said range may be about 99, 98, 97, or 96 mass %. In the liquid composition containing component (C), 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 end of the range may be 1, 2, 3, or 4 wt%. Moreover, 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 component (C)-containing liquid composition may contain components other than the solvent and component (C). Examples of such components include surfactants, and nonionic surfactants are preferred. More specific examples include nonylphenol surfactants. The content of the surfactant in the liquid composition containing component (C) is, for example, 0.05 to 0.5% by mass, 0.06 to 0.4% by mass, and 0.07 to 0.3% by mass. % by mass, 0.08 to 0.2% by mass, or about 0.09 to 0.15% by mass.

When the liquid composition containing component (C) is absorbed into the composition containing (A) and (B), the composition containing (A) and (B) and the composition containing (A) and (B) The mass ratio of the liquid composition containing component (C) that the composition absorbs is preferably about 1:1 to 30, more preferably about 1:1 to 25, and more preferably about 1:1 to 20. It is more preferable that it is a degree. The upper mass limit 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 30 or so.

The present invention also includes embodiments in which compositions containing (A) and (B) are used, particularly for absorbing volatile substance-containing liquid compositions. That is, the present invention also includes a composition containing components (A) and (B) for absorbing a volatile substance-containing liquid composition. The present invention also provides a method for releasing volatile substances in a volatile substance-containing liquid composition into the atmosphere, comprising the step of allowing a composition containing (A) and (B) to absorb the volatile substance-containing liquid composition. It also includes methods of increasing persistence. Various conditions for these embodiments are similar to those described above.

In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Also, the various characteristics (property, structure, function, etc.) described for each of the embodiments of the invention described above may be combined in any way to identify subject matter encompassed by the invention. That is, the invention encompasses all subject matter consisting of any and all possible combinations of the features described herein.

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

[Evaluation method]
The water absorption capacity, water elution amount, and median diameter (when further pulverized after production) of the polyalkylene oxide-modified products described in the production examples below were measured according to the following methods.
(1) Water absorption capacity The water absorption capacity of the modified polyalkylene oxide was measured by the following method.

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

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

Water elution (mass%) = {(AC) / A} × 100
(3) Median diameter The median diameter was determined by a dry sieving method (JIS Z8815). Specifically, 50 g of the obtained sample is weighed, sieved using a JIS standard sieve (JIS Z8801), and then each sieve is weighed. I found the dimension.

Production Example I: Production of Modified Polyalkylene Oxide 100 parts by mass of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000 and 0.9 of 1,4-butanediol were placed in a storage tank A equipped with a stirrer kept at 80°C. Parts by mass and 0.1 part by mass of dioctyltin dilaurate were added and stirred in a nitrogen gas atmosphere to form a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was put into a storage tank B kept at 30° C. and stored under a nitrogen gas atmosphere.

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 to 110-140° C. using metering pumps. continuously supplied to a twin-screw extruder (R value = 1.00), mixed in the extruder to react, extruded strands from the extruder outlet, pelletized by a pelletizer, polyalkylene oxide modified product got The polyalkylene oxide-modified product pellets obtained in Production Example I were used as the polyalkylene oxide-modified product in the following examples.

The obtained polyalkylene oxide-modified product had a water absorption capacity of 25 g/g and a water elution content of 19% by mass.

Production Example II: Production of polyalkylene oxide-modified product An ethylene oxide/propylene oxide (mass ratio: 90/10) copolymer having a number average molecular weight of 15,000 was added at a rate of 250 g/min, and ethylene glycol heated to 40°C was added. At a rate of 2.1 g/min, both were supplied to a 40 mmφ single-screw extruder (L/D=40, set temperature: 90° C.) and 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 analyzed by HPLC to confirm that it was mixed at the charging ratio) was passed through a 30 mmφ twin-screw extruder (L/D = 41.0 mm). It was continuously supplied to the hopper mouth (set temperature: 80°C) of 5). At the same time, dioctyltin dilaurate was supplied to the hopper port of the twin-screw extruder at a rate of 0.5 g/min.

