JP2015117368A - Foam for organic solvent absorption - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic solvent absorber which is not bulky during storage, has a high absorption capacity per volume, and is easy to recover after absorption.SOLUTION: Provided is a foam forming composition for organic solvent absorption comprising: a polyether polyol containing a polyether diol having a functional group number of 2 and a hydroxyl value of 25 to 100 mgKOH/g and a polyether polyol having a functional group number of 3 to 8 and a hydroxyl value of 25 to 500 mgKOH/g; a polyisocyanate; a foaming agent; a foam stabilizer; and a catalyst. Also provided are a foam for organic solvent absorption obtained by reacting the composition; and a foam molding for organic solvent absorption obtained by fabricating the foam.

Description

  The present invention relates to an organic solvent absorbing foam.

  Conventionally, as organic solvent absorbents, nonwoven fabrics made of short fibers of polypropylene resin (for example, see Patent Document 1) and absorbent resins made of acrylic resin (for example, see Patent Document 2) are known.

US Pat. No. 6,586,073 JP 2003-251178 A

However, the solvent absorbent described in Patent Document 1 can absorb the solvent between the short fibers of the polypropylene resin by a capillary phenomenon, but the outer dimensions of the nonwoven fabric do not change. For example, a solvent storage tank or a solvent is used. When the solvent leaks from the reaction vessel, the solvent is absorbed and recovered, but the dimensions of the absorbent material do not change, so it is bulky in the storage area until it leaks, or is enclosed in a storage battery cell in a non-aqueous storage battery system When the non-aqueous electrolyte leaks due to an accident or disaster, we want to reduce the volume of the solvent absorbent in the non-aqueous storage battery system, but the outer dimensions of the non-aqueous storage battery system are designed to ensure the absorption by the solvent absorbent. There was a problem of getting bigger.
Further, the onium salt of the acrylic resin described in Patent Document 2 is in the form of particles and absorbs the solvent and expands several tens to several hundreds times, but there is a problem that recovery after absorption is difficult.
That is, an object of the present invention is to provide an organic solvent absorbent that is not bulky during storage, has a large amount of absorption per volume, and is easy to recover after absorption.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a polyether diol (A1) having a hydroxyl value of 25 to 100 mgKOH / g having 2 functional groups and a polyether polyol (A2) having a hydroxyl value of 25 to 500 mgKOH / g having 3 to 8 functional groups. ) -Containing polyether polyol (A), polyisocyanate (B), foaming agent (C), foam stabilizer (D) and catalyst (E). P); organic solvent absorbing foam (Q) formed by reacting the composition; organic solvent absorbing foam molded body (R) formed by molding the foam.

The foam-forming composition for absorbing an organic solvent of the present invention has the following effects.
(1) The organic solvent absorbent foam molded body obtained by reacting the composition has a large amount of absorption per volume because the organic solvent absorbent is not bulky during storage.
(2) Since the organic solvent-absorbing foam molded body can maintain the shape after absorption, it can be easily recovered after absorption of the organic solvent.

[Polyetherdiol (A1)]
The polyether diol (A1) in the present invention is a polyol having a hydroxyl number of 25 to 100 mgKOH / g (only numerical values may be shown below) having 2 functional groups, and the hydroxyl value is preferably 30 to 90. More preferably, it is 40-80. If the hydroxyl value is less than 25 mgKOH / g, the organic solvent absorbing foam molded article cannot be maintained when it is lifted after absorbing the organic solvent, and the absorbed organic solvent starts dripping. The body becomes hard and cracks and breaks occur during recovery.
In the present invention, the organic solvent may be abbreviated as a solvent.

