JP2688815B2 - Synthetic resin foam with excellent deodorizing effect - Google Patents

Description

TECHNICAL FIELD The present invention relates to a synthetic resin foam having an excellent deodorizing effect. (Prior Art) Conventionally, a deodorant composed of a combination of an iron (II) compound and an organic acid such as L-ascorbic acid, ethylenediaminetetraacetic acid, and myoban has been known. This deodorant is usually
It is used in the form of an aqueous solution, and when it is used in a solid state, its ability can be exhibited by using it together with a porous filler such as activated carbon and a water absorbing substance. However, unless the water-absorbing substance is properly mixed and mixed, the iron (II) compound and the acidic substance cannot form a chelate well. Therefore, it is necessary to control the water content sufficient for the reaction of these compounds, but the water content cannot be sufficiently controlled only by mixing the above-mentioned formulation. Examples of the water-absorbing substance include hydrophilic polymer substances and deliquescent substances, but when these are mixed with a deodorizing agent, if they absorb water to a position where the deodorizing effect can be sufficiently exerted, they will be deodorized. The whole agent system gets wet with water and leaks out of the bag in use and contaminates the outside. Further, in the system of iron (II) compound and L-ascorbic acid described in JP-A-59-132937 and JP-A-61-106161,
It also has a drawback that the deodorant discolors after absorbing a malodorous substance and contaminates the outside. Furthermore, as mentioned above, iron (II)
Aqueous solutions, powders and the like are known as the usages of compound type deodorants, but no specific usages as molded articles are known at all. (Problems to be Solved by the Invention) An object of the present invention is to constantly provide water capable of sufficiently exerting the effect of the deodorant, and also in that case, the deodorant dissolves with this water. It is to provide a synthetic resin foam having an excellent deodorizing effect. Another object of the present invention is to provide a synthetic resin foam which has an excellent deodorizing action with an extremely fast deodorizing rate. Another object of the present invention is to provide a synthetic resin foam having an excellent deodorizing effect, which does not elute or discolor the deodorant and does not contaminate the outside. (Means for Solving Problems) The present invention is an iron (II) compound (excluding iron phthalocyanine).
A synthetic resin foam having a deodorizing effect in which a system deodorant is integrated with a synthetic resin foam, wherein an iron (II) compound deodorant is attached to the synthetic resin foam using a nonionic emulsion And a synthetic resin foam having an excellent deodorizing effect. As the synthetic resin foam in the present invention, various resin foams such as polyethylene, polypropylene, polyvinyl chloride, urea resin, polystyrene, ABS resin, polyurethane, ethylene-vinyl alcohol copolymer, polyester resin, and acrylic resin may be used. However, a polyurethane foam having a strong polarity is preferable from the viewpoint of the retention of deposits. The apparent specific gravity of this foam is preferably 0.008 due to the stability of the processing step and the size of the deodorant adhering surface area.
