JP2009179707A - Deodorizing polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorizing polyurethane foam wherein a volatile organic compound (VOC) contained in a raw material, a VOC generated in reaction and foaming steps and a VOC during use can be rapidly oxidized, decomposed and made harmless and its performance can be exhibited for a long period of time. <P>SOLUTION: The deodorizing polyurethane foam is obtained by reaction and foaming of a material for the polyurethane foam containing polyols, polyisocyanates, a catalyst, a foaming agent and a deodorant. The deodorant is a metal compound carrying inorganic porous material. The metal compound oxidizes and decomposes the VOC such as aldehydes and the metal compound itself is also oxidized and reduced by water after oxidation and decomposition to be returned to the original metal compound. The particle diameter of the deodorant is larger than the width of a cell backbone which constitutes the polyurethane foam. An iron based compound such as iron(II) sulfate or silver based compound such as silver oxide is preferable as the deodorant. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a deodorant polyurethane foam used, for example, as an interior material for a house or an automobile.

In recent years, environmental standards for volatile organic compounds [VOC (Volatile Organic Compounds)] have become stricter with respect to interior materials for homes and automobiles, and strict regulations have been stipulated especially for formaldehyde and acetaldehyde, which are the cause of sick house syndrome. Therefore, a technique for adsorbing VOC by incorporating a porous inorganic substance such as activated carbon or zeolite as an adsorbent into a polyurethane foam used as an interior material for a house or an automobile is known.

In addition, the applicant of the present application contacts a raw material containing aldehydes with an adsorbent capable of adsorbing aldehydes, removes the aldehydes contained in the raw material with the adsorbent, and then adsorbs the aldehydes. A technique for producing a polyurethane foam from a raw material obtained by separating and removing the resin was proposed (see, for example, Patent Document 1). As the adsorbent, a monohydrazide compound or a dihydrazide compound is used.
JP 2006-77128 A (pages 2 and 6)

However, when a polyurethane foam contains a porous inorganic substance as an adsorbent, aldehydes adsorbed on the porous inorganic substance are released into the air again due to external factors such as heating and vibration. The Therefore, although the concentration of aldehydes in the room once decreases, there is a problem that it tends to increase again.

Moreover, in the polyurethane foam described in Patent Document 1, the raw material of the polyurethane foam is previously adsorbed with an adsorbent, and after removing the adsorbent adsorbed with aldehydes, the raw material is reacted and foamed. Thus, a polyurethane foam is produced. Therefore, VOC generated in the reaction and foaming process, and further, VOC in the atmosphere when using the polyurethane foam could not be reduced. Further, in automobile interior materials, it has not been satisfactory to quickly deodorize aldehydes caused by tobacco smoking by passengers.

Therefore, the object of the present invention is to oxidize, decompose and detoxify VOCs contained in the raw materials, VOCs generated by reaction and foaming, and VOCs during use, and demonstrate their performance over a long period of time. An object of the present invention is to provide a deodorant polyurethane foam that can improve the adsorption rate and quickly exhibit the deodorization performance.

In order to achieve the above object, the deodorant polyurethane foam of the invention described in claim 1 is obtained by reacting a raw material of a polyurethane foam containing polyols, polyisocyanates, a catalyst, a foaming agent and a deodorant. A deodorant polyurethane foam obtained by foaming, wherein the deodorizer is an inorganic porous body supporting a metal compound, and the metal compound oxidizes and decomposes a volatile organic compound itself. Is also a compound that is reduced by moisture and returns to the original metal compound after the oxidation and decomposition, and the particle size of the deodorant is larger than the width of the cell skeleton constituting the cells of the polyurethane foam It is characterized by this.

The deodorant polyurethane foam of the invention according to claim 2 is characterized in that, in the invention according to claim 1, the content of the deodorizer is 5 to 40 parts by mass per 100 parts by mass of polyols. To do. The deodorant polyurethane foam of the invention described in claim 3 is characterized in that, in the invention according to claim 2, the metal compound of the deodorizer is an iron compound or a silver compound. It is. Furthermore, the deodorant polyurethane foam of the invention according to claim 4 is the invention according to any one of claims 1 to 3, wherein the volatile organic compound is an aldehyde. It is what.