  As the polyether diol (A1), the following (a1) low molecular weight diol having a molecular weight of 60 to 400, (a2) divalent phenol, and alkylamine having 1 to 20 carbon atoms (n-butylamine, octylamine, etc.) And an alkylene oxide (hereinafter referred to as AO) added thereto. AO has 2 to 12 carbon atoms, such as ethylene oxide (hereinafter referred to as EO), 1,2-propylene oxide (hereinafter referred to as PO), 1,3-propylene oxide, 1,2-, 1,3-. And 2,3-butylene oxide (hereinafter referred to as BO), tetrahydrofuran (THF), substituted AO [epoxidized product of α-olefin having 5 to 12 carbon atoms, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin, etc.), etc. Preferred is EO, PO, and a combination thereof, and when AO is used in combination, the combination may be a block addition, a random addition, or a combination thereof.

(A1) Low molecular diol 2 to 20 or more dihydric alcohol having carbon number (hereinafter abbreviated as C), for example, aliphatic dihydric alcohol having 2 to 12 carbon atoms [(di) alkylene glycol, For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentane Diol, dodecanediol, etc.], alicyclic divalent alcohols having 6 to 10 carbon atoms [1,4-cyclohexanediol, cyclohexanedimethanol, etc.] and the like.

(A2) Divalent phenols C6-18 divalent phenols such as monocyclic divalent phenols (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenols (bisphenol A, -F, -C, -B, -AD) And -S, dihydroxybiphenyl, 4,4′-dihydroxydiphenyl-2,2-butane, etc.), and condensed polycyclic dihydric phenols [dihydroxynaphthalene (1,5-dihydroxynaphthalene, etc.), binaphthol, etc.] and the like.

Of these, from the viewpoint of maintaining the shape of the foam molded product for absorbing an organic solvent after absorbing the solvent, the low molecular diol described in (a1) is preferably added with AO, more preferably an aliphatic dihydric alcohol. To which AO is added.
The above (A1) may be used alone or in combination of two or more.

[Polyether polyol (A2)]
The polyether polyol (A2) in the present invention is a polyol having a functional group number of 3 to 8 and a hydroxyl value of 25 to 500 mgKOH / g (only numerical values may be shown below), and the hydroxyl value is preferably 30. ˜450, more preferably 35˜400. If the hydroxyl value is less than 25 mg KOH / g, the organic solvent absorbing foam molded body cannot maintain its shape when it is lifted after absorbing the solvent, and the absorbed solvent drips, and if it exceeds 500 mg KOH / g, the organic solvent absorbing foam molded body is Hardens and cracks and breaks during collection.

  Examples of the polyether polyol (A2) include those obtained by adding AO to (a3) a low molecular polyol, (a4) a polyhydric phenol, and (a5) a low molecular amine having a molecular weight of 60 to 400 described below. Examples of AO include AO described in polyether diol (A1). Preference is given to EO, PO and combinations thereof. When AO is used in combination, the combination form may be block addition, random addition, or a combination thereof.

(A3) Low molecular polyols Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol , 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and derivatives thereof such as sucrose, glucose, fructose, mannose, lactose, and glycosides (methyl Glucoside, etc.)] and the like.

(A4) Polyhydric phenols Trivalent to octavalent or higher polyhydric phenols such as monocyclic polyphenols (pyrogallol, phloroglucinol, and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) Aldehyde or ketone (formaldehyde, glutaraldehyde, glyoxal, acetone) low condensate (phenol or cresol novolac resin, intermediate of resole, polyphenol obtained by condensation reaction of phenol and glyoxal or glutaraldehyde, and condensation of resorcin with acetone Polyphenol obtained by reaction) and the like.

(A5) Low molecular amine Ammonia; Aliphatic mono- or polyamine having 2 to 20 carbon atoms [alkanolamine having 2 to 20 carbon atoms (mono-, di- and triethanolamine, isopropanolamine, etc.), 2 to 6 carbon atoms Alkylene diamine (ethylene diamine, propylene diamine, hexamethylene diamine, etc.), polyalkylene polyamine having 4 to 20 carbon atoms (dialkylene triamine to hexaalkylene heptamine having 2 to 6 carbon atoms in the alkylene group, for example, diethylene triamine and triethylene tetramine) )]; Aromatic mono- or polyamines having 6 to 20 carbon atoms (phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, diphenyletherdiamine, etc.), alicyclic rings having 4 to 20 carbon atoms Containing mono- or polyamines (cyclohexylamine, isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine, etc.), C4-C20 heterocycle-containing amines (piperazine, aminoethylpiperazine, etc.) and the like.