Furthermore, dicyclohexylmethane-4,4′-diisocyanate adjusted to 30° C. was also supplied at a rate of 12.4 g/min to the screw barrel portion located downstream of the hopper port of the twin-screw extruder (R value = 0.95) and reacted continuously under a nitrogen atmosphere (set temperature: 180°C). After cooling the strand obtained from the exit of the twin-screw extruder, it was pelletized by a pelletizer to obtain a modified polyalkylene oxide.

The obtained polyalkylene oxide-modified product had a water absorption capacity of 20 g/g and a water elution content of 15% by mass.

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

In addition, various fillers were purchased and used on the market. 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 is a value measured by a method described in JIS K5101-13-2:2004.
Filler (1): Organized smectite Sumecton SAN [manufactured by Kunimine Industries Co., Ltd.]
Filler (2): Organized smectite Sumecton STN [manufactured by Kunimine Industries Co., Ltd.]
Filler (3): Silica beads Nip Seal EL [manufactured by Tosoh Silica Corporation] (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) [manufactured by Hayashi Pure Chemical]

Examples 1-17
The compositions obtained in Production Examples 1 to 16 were cut into pellets of 4 mm square in length and width using a super straight cutter (manufactured by Dumbbell Co., Ltd. (model: SSK-1000S-D, punching dimension (L): 100 mm)). It was molded to obtain pellets of various compositions (longitudinal, transverse, thickness: 4 mm, 4 mm, 2 mm). These were used in Examples 1-16, respectively. Among these pellets, the pellets obtained from the composition obtained in Production Example 16 were immersed in liquid nitrogen and then pulverized to a median diameter of 60 μm to obtain a powder of the composition. This powder was used in Example 17.

1 g of the obtained pellets or powder of various compositions (number of pellets: about 20) is immersed in 10 g of volatile substance-containing liquid A, B, or C, and allowed to absorb for 24 hours. Only the surplus volatile substance-containing liquid that was not absorbed by the pellets or powder of the product was separated to obtain a pellet-shaped or powder-shaped liquid-absorbing composition (that is, a volatile substance-dispersing composition). (Examples 1-17). Table 5 summarizes the obtained various absorbent compositions.

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 are examples using volatile substance-containing liquid A, Examples 1b to 16b are examples using volatile substance-containing liquid B, and volatile substance-containing liquid C is used. The examples used are referred to as Examples 1c-16c. An example using the volatile substance-containing liquid A in Example 17 is referred to as Example 17a.

Among the liquid-absorbent 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 bottle, and then placed in a head space of 40 ° C. Analyze the amount of volatile components released from the liquid-absorbing composition by maintaining in the oven for 17 minutes and quantitatively analyzing the gas in the gas phase in the 25 mL vial by GC analysis (headspace method). did. In addition, of the absorbent composition obtained in Example 17, 0.1 g of the composition prepared by absorbing the volatile substance-containing liquid A was collected in a vial bottle, and the absorbent composition was prepared in the same manner. The amount of volatile components released from the material was analyzed.

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

Table 7 shows the area value (peak area value) of limonene detected from the liquid-absorbent composition that absorbed 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 release amount change over time of the volatile substance-containing liquid component, among various volatile components, almost all volatile components Since the released amount showed the same behavior (change in released amount) as limonene, limonene was selected and evaluated as a representative component. In addition, the area value is the corrected area value ("area value/substantial weight of 3 pellets" or "area value/powder The actual weight of the body (0.1 g)", ie the area value of limonene released per g of pellets or powder). Hereinafter, the area value of limonene released per 1 g of pellets or powder may be referred to as the limonene corrected area value.