According to the present invention, the following effects can be exhibited. In the deodorant polyurethane foam of the invention described in claim 1, since the deodorizer is made of an inorganic porous material, it is easy to adsorb volatile organic compounds quickly. Furthermore, since a metal compound is supported on the inorganic porous body, for example, when the obtained deodorant polyurethane foam is exposed to a VOC atmosphere such as aldehydes, the deodorant contained in the foam will remove aldehydes. Oxidation modifies to carboxylic acid, and further promotes oxidation to decompose carboxylic acid into carbon dioxide and water. At this time, the deodorant itself is denatured into an oxidized state, but is reduced by moisture in the air, returns to the original reduced state, and again functions as a deodorant.

Therefore, VOC contained in the raw material, VOC generated by reaction and foaming, and further VOC in use can be oxidized and decomposed to be harmless, and its performance can be demonstrated over a long period of time. it can. Furthermore, since the particle size of the deodorant is larger than the width of the cell skeleton constituting the cells of the polyurethane foam, the adsorption rate is very fast.

In the deodorant polyurethane foam of the invention according to claim 2, since it is 5 to 40 parts by mass per 100 parts by mass of the polyols, in addition to the effect of the invention according to claim 1, the deodorant polyurethane foam is more reliably extinguished over a long period of time. The odor performance can be exhibited, the adsorption capacity is increased, and the action of maintaining the deodorizing property can be improved. When the addition amount is less than 5 parts by mass, the predetermined deodorizing performance cannot be exhibited and the deodorizing speed is slow. On the other hand, when it exceeds 40 parts by mass, the mechanical properties are inferior in flexibility, and as a soft polyurethane foam, it becomes unsatisfactory or an appropriate foam cannot be obtained.

In the deodorant polyurethane foam of the invention according to claim 3, since the deodorizer is an iron-based compound or a silver-based compound, in addition to the effect of the invention according to claim 2, oxidation and decomposition action of VOC And it is possible to improve its own reducing action.

In the deodorant polyurethane foam of the invention according to claim 4, since the volatile organic compound is an aldehyde, in addition to the effect of the invention according to any one of claims 1 to 3, Aldehydes such as acetaldehyde and formaldehyde can be easily oxidized and decomposed to make them harmless.

In the following, embodiments that are considered to be the best of the present invention will be described in detail. The deodorant polyurethane foam in the present embodiment (hereinafter, also referred to as polyurethane foam or simply foam) reacts with a polyurethane foam material containing polyols, polyisocyanates, catalyst, foaming agent and deodorant compound. And obtained by foaming. At that time, the raw material of the polyurethane foam is a metal compound that is a compound that oxidizes and decomposes VOC as a deodorant and also oxidizes itself, and returns itself to the original metal compound after the oxidation and decomposition. An inorganic porous body supporting s is included.

Moreover, since the particle size of the deodorant is larger than the width of the cell skeleton constituting the cell of the deodorant polyurethane foam, the deodorant particles are not completely included in the polyurethane resin and are covered with the polyurethane resin. As a result, a deodorant polyurethane foam having a high adsorption rate can be obtained.
Here, the polyurethane foam is generally composed of a cell skeleton and a cell membrane. In the present invention, the “cell skeleton” means a column portion of a three-dimensional structure of the polyurethane foam matrix.
In addition, content of the deodorizer is set to 5-40 mass parts per 100 mass parts of polyols. By blending a predetermined amount of this deodorant, the polyurethane foam retains its mechanical properties and removes VOCs typified by aldehydes such as acetaldehyde and formaldehyde by oxidizing and decomposing them. It is done.

First, the raw material of a polyurethane foam is demonstrated in order. (Polyols) As the polyols, polyether polyols, polyether ester polyols, or polyester polyols may be used alone or in combination. However, the polyethers have good reactivity with polyisocyanates and are difficult to hydrolyze. Polyols are preferred.