Among these, from the viewpoint of maintaining the shape of the foamed product for organic solvent absorption after solvent absorption, preferably, the low molecular polyol described in (a3) is added with AO, more preferably sucrose and glycerin. AO is added.
The above (A2) may be used alone or in combination of two or more.

[Polyether polyol (A)]
The polyether polyol (A) in the present invention contains the polyether diol (A1) and the polyether polyol (A2).
The content of (A1) based on the polyether polyol (A) is preferably 50 to 99% by weight, more preferably based on (A), from the viewpoint of maintaining the shape of the foamed product for organic solvent absorption after absorbing the solvent. Is 55 to 95% by weight, particularly preferably 60 to 90% by weight. If the amount is less than 50% by weight, the shape of the foamed product for absorbing an organic solvent after solvent absorption tends to collapse, and if it exceeds 99% by weight, the shape of the foamed product for absorbing organic solvent dissolves in the solvent after absorbing the solvent and the shape tends to disappear. become.

[Polyisocyanate (B)]
Examples of the polyisocyanate (B) in the present invention include aromatic polyisocyanates (hereinafter referred to as PI), aliphatic PIs, alicyclic PIs, araliphatic PIs, and modified products of these PIs.

  The aromatic PI includes 6 to 20 carbon atoms (excluding carbon in the NCO group, hereinafter abbreviated as C), such as diisocyanate (hereinafter abbreviated as DI) [1,3- and / or 1,4-phenylene DI, 2 , 4- and / or 2,6-tolylene DI (TDI), 4,4′- and / or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4 ′ -Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1,5-naphthylene DI]; trifunctional The above-mentioned PI (triisocyanate etc.) [crude TDI, crude MDI (polymethylene polyphenyl polyisocyanate) etc.] can be mentioned.

  Aliphatic PIs include C2-18, such as DI [ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or Or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate and bis (2- Isocyanatoethyl) carbonate]; trifunctional or higher functional PI (triisocyanate and the like) [1,6,11 1-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylenetri Isocyanates and lysine esters triisocyanate (Phosgenated product of reaction product of lysine and alkanolamine), 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-di Isocyanatohexanoate etc.].

As alicyclic PI, C4-15, for example, DI [isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanato] Ethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI etc.];
Trifunctional or higher functional PI (triisocyanate etc.) [bicycloheptane triisocyanate etc.] can be mentioned.

  The araliphatic PI includes C8-15, such as m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ', α'-tetramethylxylylene DI (TMXDI).

  Examples of modified products of PI include modified products having a carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione group), such as urethane-modified products such as MDI, TDI, HDI and IPDI (described above). NCO-terminated urethane prepolymers obtained by reacting an excess of PI with a polyether polyol, etc.), biuret modified products, isocyanurate modified products, trihydrocarbyl phosphate modified products, and mixtures thereof.

Among these, preferred are C6-15 aromatic polyisocyanates from the viewpoint of maintaining the shape of the solvent-absorbing foam molded article after solvent absorption, and particularly preferred are crude MDI, TDI, and mixtures thereof. .
The above (B) may be used alone or in combination of two or more.

  The weight ratio [(A) / (B)] of the polyether polyol (A) and the polyisocyanate (B) is preferably 50/50 to 90/10 from the viewpoint of moldability of the organic solvent absorbing foam.

[Foaming agent (C)]
As the foaming agent (C) in the present invention, a known foaming agent can be used, and examples thereof include water, hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons, and liquefied carbon dioxide gas. May be. Specific examples of the hydrogen atom-containing halogenated hydrocarbon include methylene chloride, HCFC (hydrochlorofluorocarbon) (for example, HCFC-123 and HCFC-141b); HFC (hydrofluorocarbon) (for example, HFC-245fa and HFC-365mfc), etc. Is mentioned.
The low boiling point hydrocarbon is a hydrocarbon having a boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, and cyclopentane.
When (C) is water, the use amount of (C) is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight, and (C) is based on (A). In the case of a hydrogen atom-containing halogenated hydrocarbon or low boiling point hydrocarbon, it is preferably 10% by weight or less, more preferably 5% by weight or less.