Further, among the liquid-absorbing compositions obtained in Examples 1 to 17, pellets or powder of the composition prepared by absorbing the volatile substance-containing liquid A was placed in a blower dryer set at 40 ° C. 6 It was allowed to stand for hours or 12 hours to evaporate the absorbed volatile components. After that, 3 pellets of the liquid-absorbing composition were collected in a 25 mL vial and maintained in a head space oven at 40° C. for 17 minutes, and the gas in the gas phase in the 25 mL vial was analyzed by GC analysis (head The amount of evaporated volatile components was analyzed by quantitative analysis using the space method). Table 7 shows the limonene corrected 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 were corrected for limonene detected by GC analysis in the same manner as described above. Find the area value. Table 8 shows the results. In the composition prepared by absorbing the volatile substance-containing liquid B, similarly to the composition prepared by absorbing the volatile substance-containing liquid A, the amount of the volatile substance-containing liquid component released over time In the evaluation of the change, among the various volatile components, almost all of the volatile components released showed the same behavior (release amount change) as limonene, so limonene was selected as a representative component. and evaluated.

Further, among the absorbent compositions obtained in Examples 1 to 16, pellets of compositions prepared by absorbing the volatile substance-containing liquid C were subjected to GC analysis in the same manner as described above.
In addition, in the composition prepared by absorbing the volatile substance-containing liquid C, in the evaluation of the release amount change over time of the volatile substance-containing liquid component, almost all volatile components among various volatile components Z-9-tricosene was selected and evaluated as a representative component because the released amount of the component showed behavior (change in released amount) similar to that of Z-9-tricosene. In the same manner as the evaluation of the composition prepared by absorbing the volatile substance-containing liquid A, for the composition prepared by absorbing the volatile substance-containing liquid C, Z-9 released per 1 g of pellets - Tricosene area value (Z-9-trichosene corrected area value) was calculated. Table 9 shows the results.

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

In addition, the pellets of the liquid-absorbing modified polyalkylene oxide were placed in a blower dryer set at 40° C., and the absorbed hydrophobic components were allowed to stand for 6 hours or 12 hours to evaporate the absorbed volatile components. After that, three pellets of the liquid-absorbing polyalkylene oxide-modified product 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. The amount of evaporated volatile components was analyzed by quantitative analysis by analysis (headspace method).

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

Table 11 shows the Z-9-tricosene corrected area value detected by GC analysis from the polyalkylene oxide-modified material that absorbed the volatile substance-containing liquid C.

Claims (8)

(A) a modified polyalkylene oxide obtained by reacting a polyalkylene oxide compound having a number average molecular weight of 5,000 to 50,000 , a diol compound, and a diisocyanate compound;
(B) a filler; and (C) a volatile substance-dissipating composition (excluding a composition whose surface is coated with silica) . 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. 2. The volatile substance-dissipating composition according to claim 1, comprising at least one selected from the group consisting of copolymers. The diol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3. The volatile substance-dissipating composition according to claim 1, comprising at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol. The diisocyanate compound is 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 3-isocyanatomethyl-3, 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 volatile substance dissipation according to any one of claims 1 to 3. (B) 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, any one of claims 1 to 4. The composition for volatile substance dissipation according to 1. (C) The volatile substance dispersing material according to any one of claims 1 to 5, wherein the volatile substance is one or more selected from the group consisting of fragrances, pest or pest pheromones, and pesticides. Composition. A composition containing the following components (A) and (B) for absorbing a volatile substance-containing liquid composition (excluding a composition whose surface is coated with silica) .
(A) Modified polyalkylene oxide obtained by reacting a polyalkylene oxide compound having a number average molecular weight of 5000 to 50000 , a diol compound, and a diisocyanate compound (B) Filler comprising the step of allowing a composition containing the following components (A) and (B) (excluding compositions whose surface is coated with silica) to absorb a volatile substance-containing liquid composition: A method for increasing the sustained release of volatile substances into the atmosphere in a substance-blended liquid composition.
(A) Modified polyalkylene oxide obtained by reacting a polyalkylene oxide compound having a number average molecular weight of 5000 to 50000 , a diol compound, and a diisocyanate compound (B) Filler