As the polyether polyol, a polyether polyol composed of a polymer obtained by addition polymerization of propylene oxide and ethylene oxide to a polyhydric alcohol, a modified product thereof, and the like are used. Examples of the modified product include those obtained by adding acrylonitrile or styrene to the polyether polyol, or those obtained by adding both acrylonitrile and styrene. Here, the polyhydric alcohol is a compound having a plurality of hydroxyl groups in one molecule, and examples thereof include glycerin and dipropylene glycol. Specific examples of polyether polyols include triols obtained by addition polymerization of propylene oxide to glycerin and addition polymerization of ethylene oxide, and diols obtained by addition polymerization of propylene oxide to dipropylene glycol and addition polymerization of ethylene oxide. .

The polyether ester polyol is a compound obtained by reacting a polyoxyalkylene polyol with a polycarboxylic acid anhydride and a compound having a cyclic ether group. Examples of polyoxyalkylene polyols include polyethylene glycol, polypropylene glycol, and propylene oxide adducts of glycerin. Examples of polycarboxylic acid anhydrides include succinic acid, adipic acid, phthalic acid, trimellitic acid, and other anhydrides. Examples of the compound having a cyclic ether group include ethylene oxide and propylene oxide. The order in which these three components are reacted is not particularly limited. For example, a method in which three components are reacted at the same time, a method in which a compound having a cyclic ether group is blown into polyoxyalkylene polyol and polycarboxylic acid anhydride, and a reaction in which a part of polyoxyalkylene polyol and polycarboxylic acid anhydride is reacted. And a method of reacting the compound having a cyclic ether group with the remainder of the polycarboxylic acid anhydride. As polyester polyols, in addition to condensation polyester polyols obtained by reacting polycarboxylic acids such as adipic acid and phthalic acid with polyols such as ethylene glycol, diethylene glycol, propylene glycol and glycerin, lactone polyester polyols and polycarbonate systems A polyol is used.

These polyols can change the number of functional groups and the hydroxyl value of the hydroxyl group by adjusting the kind of raw material component, the molecular weight, the degree of condensation, and the like. (Polyisocyanates) Next, polyisocyanates to be reacted with polyols are compounds having a plurality of isocyanate groups, specifically tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1 , 5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and modified products thereof.

The isocyanate index (isocyanate index) of the polyisocyanates is preferably set in the range of 100 to 130. When the isocyanate index is less than 100, physical properties such as hardness and tensile strength of the polyurethane foam deteriorate, and when it exceeds 130, the crosslinking density of the polyurethane foam becomes too high. Here, the isocyanate index represents the equivalent ratio of the isocyanate groups of the polyisocyanates to the active hydrogen groups such as the hydroxyl groups of the polyols and water as a blowing agent in percentage. Therefore, an isocyanate index exceeding 100 means that polyisocyanates are in excess of polyols. (Foaming agent) The foaming agent is for foaming a polyurethane resin to form a polyurethane foam. For example, dichloromethane (methylene chloride), pentane, cyclopentane, hexane, cyclohexane, carbon dioxide, etc. are used in addition to water. Of these foaming agents, water is preferable because it can react quickly with polyisocyanates to generate sufficient carbon dioxide gas and can be handled easily. It is preferable that content of a foaming agent is 1-5 mass parts per 100 mass parts of polyols. When the content of the foaming agent is less than 1 part by mass, foaming is insufficient and it is difficult to obtain a low-density foam. On the other hand, when it exceeds 5 parts by mass, foaming becomes excessive and physical properties such as hardness and tensile strength of the foam are lowered. (Catalyst) The catalyst is mainly for accelerating the urethanization reaction between polyols and polyisocyanates and the foaming reaction between polyisocyanates and water as a blowing agent. Specific examples of the catalyst include tertiary amines (amine catalysts) such as triethylenediamine, N, N-dimethylaminoethanol, N, N ′, N′-trimethylaminoethylpiperazine, tin octylate (tin octoate), Organometallic compounds (metal catalysts) such as dibutyltin laurate (dibutyltin dilaurate), acetates, alkali metal alcoholates and the like are used alone or in combination. As the catalyst, it is preferable to use a combination of an amine catalyst and a metal catalyst in order to enhance the effect.