[Foam stabilizer (D)]
As the foam stabilizer (D) in the present invention, a silicon foam stabilizer (for example, dimethylpolysiloxane, non-reacted in which main chain and / or side chain and / or terminal is modified with polyoxyalkylene, phenyl, alkyl, aralkyl, etc. Dimethyl siloxane).
The amount of (D) used is preferably 0.5 to 3% by weight, more preferably 0.8 to 2% by weight, based on (A).

[Catalyst (E)]
As the catalyst (E) in the present invention, all usual catalysts for promoting the urethanization reaction can be used. Examples include triethylenediamine, bis (N, N-dimethylamino-2-ethyl) ether, N, N, N ', N'-tetramethylhexamethylenediamine, diazabicycloalkene [for example, 1,8-diazabicyclo [5,4,0] undecene-7 or 1,5-diazabicyclo [4,3,0] nonene-5, etc. Tertiary amines and aliphatic carboxylic acids (monocarboxylic acids such as formic acid, acetic acid and octylic acid, polycarboxylic acids such as succinic acid and adipic acid), aromatic carboxylic acids (monocarboxylic acids such as benzoic acid, phthalic acid) , Polycarboxylic acids such as trimellitic acid), phenols (phenol, catechol, etc.), sulfonic acids (p-toluenesulfonic acid, methanesulfuric acid) Acid, etc.) and inorganic acids (carbonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc.)]], potassium acetate, potassium octylate, stannous octylate, dibutylstannic dilaurate, lead octylate And organometallic compounds such as bismuth octylate.
The use amount (pure content) of the catalyst (E) is preferably 0.1 to 0.5% by weight, more preferably 0.15 to 0.3% by weight based on the above (A).

[Organic solvent absorbing foam-forming composition (P)]
The foam-forming composition (P) for absorbing an organic solvent of the present invention contains the polyether polyol (A), polyisocyanate (B), foaming agent (C), foam stabilizer (D) and catalyst (E). Do it.

The (P) may further contain a chain extender (F) and / or a crosslinking agent (G) for the purpose of increasing the strength of the molded product after absorbing the solvent.
The chain extender (F) is (a1) to (a2) having the above-described molecular weight of 60 to 400, and the crosslinking agent (G) is (a3) to (a5) having the above-described molecular weight of 60 to 400. .
The total content of the chain extender (F) and the crosslinking agent (G) is preferably 0.1 to 5% by weight, more preferably 0.5 to 3 based on the total weight of (A) and (B). % By weight.

The (P) may further contain monool (H) for the purpose of increasing the solvent absorption of the molded product.
Monools (H) include aliphatic monools having 1 to 8 carbon atoms [linear monools (methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, stearyl alcohol, etc.) and monomers having a branched chain. All (isopropyl alcohol, neopentyl alcohol, 3-methyl-pentanol and 2-ethylhexanol)]; monools having a cyclic group having 6 to 12 carbon atoms [alicyclic group-containing monools (cyclohexanol, etc.) and C7-12 aromatic ring-containing monool (such as benzyl alcohol and naphthylethanol)] and their AO.
The total content of monool (H) is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of (A) and (B).

The (P) may further contain a polyol (I) other than the polyether polyol (A) for the purpose of increasing the strength of the molded product after absorbing the solvent.
Examples of the polyol (I) include polyester polyol and polycarbonate polyol.
The total content of polyol (I) is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of (A) and (B).