~ 0.1, more preferably 0.01-0.03. As the nonionic emulsion, various kinds can be used, and examples thereof include vinyl acetate-based, acrylic-based, urethane-based and polyester-based emulsions. Among them, considering the adhesiveness to the foam, it is desirable to use an emulsion of the same quality as that of the foam. For example, when a polyurethane foam is used, it is desirable to use a polyurethane emulsion. Further, the emulsion may be a usual emulsion, but preferably a self-emulsifying type. The reason is that the self-emulsifying type contains a hydrophilic part in the molecule, and when the iron (II) compound deodorant is attached to the foam by the polymer component in this emulsion, a malodorous substance is generated. Since it is a hydrophilic substance such as ammonia, mercaptan, hydrogen sulfide, various amines, etc., the incorporation rate into the polyurethane resin containing the iron (II) compound deodorizing agent is non-emulsified by using a surfactant or the like. This is because it is larger than that of the self-emulsifying emulsion. As an example of the nonionic emulsion of the present invention, a polyurethane emulsion will be described as an example. The polyurethane emulsion contains a hydrophilic polyol, a hydrophobic polyol, a diisocyanate as a resin component, and optionally a chain extender. Contains. As the hydrophilic polyol, polyethylene glycol, polyvinyl alcohol, polysiloxane, vinyl acetate copolymer and the like can be used. As the hydrophobic polyol, polyester polyol, polyether polyol, and other polyols can be used. As the polyester polyol, for example, an aliphatic dicarboxylic acid having 4 to 20 carbon atoms such as adipic acid, suberic acid, sebacic acid, and brassinic acid, terephthalic acid, isophthalic acid, etc. are used as acid components, and ethylene glycol, propylene glycol, neopentyl glycol, An aliphatic diol having 1 to 6 carbon atoms such as hexamethylene glycol, diethylene glycol,
Ether glycols such as dipropylene glycol, spiroglycols, N such as N-methyldiethanolamine
Polyester polyol or polycaprolactone polyol having a polyol component such as an alkyl dialkanol amine can be used, and specific examples thereof include adipate polyols such as polyethylene adipate polyol, polybutylene adipate polyol, polyethylene propylene adipate polyol, and terephthalate. Acid-based polyol (eg, Toyobo Co., Ltd., trade name Byron RU
X, Byron RV-200L), polycaprolactone polyol (eg, Daicel chemistry, trade name Praxel 212, Praxel 220) and the like. Specific examples of the polyether polyol include polyoxypropylene polyol and polyoxytetramethylene polyol. Further, as other polyols, polycarbonate polyol (eg West Germany, Bayer AG, trade name Desmofuen 2020E), polybutadiene polyol (eg Nippon Soda, trade name G-1000, G-2000, G-3000, Idemitsu Petrochemical, trade name Poly bdR-45HT), polypentadiene polyol, castor oil-based polyol, and the like.
Further, epoxy resins having a hydroxyl group such as bisphenol A type epoxy resin, novolak type epoxy resin, and epoxidized olefin type epoxy resin can also be used. These polyols may be used either individually or in combination of two or more. In addition, these hydrophilic polyols and hydrophobic polyols can be mixed and used,
It is also possible to use a copolymer of both. As the diisocyanate, various known polyfunctional aliphatic, alicyclic and aromatic isocyanates in the field of polyurethane production can be used, and examples thereof include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4-dicyclohexylmethane. Diisocyanate (HMDI), 2,4-tolylene diisocyanate (2,4-
TDI), 2,6-tolylene diisocyanate (2,6-TDI),
4,4-diphenylmethane diisocyanate (MDI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), lysine diisocyanate (LDI) and the like can be mentioned. Further, a usual chain extender can be used if necessary. Examples of the chain extender include 2 to 6 having a molecular weight of 500 or less.
Examples include functional polyols and diamines having a molecular weight of 500 or less and having a primary or secondary terminal amino group. Examples of suitable chain extenders include (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol,
Polyols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and xylylene glycol (b) Diamines such as hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine and 1,4-cyclohexanediamine (c) Alkanolamines such as ethanolamine, diethanolamine and triethanolamine (d) Hydroquinone, pyrogallol, 4,4-isopropylidene diphenol, aniline and the above polyols, diamines and alkanolamines with propylene oxide and / or ethylene oxide. Examples thereof include polyols having a molecular weight of 500 or less obtained by adding them in any order. In the present invention, each component may be appropriately selected from a wide range depending on the application, in which case the chemical equivalent ratio of NCO / active hydrogen (NCO index) is about 0.8 to 4.0, preferably about 1.0.
It is preferable to react in the range of to 3.0. The reaction is usually preferably carried out at about 50 to 150 ° C. A known urethanization catalyst and the like can be added. The urethane prepolymer thus synthesized can be easily dispersed in water, and the required nonionic urethane emulsion can be obtained. In order to suppress foaming during emulsification, it is optional to use an aqueous defoaming agent (eg, Torre Silicone, SM-5512, San Nopco, SN Defomer 133, 432, etc.). At the time of prepolymer synthesis or emulsification, use an organic solvent that is inert to NCO groups and soluble in water and dissolves the prepolymer, and use this organic solvent at the end of prepolymer synthesis or emulsion. It is also optional to recover by a method such as distillation or reduced pressure after the conversion. In the present invention, iron (II) is added to the nonionic emulsion.