The catalyst content is preferably 0.05 to 2.0 parts by mass per 100 parts by mass of polyols. When the content of the catalyst is less than 0.05 parts by mass, the urethanization reaction and the foaming reaction are not sufficiently progressed, and the mechanical properties of the foam tend to decrease. On the other hand, when it exceeds 2.0 parts by mass, the urethanization reaction and the foaming reaction are excessively promoted, the balance between the two reactions is deteriorated, and the distortion characteristic of the foam is deteriorated.

(Deodorant) This deodorant is a room-temperature solid inorganic porous material supporting a specific metal compound, and the inorganic porous material contains an adsorbent having a physical adsorption action such as zeolite. be able to. In addition, the above specific metal compound is a property that expresses a deodorizing function by oxidizing and decomposing VOCs such as aldehydes and the like, and is oxidized, and the oxidized itself is reduced with moisture to return to the original metal compound. It is a compound having Examples of such a metal compound include iron-based compounds such as ferrous sulfate (FeSO ₄ ), ferrous oxide (FeO), and ferrous chloride (FeCl ₂ ), silver oxide (Ag ₂ O), and silver nitrate (AgNO). ₃ ), silver compounds such as silver chloride (AgCl) and silver sulfate (Ag ₂ SO ₄ ), zinc compounds and the like are used. Such a deodorant containing a metal compound preferably contains a chelating agent such as EDTA (ethylenediaminetetraacetic acid) in order to form and stabilize a chelate compound with metal ions.

In addition, examples of the solid inorganic porous body that supports the metal compound include zeolite, sepiolite, aluminum oxide, and silica. The content of the metal compound supported on the inorganic porous body is preferably in the range of 0.3 to 6.0%. Further, since the content of the metal compound relative to the deodorant polyurethane foam is supported on the inorganic porous body, the range of 0.01 to 1.5 parts by mass per 100 parts by mass of polyols is the deodorant. This is preferable in that the performance is exhibited quickly and over a long period of time.

The deodorizing mechanism of the metal compound having deodorizing performance is described below. For example, as shown in the following formula, acetaldehyde (CH ₃ CHO) is oxidized by a deodorant to become acetic acid (CH ₃ COOH), and the acetic acid is further oxidized and decomposed by the deodorant to carbon dioxide (CO ₂ ). And water (H ₂ O).

CH ₃ CHO → CH ₃ COOH → CO ₂ + H ₂ O Further, formaldehyde (HCHO) is oxidized by a deodorant to form formic acid (HCOOH), and the formic acid is further oxidized by the deodorant. It is decomposed into carbon dioxide (CO ₂ ) and water (H ₂ O).

HCHO → HCOOH → CO ₂ + H ₂ O In the process of oxidation, oxidation or decomposition, ferrous sulfate as a deodorant becomes ferric sulfate [(Fe) ₂ (SO ₄ ) ₃ ], Silver oxide (Ag ₂ O) becomes divalent silver oxide (AgO). That is, the deodorizer itself changes to an oxidized state in the process of oxidizing, oxidizing, or decomposing aldehydes. However, the deodorant in the oxidized state is reduced by moisture in the air (reducing agent), ferric sulfate is converted to ferrous sulfate, and divalent silver oxide (AgO) is converted to monovalent silver oxide ( Return to Ag ₂ O). Therefore, this deodorant can again oxidize and decompose VOCs such as aldehydes, and in addition, the cycle of returning from the reduced state to the reduced state through the oxidized state is repeated, for example, 10 times or more. A deodorizing function can be developed across.

The content of the deodorant is preferably 5 to 40 parts by mass per 100 parts by mass of polyols. When this content is less than 5 parts by mass, the deodorant has insufficient function expression and insufficient oxidation and decomposition of VOCs such as aldehydes. On the other hand, when it exceeds 40 parts by mass, the function of oxidizing and decomposing VOCs such as aldehydes is sufficient, but the mechanical properties of the polyurethane foam are remarkably lowered by an excessive deodorant.

Moreover, it is preferable that the particle size of the deodorant is 20 to 100 μm because it can quickly exhibit deodorant properties. If the particle size is less than 20 μm, long-term deodorizing performance will function, but since the particle size will be smaller than the width of the cell skeleton of the polyurethane foam, it is difficult to obtain rapid deodorizing performance.
On the other hand, if the particle diameter is larger than 100 μm, foaming stability of the foam may be hindered when producing a polyurethane foam, and the deodorant is too large than the cell skeleton, and the particulate deodorization There is a risk of dropping off the agent.