The organic solvent-absorbing foam-forming composition (P) of the present invention may further contain additives (J) in order to improve the moldability and other functions of the molded body, as necessary within the range not impairing the effects of the present invention. ) May be contained. The total content of the additive (J) is usually 10% by weight or less, preferably 0.5 to 8% by weight, based on the total weight of (A) and (B).
Examples of such (J) include colorants (metal oxides, disazo pigments, etc.), antioxidants (nickel dibutyldithiocarbamate, hindered phenols, etc.), lubricants (calcium stearate, ethylenediamine distearylamide, etc.), light stability Agent [ultraviolet absorber [benzophenone (2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.)], quencher [nickel chelate, etc.], salicylic acid [phenyl salicylate, etc.], radical scavenging Agent [hindered amine type ((bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc.)], flame retardant [nitrogen-containing flame retardant (urea compound, guanidine compound, etc.), sulfur-containing flame retardant (sulfate ester) , Sulfamic acid, etc.), phosphorus-containing flame retardants (phosphoric acid, phosphine) Etc.)], antibacterial agents [antibacterial zeolite compounds, quaternary ammonium salts (didecyldimethylammonium chloride, etc.), organic iodine antibacterial agents (4-chlorophenyl-3-iodopropargyl formal, 3-iodo-2 -Propenyl butyl carbamate, etc.), organic nitrogen-sulfur antibacterial agents (benzothiazole, 2,4-thiazolylbenzimidazole, etc.)], antistatic agents [anionic surfactants [phosphate ester salts (eg, polyoxyalkylene, etc.) Compound monophosphate esters, diphosphate esters, etc.), alkylbenzene sulfonates, etc.], cationic surfactants, nonionic surfactants, etc.], plasticizers (dibutyl phthalate, di-2-ethylhexyl adipate, etc.) One or more selected from these may be added.

[Organic solvent absorption foam (Q)]
The organic solvent absorbing foam of the present invention is obtained by reacting the composition (P). The ratio of the polyol (A) and the polyisocyanate (B) can be varied, but the isocyanate index [[equivalent of NCO group of (B) / equivalent of active hydrogen of (A)] × 100] From the viewpoint of maintaining the shape of the foam molded product after solvent absorption, it is preferably 80 to 120, more preferably 85 to 115, and particularly preferably 90 to 110.
In addition, when the composition (P) contains a chain extender (F) and / or a crosslinking agent (G), the isocyanate index is represented by the following formula.

Isocyanate index = 100 × [[equivalent of NCO group of (B)]
/ [Equivalent of total active hydrogen of (A), (F) and (G)]]

  Although it does not specifically limit as a manufacturing method of said (Q), For example, a polyol (A), polyisocyanate (B), a foaming agent (C), a foam stabilizer (D), and a catalyst (E) are mixed and mixed. A method of obtaining (Q) by obtaining a liquid and reacting and curing by heating (for example, at 70 to 130 ° C. for 0.5 to 10 hours) may be mentioned.

[Organic solvent absorbing foam molding (R)]
The organic solvent absorbing foam molded article (R) of the present invention comprises the organic solvent absorbing foam (Q). That is, the molded body (R) is obtained by subjecting the foam (Q) to processing such as cutting, cutting, punching, and hot pressing as necessary. The organic solvent-absorbing foam-forming composition (P) is cast into a mold or a resin mold and reacted and cured to obtain an organic solvent-absorbing foam (Q), which is formed into a molded body (R). It is good. When casting into a mold, a resin mold, or the like, streaks, protrusions, holes, and the like can be imparted by applying a specific shape to the mold, the resin mold, or the like. Furthermore, you may have the surface (skin layer) which a metal mold | die, a resin mold | die, etc. are contacting. Although it does not limit about the shape of this molded object (R), It can select according to places to use, such as a sheet form, a rectangular shape, and a column shape.

The density of the organic solvent-absorbing foam (Q) and the organic solvent-absorbing foam molded body (R) is preferably 100 to 400 kg / m ³ , more preferably from the viewpoint of liquid dripping and absorption rate when lifted after absorption. 150-350 kg / m ³ . If it is 100 kg / m ³ or less, there is a tendency for liquid dripping when it is lifted after absorption, and if it is 400 kg / m ³ or more, the rate of absorbing the solvent tends to be slow.