The compound type deodorant is mixed and stirred, rubbed into the synthetic resin foam, and then dried, whereby the deodorant can be entrapped and fixed on the surface of the foam. Drying can usually be performed at about 40 to 100 ° C. Examples of the iron (II) compound-based deodorant include iron (II) compound (excluding iron phthalocyanine) compound alone or a mixture thereof with an organic acid, ethylenediaminetetraacetic acid or myoban. Examples of the iron (II) compound include sulfate, nitrate, chloride, bromide, iodide and the like. This iron (II) compound is a source of Fe ²⁺ and reacts with a malodorous component to immobilize it. Examples of the organic acid include L-ascorbic acid, erythorbic acid, citric acid, malic acid,
Examples thereof include various carboxylic acids such as maleic acid, fumaric acid, sorbic acid, acetic acid, propionic acid, adipic acid, benzoic acid, glycine and glutamic acid, oxycarboxylic acids, amino acids and the like. Further, in the present invention, it is also possible to use a filler together, for example, activated carbon, zeolite, perlite, vermiyukirite, diatomaceous earth, kaolin, loess, magnesia, magnesium hydroxide, calcium hydroxide, alumina, silica, wood powder, paper powder. , Clay, talc, acid clay,
Examples include powders of calcium sulfite, calcium carbonate, magnesium carbonate, gypsum dihydrate, blast furnace slag, urea / formalin resin, and the like. Among them, it is desirable to use a filler having an adsorbing ability for the iron (II) compound in combination. The reason is that the iron (II) compound type deodorant is used as an aqueous solution at the time of processing and is immobilized on the foam through a nonionic emulsion. This is because the discolored iron (II) compound is prevented from leaking to the outside, and thus has an action of preventing external pollution.
Specific examples thereof include activated carbon, silica gel, alumina, wood powder, paper powder and the like, among which activated carbon is preferable. Furthermore, when this filler is used, its amount depends on the kind of the iron (II) compound, but it is preferably 20% by weight or more, preferably 50 to 1500% by weight of the iron (II) compound. In the present invention, the iron (II) compound-based deodorant and the nonionic emulsion have a solid content of the nonionic emulsion of 5% by weight based on the total amount of the iron (II) compound and the filler.
Above, it is preferable to use it so as to be 10 to 300% by weight. The reason for this is that if the solid content of emulsion is too low, the deodorant system including the filler adheres to and retained on the foam, and the deodorizing effect cannot be maintained. The amount of the iron (II) compound-based deodorant in the synthetic resin foam of the present invention is usually 10 to 1500% by weight, preferably 50 to 500% by weight, based on the synthetic resin foam. (Effects of the Invention) In the present invention, since the iron (II) compound-based deodorant is attached to the foam having a large surface area, the deodorant having a very large contact area with air and thus an extremely large deodorizing effect is provided. You can In addition, by using an adhesive filler such as activated carbon in combination, the problem of external pollution, which is a conventional defect, is solved, and by using nonionic emulsion, the performance can be improved over a long period of time. Can be maintained over time. Further, if this nonionic emulsion is a self-emulsifying type, it contains a hydrophilic group in its molecule, and therefore it is incorporated into the deodorant system such as ammonia, mercaptan, hydrogen sulfide and amines, which are malodorous substances. The speed is increased and the deodorizing effect is further enhanced. Furthermore, in order to maintain this large deodorizing effect for a long period of time, the foam and the nonionic emulsion are of the same quality,
For example, when both are urethane type, the bond retention of both is good. The deodorant system thus obtained had an extremely excellent deodorizing effect, did not contaminate the outside, and could maintain the effect for a long period of time. (Examples) The production examples and examples of the present invention will be described. Two types of nonionic polyurethane emulsion were prepared by the following method. Production Example 1 Polytetramethylene glycol (PTMG # 1000) 60 g,
25 g of polyethylene glycol (PEG # 6000), 15 g of diethylene glycol (DEG) and 52 g of tolylene diisocyanate (TDI-80) were mixed and reacted at 120 ° C. for 3 hours.