(Foam stabilizer) The foam stabilizer is preferably blended with the raw material of the polyurethane foam in order to smoothly foam, and as the foam stabilizer, those generally used in the production of polyurethane foams should be used. Can do. Specific examples of the foam stabilizer include silicone compounds, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate, polyether siloxane, and phenolic compounds. Among these, a linear or branched polyether-siloxane copolymer is preferable, and a linear polysiloxane-polyoxyalkylene copolymer having a low foam regulating power is particularly preferable in order to improve the connectivity. The content of the foam stabilizer is preferably 0.5 to 2.5 parts by mass per 100 parts by mass of polyols. When this content is less than 0.5 part by mass, the foam regulating action at the time of foaming of the raw material of the polyurethane foam is not sufficiently exhibited, and it becomes difficult to obtain a good foam. On the other hand, when it exceeds 2.5 parts by mass, the foam regulating action becomes stronger and the cell connectivity tends to be lowered. (Other compounding agents) In addition to the raw materials of the polyurethane foam, a crosslinking agent, an antioxidant, a filler, a stabilizer, a colorant, a flame retardant, a plasticizer, and the like can be blended according to a conventional method as necessary. .

(Manufacture of a polyurethane foam) Next, when manufacturing a deodorant polyurethane foam using the raw material of said polyurethane foam, it is performed according to a conventional method. That is, in the production of a foam, a one-shot method in which polyols and polyisocyanates are directly reacted, or a prepolymer having an isocyanate group at the terminal is obtained by reacting polyols and polyisocyanates in advance. Both of the prepolymer methods in which polyols are reacted are employed. Then, a foaming agent is mixed in a mixed liquid of polyols and polyisocyanates, or a mixed liquid of prepolymer and polyols, and a foam stabilizer, a catalyst, a deodorizing agent, etc. are added and stirred and mixed. These raw materials are reacted by urethanization reaction, cross-linking reaction, etc. and foamed by foaming reaction.

Thus, the deodorizing polyurethane foam according to the present invention, for example, the deodorizing soft polyurethane foam is obtained. Here, the soft polyurethane foam having a deodorizing property exhibits a deodorizing performance, is lightweight, has an open cell structure in which cells (bubbles) communicate with each other, is flexible, and has a resilience. What you have. Therefore, the deodorizing soft polyurethane foam according to the present invention can exhibit characteristics such as cushioning properties, impact absorption properties, high elasticity, low resilience. The soft polyurethane foam in the present invention has an open-cell structure, and a portion surrounded by the cell skeleton, that is, a part of the cell membrane portion has voids, so that the deodorant made of an inorganic porous material is used. Since a part of the agent is exposed without being covered with the resin, the deodorizing speed is fast, which is preferable as a deodorant polyurethane foam.

As a foaming form, in addition to mold foaming using a mold, slab foaming that spontaneously foams is adopted, but slab foaming is preferable from the viewpoint of ease of foaming and productivity. The slab foaming is performed by discharging the agitated and mixed raw material onto a belt conveyor, and the raw material reacts at room temperature and atmospheric pressure while the belt conveyor moves and spontaneously foams. Then, a slab foam is obtained by hardening (curing) in a drying furnace. The reaction when producing a polyurethane foam is complicated, but basically the following reaction is mainly used. That is, a urethanation reaction in which polyols and polyisocyanates are addition-polymerized, a foaming reaction between polyisocyanates and water as a blowing agent, and a crosslinking reaction between these reaction products and polyisocyanates.

The polyurethane foam obtained as described above can oxidize and decompose VOCs such as aldehydes quickly and in a short time and can be rendered almost harmless by containing the deodorant.

In addition, the physical properties of the polyurethane foam are appropriately adjusted, but the apparent density is, for example, 20 to 100 kg / m ³ , the mechanical properties are, for example, hardness of 50 to 250 N, the number of cells is 8 to 80 (pieces / 25 mm), Air permeability is formed to 10 to 400 (ml / cm ² / sec).