Although it will not specifically limit if it is an organic solvent as an organic solvent in this invention, For example, C5-C18 hydrocarbon solvent (For example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i -Heptane, n-octane, i-octane, cyclohexane, methylcyclohexane, etc.), C6-C12 aromatic hydrocarbon solvents (for example, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc.), C1-C8 monoalcohol ( For example, methanol, ethanol, n-propanol, i-propanol, benzyl alcohol, etc.), C3-C9 ketone solvents (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), C2-C10 ester solvents (for example, methyl formate, Methyl acetate, ethyl acetate, butyrate , Γ-butyrolactone, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.)], C4 to C10 ether solvents (diethyl ether, THF, dioxane, etc.)], C3 to C4 amide solvents (dimethylformamide, dimethylacetamide, etc.) Dimethyl sulfoxide, ionic liquid (for example, imidazolium salt, pyridinium salt, aliphatic quaternary ammonium salt, etc.) and a mixture of two or more of the above organic solvents.
In addition, a non-aqueous electrolyte solution containing an electrolyte contained in a non-aqueous secondary battery cell (for example, LiBF ₄ , LiPF ₆ , LiClO ₄ , etc. in a solvent such as γ-butyrolactone, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.) Dissolved electrolyte solution), polymer solution (for example, solution of ethyl acetate, toluene, etc. containing acrylic resin, polyester resin, etc.), solution and suspension of the above organic solvent containing water are also organic in the present invention. Included as solvent.
In particular, the organic solvent-absorbing foam molded article (R) is useful for absorbing a nonaqueous electrolytic solution.

[Forming molded article for organic solvent absorption (X)]
The organic solvent-absorbing foam molded article (X) of the present invention is obtained by fixing or adhering the organic solvent-absorbing foam molded body (R) to a sheet, tray, or cup made of, for example, a resin (polyethylene, polypropylene, etc.) It can be used as a foam molded article (X) for absorbing an organic solvent that can be absorbed and recovered.
The shape of the sheet, tray, or cup is not particularly limited. The method for fixing or bonding the molded body (R) to the resin is not particularly limited. For example, as a method for fixing, the tray and the molded body (R) are made of resin (polyethylene, polypropylene, etc.) yarn. As a method of adhering, a double-sided tape is applied to a sheet or the like, or an adhesive (for example, an adhesive made of a solvent solution of synthetic rubber, 2 liquid urethane, and the like) For example, an epoxy-curing adhesive or the like may be applied and then the organic solvent-absorbing foam molded product (R) may be attached. Moreover, as a method of fixing, even if there is no material to fix, when the size of the hole of the cup and the molded body (R) are the same size or (R) is large, it can be inserted into the cup or pushed in.
The non-aqueous secondary battery of the present invention is a non-aqueous secondary battery comprising the organic solvent-absorbing foam molded article (R) and / or the organic solvent-absorbing foam molded article (X). That is, the non-aqueous secondary battery includes one or a plurality of non-aqueous secondary battery cells, and the non-aqueous secondary battery cell includes a molded body (R) and / or a molded article (X). And when electrolyte solution leaks in a non-aqueous secondary battery cell, it can prevent that electrolyte solution leaks out of a non-aqueous secondary battery by absorbing electrolyte solution rapidly.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. In addition, the part in an Example represents a weight part and% represents weight%.

  The compositions, symbols, etc. of the raw materials used in Examples and Comparative Examples described in Tables 1 and 2 are as follows. The number average molecular weight was abbreviated as Mn.