After further cooling to 80 ° C., 50 g of MEK was added and well stirred to obtain a urethane prepolymer solution. 228 g of water was added to the obtained prepolymer solution and mixed and emulsified at room temperature with a homomixer.
The emulsion obtained in this way is heated (decompression is also possible)
MEK was distilled off to obtain the desired polyurethane emulsion. 40% solid content of emulsion, viscosity 1200cps / 25 ℃, pH
Was 5.5. Production Example 2 Epicoat 1001 (165 g), polyethylene glycol (PEG # 1540) 385 g and isophorone diisocyanate (I
194.7 g of PDI) were mixed and reacted at 120 ° C. for 3 hours. 80 ℃
After cooling to 24.degree. C., 248.2 g of dioxane was added and well stirred to obtain a urethane prepolymer solution. To 100 g of the obtained urethane prepolymer solution, 200 g of water was added and well stirred to obtain the desired polyurethane emulsion. The solid content of emulsion was 27%, the viscosity was 400 cps / 25 ° C, and the pH was 6.3. Example 1 FeSO ₄ .7H ₂ O was added to ₄ g of the urethane emulsion of Production Example 1.
(1 g), 3 g of activated carbon and 9 g of water were mixed and stirred, and then urethane foam (100 x 100 x 5 mm) was impregnated with this and dried, and then dried at 60 ° C for 2 hours to contain a deodorant synthetic resin. A foam was obtained. Table 1 shows the specific gravity, adhesiveness and discoloration of the obtained synthetic resin foam. Adhesion is determined by rubbing the foams together after drying and observing the degree of fall of the adhering substances. Also, the color fading is absorbed by ammonia, wrapped in a white cloth, and left for 5 days in a wet state. It was measured by observing. In that determination, ⊚ indicates that the characteristic (effect) is particularly excellent, ∘ indicates that the characteristic (effect) is excellent, and Δ indicates that the characteristic (effect) is inferior, but × indicates that the characteristic (effect) does not exist. Examples 2 to 9 Synthetic resin foams containing a deodorant were obtained in the same manner as in Example 1 by using the components shown in Table 1, and their properties were examined. The results are shown in Table 1. [Deodorization test] 2 g of the foamed product of each example was cut out and used as a sample. 0.5 ml of 28% ammonia water was placed in a 450 ml wide-mouthed bottle, and a 20 ml beaker containing a sample was further placed. After 4 hours, the presence or absence of ammonia odor was checked. As a result, there was no aminian odor in all the examples.

Claims (1)

(57) [Claims] A synthetic resin foam having an iron (II) compound (excluding iron phthalocyanine) -based deodorant integrated with a synthetic resin foam and having a deodorizing effect, wherein the iron (II) compound-based deodorant is a nonionic emulsion. A synthetic resin foam having an excellent deodorizing effect, characterized in that it is applied to a synthetic resin foam. 2. The synthetic resin foam according to claim 1, wherein the synthetic resin foam is a urethane foam having an apparent specific gravity of 0.008 to 0.1. 3. The synthetic resin foam according to claim 1, wherein the nonionic emulsion is a urethane emulsion. 4. The synthetic resin foam according to claim 3, wherein the urethane emulsion is a self-emulsifying type. 5. The synthetic resin foam according to claim 1, further comprising a filler having an adsorbing ability for the iron (II) compound. 6. The filler is activated carbon, which is an iron (II) compound
The synthetic resin foam according to claim 5, which contains 20% by weight or more. 7. The synthetic resin foam according to claim 5, wherein the solid content of the nonionic emulsion is 5% by weight or more based on the total of the iron (II) compound and the filler. 8. The synthetic resin foam according to claim 1, wherein the iron (II) compound-based deodorant is an iron (II) compound alone or a mixture thereof with an organic acid, ethylenediaminetetraacetic acid or myoban.