(Operation) Now, the operation of the present embodiment will be described. The deodorant polyurethane foam is obtained by reacting and foaming a polyurethane foam raw material containing polyols, polyisocyanates, a catalyst, a foaming agent and a deodorant according to a conventional method. Is obtained. In this case, the foam raw material contains 5 to 40 parts by mass of a deodorant composed of an inorganic porous material carrying a deodorizing metal compound such as ferrous sulfate and silver oxide per 100 parts by mass of polyols. include. Therefore, in addition to aldehydes contained in the raw material of the foam, aldehydes that may be generated during the reaction and foaming process are oxidized and decomposed by the deodorant. For example, acetaldehyde is oxidized and converted into acetic acid, which is further oxidized and decomposed into carbon dioxide and water, and acetaldehyde is debrominated and detoxified. When such oxidation and decomposition are performed, the deodorant itself changes to an oxidized state, but is reduced by moisture in the air, returns to the original deodorized agent, and exhibits its function again. Since such oxidation and reduction of the deodorant are repeated and the deodorant can always maintain its function, the deodorizing action is maintained.

Moreover, in the particulate deodorant, when the particle diameter is reduced, the surface area as a whole is increased on a weight basis, and thus the adsorption rate is thought to be increased. However, when producing a polyurethane foam as in the present invention, in a foam obtained by mixing and reacting a deodorant with a blending raw material such as a polyol, the larger the particle size of the deodorant, It was found that the use of a larger particle size than the cell skeleton resulted in a faster adsorption / decomposition rate and improved usability. That is, when the particle size of the deodorant is larger than the width of the cell skeleton constituting the cell of the deodorant polyurethane foam, the deodorant particles are not completely included in the polyurethane resin, so the adsorption rate Becomes faster and has better deodorization speed. In particular, in the case of a soft polyurethane foam having an open cell structure, at least a part of the cell membrane has an open cell structure. For this reason, a part of the deodorant made of an inorganic porous material is exposed to the void part surrounded by the cell skeleton, the so-called cell window, and the surface of the deodorant particles is partially in contact with the outside air, so that the deodorant is exposed. The speed seems to be faster.

(Summary of effects) The effects exhibited by the above embodiment will be collectively described below. In the deodorant polyurethane foam of the present embodiment, a specific deodorant is blended in the raw material of the polyurethane foam, and the foam has an open cell structure. Moreover, since the particulate deodorant has a particle size larger than the width of the cell skeleton, the adsorption rate of the deodorant component is very fast.

In the deodorant polyurethane foam of this embodiment, the deodorizer is mix | blended with the raw material of a polyurethane foam 5-100 mass parts per 100 mass parts of polyols. Since this deodorizer exhibits the function of oxidizing and decomposing VOCs such as aldehydes, VOCs contained in the raw material of the foam, VOCs generated by reaction and foaming, and further in the atmosphere during use VOC can be oxidized and decomposed to be detoxified, and its performance can be demonstrated over a long period of time.

When the iron-based compound or the silver-based compound is supported on the inorganic porous body, the deodorizing agent effectively expresses the oxidation, decomposition, and reduction of the VOC. Since the volatile organic compounds are aldehydes such as acetaldehyde and formaldehyde in particular, such aldehydes can be easily oxidized and decomposed to be harmless. In addition to the aldehyde compound, the volatile organic compound may be an organic compound such as an aliphatic compound such as acetic acid or ethyl acetate, or an aromatic compound such as toluene or ethylbenzene, and the deodorizing polyurethane according to the present invention. It becomes an object to be deodorized by the foam.

By using a silver-based compound such as silver oxide as a deodorant, the resulting polyurethane foam can exhibit an antibacterial effect.

Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. (Examples 1-9 and Comparative Examples 1-6) First, the raw material of the polyurethane foam containing the polyols, polyisocyanates, foaming agent, foam stabilizer, catalyst, and deodorant used in each Example and Comparative Example Is shown below.