[Polyetherdiol (A1)]
Polyether diol (a1-1):
Propylene glycol PO adduct [number of functional groups 2, hydroxyl value 37 mgKOH / g,
Mn 3,000]
Polyether diol (a1-2):
Propylene glycol PO adduct [number of functional groups 2, hydroxyl value 56 mgKOH / g,
Mn2,000]
Polyether diol (a1-3):
PO adduct of bisphenol A [functional group number 2, hydroxyl value 280 mgKOH / g,
Mn400]
Polyether diol (a1-4):
Copolymer of random addition of PO and EO to propylene glycol [number of functional groups: 2,
Hydroxyl value 56 mg KOH / g, Mn 4,000], EO content = 80%]

[Polyether polyol (A2)]
Polyether polyol (a2-1):
Mixture of sucrose PO adduct and glycerin PO adduct [functional group number 6.7,
Hydroxyl value 450 mgKOH / g, Mn835]
Polyether polyol (a2-2):
Copolymer having EO added to the terminal of PO adduct of glycerin [functional group number 3,
Hydroxyl value 33 mg KOH / g, Mn 5,100]
Polyether polyol (a2-3):
PO addition product of glycerin [number of functional groups 3, hydroxyl value 400 mgKOH / g, Mn420]

[Polyisocyanate (B)]
Polyisocyanate (b-1):
Product name “Millionate MR-200”, manufactured by Nippon Polyurethane Industry Co., Ltd., crude MDI,
NCO% 31.3
Polyisocyanate (b-2):
Product name “Coronate T-80”, manufactured by Nippon Polyurethane Industry Co., Ltd., TDI

[Foaming agent (C)]
Foaming agent (c-1): water [foam stabilizer (D)]
Foam stabilizer (d-1): trade name “SZ-1671”,
Toray Dow Corning Co., Ltd., silicone foam stabilizer foam stabilizer (d-2): trade name “SZ-1642”,
Silicone foam stabilizer manufactured by Toray Dow Corning Co., Ltd.

[Catalyst (E)]
Catalyst (e-1):
Product name "Neostan U-28", manufactured by Nitto Kasei Corporation,
(2-Ethylhexanoic acid) stannous acid catalyst (e-2):
Product name “Neostan U-600”, Nitto Kasei Co., Ltd.,
Tris (2-ethylhexanoic acid) bismuth (content: 55-58 wt%) 2-ethylhexanoic acid solution catalyst (e-3):
Product name “TOYOCAT ET”, manufactured by Tosoh Corporation,
70% dipropylene glycol solution of bis (dimethylaminoethyl) ether

[Chain extender (F)]
Chain extender (f-1): ethylene glycol [crosslinking agent (G)]
Crosslinker (g-1): Triethanolamine Crosslinker (g-2): Diethanolamine

[Electrolyte]
Ethylene carbonate, diethyl carbonate, and dimethyl carbonate are mixed at a weight ratio of 1: 1: 1, and LiPF ₆ is dissolved at a concentration of 1.2 mol / L in the obtained mixed solvent. Further, as an additive to the mixed solvent. An electrolyte was prepared by adding 0.5% vinylene carbonate. This electrolytic solution was used for evaluation of a foam molded body for absorbing an organic solvent described later.

Examples 1 to 8 <Organic solvent absorbing foam molded article>
In the formulation shown in Table 1, polyol ether diol (a1-1) to crosslinking agent (g-2) were stirred and mixed at 25 ° C. Further, after adding polyisocyanate (b-1) to (b-2) and stirring and mixing with a homomixer to obtain a foam-forming composition for absorbing an organic solvent, the gold of 100 mm in length × 100 mm in width × 100 mm in height The resultant was poured into a mold and foamed and cured for 10 minutes at a mold temperature of 60 ° C. to obtain organic solvent-absorbing foam molded bodies (R-1) to (R-8). The evaluation results are shown in Table 2.

Comparative Examples 1-3
It carried out similarly to Examples 1-8 by the prescription of Table 1, and obtained the foam molded object for organic solvent absorption (ratio R-1)-(ratio R-3). The evaluation results are shown in Table 2.