Polyol: A polyether polyol obtained by addition polymerization of propylene oxide and ethylene oxide to glycerin, having a molecular weight of 3000, a hydroxyl group number of 3, a hydroxyl value of 56 (mgKOH / g), manufactured by Sanyo Chemical Industries, Ltd., polyol GP3050.

Polyisocyanate: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd., tolylene diisocyanate (a mixture of 80% by mass of 2,4-tolylene diisocyanate and 20% by mass of 2,6-tolylene diisocyanate).

Foam stabilizer: Silicone foam stabilizer, B8110 (manufactured by Degussa Japan Co., Ltd.) Catalyst A: Amine catalyst, Kao Riser No. 25 (Kao Corporation) Catalyst B: Metal catalyst, dibutyltin dilaurate (manufactured by Johoku Chemical Industry Co., Ltd., MRH110)

Deodorant A: 0.5 mass% ferrous sulfate (FeSO ₄ ) as a metal compound is supported on zeolite and contains a chelating agent (EDTA) and the like, and has a particle size of 30 to 50 μm (average particle size of 40 μm). Odorant. Deodorant B: Zeolite containing 0.5% by mass of ferrous sulfate (FeSO ₄ ) as a metal compound supported on zeolite and containing a chelating agent (EDTA), etc., having a particle size of 80 to 100 μm (average particle size of 90 μm) Odorant. Deodorizer C: Zeolite containing 0.5% by mass of ferrous sulfate (FeSO ₄ ) as a metal compound supported on zeolite, containing a chelating agent (EDTA), etc., having a particle size of 5 to 10 μm (average particle size of 7 μm) Odorant. Deodorant D: Deodorant having a particle size of 30 to 50 μm (average particle size of 40 μm) containing 0.5% by mass of silver oxide (Ag ₂ O) as a metal compound on zeolite and containing a chelating agent (EDTA) Agent.

Deodorant E: Activated carbon, manufactured by Nippon Enviro Chemicals Co., Ltd., granular white rabbit Gx4 / 6. Deodorant F: Molecular sieve, Union Showa Co., Ltd., Molecular sieve 3A.

And each of these raw materials was mix | blended with content shown in Table 1, Table 2, and Table 3, and the raw material of the polyurethane foam in each Example and a comparative example was prepared. Then, the raw material of these polyurethane foams is used as a raw material of these polyurethane foams using a low pressure foaming machine (manufactured by Nippon Sosei Kogyo Co., Ltd., SUPER SHOT (2-component automatic lightweight mixing and discharging machine), model: EX-303P). Was injected into a foam container having a length and width of 500 mm each, foamed at normal temperature and atmospheric pressure, and then placed in a heating furnace to be crosslinked (cured) to obtain a flexible polyurethane foam. During the process, the foamed state was visually observed.

In order to investigate the relationship between the particle size of the deodorant and the cell skeleton, in the present invention, a deodorant having a different particle size is blended with the polyurethane raw material, and the chamber internal pressure is controlled to control the cell skeleton. Controlled. Specifically, the cell skeleton can be thickened by increasing the chamber internal pressure.
In Examples, a flexible polyurethane foam was obtained by changing the nozzle diameter to φ = 15 mm and φ = 10 mm in the same formulation in a low-pressure foaming machine in order to vary the chamber internal pressure.

Examples 1 and 2 show a deodorant carrying an iron-based metal compound and using a deodorant whose particle diameter is changed. Examples 3 and 4 are the same as in Examples 1 and 2, but using a deodorant carrying an iron-based metal compound having a different particle diameter and changing the width of the cell skeleton from Examples 1 and 2. . Examples 5 and 6 show examples in which the cell skeleton width was changed using a deodorant carrying a silver-based metal compound. Further, Examples 7, 8, and 9 show the formulations of Example 1 with the amount of deodorant reduced.

On the other hand, Comparative Example 1 is an example in which no deodorant is blended. In Comparative Example 2, activated carbon (deodorant E) is used as the deodorant, and in Comparative Example 3, molecular sieve (deodorant) is used as the deodorant. Those using odorant F) are shown. Moreover, in Comparative Example 4 and Comparative Example 5, both use the fine deodorant C having an average particle diameter of 7 μm as the deodorant and change the width of the cell skeleton. In Comparative Example 6, a deodorant having a fine particle size was used in the formulation of Example 9.