<Test method>
The measurement method for each item is as follows.
(1) Density:
Conforms to JIS K7222, unit is g / cm ³ .
(2) Solvent absorption rate and dripping solvent rate:
What cut each compact | molding | casting into the magnitude | size of 50x50x5 mm was used as the test piece, and was weighed [W1 (g)]. 200 ml of the solvent was placed in a 100 × 100 × 50 mm metal container, and the test piece measured for the weight before absorbing the solvent was placed on the liquid surface of the solvent so that the 50 × 50 mm surface was up. After 10 minutes, pick up and lift one corner of the 50 × 50 mm surface of the test piece that has absorbed the solvent with tweezers so that the diagonal of the picked corner is at the bottom and 30 seconds so that the test piece does not attach underneath. The solvent dripping down was collected and weighed [W2 (g)]. Moreover, the test piece after dripping was also weighed [W3 (g)].
In this test, each solvent of methanol, toluene, ethyl methyl ketone, N, N-dimethylformamide, and the above [electrolytic solution] was evaluated.
The solvent absorption rate (%) and the dripping solvent rate (%) were calculated by the following formulas.

[Solvent Absorption Rate (%)] = [(W2) + (W3) − (W1)] × 100 / (W1)

[Liquid dripping solvent ratio (%)] = (W2) × 100 / [(W2) + (W3) − (W1)]

(3) Foam shape maintenance test:
The 50 × 50 mm surface of the test piece for which the solvent absorption rate was measured was folded in half from the middle, and when it was returned, it was evaluated as “good”, and when cracked or broken, it was evaluated as “x”.

In Table 2, the foam moldings obtained from the organic solvent-absorbing foam-forming compositions (P) of Examples 1 to 8 have a sufficient solvent absorption rate as the organic solvent-absorbing foam, and the liquid when lifted up. Since the amount of dripping solvent was small enough and the foam shape was maintained when it was bent, it was easy to recover the foam after absorbing the solvent.
Compared with this, although the solvent absorption rate was large in the comparative example 1, since the amount of solvent absorption decreased by dripping, it was not satisfactory as a foam for organic solvent absorption. Further, in Comparative Examples 2 to 3, the solvent absorption rate is sufficient as a foam for absorbing organic solvents, and the amount of solvent dripping when lifted is sufficiently small, but the shape of the foam collapses when folded, so after solvent absorption Recovery of the foam was not easy, and it was not satisfactory as a solvent-absorbing foam.

  The foamed product for absorbing an organic solvent of the present invention is extremely useful because it can be widely used as a solvent absorbent used when an organic solvent spills on a floor or a desk, a tool for preventing solvent leakage in an accident or disaster, and the like. In particular, the non-aqueous secondary battery provided with the foamed article for absorbing an organic solvent of the present invention is useful because it is extremely safe even when the non-aqueous electrolyte leaks.

Claims (9)

  Polyether containing a polyether diol (A1) having a hydroxyl number of 25 to 100 mgKOH / g having 2 functional groups and a polyether polyol (A2) having a hydroxyl value of 25 to 500 mgKOH / g having 3 to 8 functional groups A foam-forming composition (P) for absorbing an organic solvent comprising an ether polyol (A), a polyisocyanate (B), a foaming agent (C), a foam stabilizer (D) and a catalyst (E).   The foam-forming composition for absorbing an organic solvent according to claim 1, further comprising a chain extender (F) and / or a crosslinking agent (G).   The foam-forming composition for absorbing an organic solvent according to claim 1 or 2, wherein the content of (A1) based on the polyether polyol (A) is 50 to 99% by weight.   The foam-forming composition for absorbing an organic solvent according to any one of claims 1 to 3, wherein the polyether polyol (A2) is an alkylene oxide adduct of sucrose and / or glycerin.   The foam for organic solvent absorption (Q) formed by making the foam-forming composition for organic solvent absorption in any one of Claims 1-4 react.   An organic solvent absorbing foam molded body (R) obtained by molding the organic solvent absorbing foam (Q) according to claim 5.   The organic solvent absorbing foam molded article according to claim 6, wherein the organic solvent to be absorbed is a non-aqueous electrolyte.   An organic solvent-absorbing foam molded article (X) obtained by fixing or adhering the organic solvent-absorbing foam molded body according to claim 6 or 7 to a sheet, tray or cup.   A non-aqueous secondary battery comprising the foam molded article for organic solvent absorption (R) according to claim 6 or 7, or the foam molded article for organic solvent absorption (X) according to claim 8.