About the obtained polyurethane foam, the apparent density, hardness, air permeability, the number of cells, and the concentration of acetaldehyde were measured according to the following measuring methods. The results are shown in Table 1, Table 2 and Table 3.

Apparent density (kg / m ³ ): Measured according to JIS K7222 (1999). Hardness (N): Measured according to JIS K6400-2 (2004, method D). Number of cells (pieces / 25 mm): Measured according to JIS K 6400-1 Appendix 1. Breathability (ml / cm ² / sec): Measured according to JIS K6400-7B method. The width of the cell skeleton was measured by taking an electron micrograph of the cross section of the obtained polyurethane foam. The average particle size of the deodorant was measured with a laser diffraction device (scattering type).

Concentration of acetaldehyde and acetic acid: After putting a sample of polyurethane foam having a length of 100 mm, a width of 100 mm and a thickness of 10 mm in a 5 L fluororesin bag, the concentration of acetaldehyde in clean air (humidity 50%) is 25 ppm. Adjusted as follows. Then, the bag was left in a thermostatic bath at 25 ° C., and the concentration of acetaldehyde was measured with a detector tube after 3 hours and 25 hours. Thereafter, the inside of the thermostatic chamber was heated to 80 ° C., and after 2 hours, the concentration of acetaldehyde was measured with a detector tube.

表１に示した結果から、実施例１〜６においては、ポリウレタン発泡体の原料に消臭剤を添加したことから、以下の結果を得る。実施例１〜２は、低圧発泡機の機械的条件を同一にすることにより、セル骨格の幅が同じであり、消臭剤の粒子径を変更したものである。セル骨格の幅よりも、消臭剤の粒子径が大きいことにより、骨格の幅よりも粒子径が小さい比較例１よりも、消臭速度・消臭効果ともに高いことが確認できる。 また、実施例３〜４は、低圧発泡機の機械的条件を変更することにより、実施例１，２と同様に発泡体を得、セル骨格の幅を実施例１、２よりも太くしたものである。セル骨格の幅が粒子径よりも大きいことから、実施例１〜２と同様に、比較例１よりも消臭速度・消臭効果が高いことが確認できる。 実施例５、６は、消臭剤を、鉄系から銀系の金属化合物に変更したものであるが、実施例１、３の鉄系の金属化合物を担持した消臭剤とほぼ同様の消臭速度・消臭効果の傾向が得られている。さらに、いずれの実施例においても、８０℃に加熱した後もアセトアルデヒドは増加することはなく、アセトアルデヒドの濃度を十分に抑制することができ、酸化、分解性能が長期に渡って発揮されることが明らかになった。

From the results shown in Table 1, in Examples 1 to 6, since the deodorizer was added to the raw material of the polyurethane foam, the following results were obtained. In Examples 1 and 2, by making the mechanical conditions of the low-pressure foaming machine the same, the width of the cell skeleton is the same, and the particle size of the deodorant is changed. It can be confirmed that both the deodorizing speed and the deodorizing effect are higher than those of Comparative Example 1 in which the particle size of the deodorant is larger than the width of the cell skeleton, and the particle size is smaller than the width of the skeleton. Also, in Examples 3 to 4, by changing the mechanical conditions of the low-pressure foaming machine, a foam was obtained in the same manner as in Examples 1 and 2, and the width of the cell skeleton was made thicker than in Examples 1 and 2. It is. Since the width | variety of a cell frame | skeleton is larger than a particle diameter, it can confirm that a deodorizing speed and a deodorizing effect are higher than the comparative example 1 similarly to Examples 1-2. In Examples 5 and 6, the deodorant was changed from an iron-based to a silver-based metal compound, but almost the same deodorant as the deodorant carrying the iron-based metal compound in Examples 1 and 3 was used. The tendency of odor speed and deodorizing effect is obtained. Furthermore, in any of the examples, acetaldehyde does not increase even after heating to 80 ° C., the concentration of acetaldehyde can be sufficiently suppressed, and oxidation and decomposition performance can be exhibited over a long period of time. It was revealed.

一方、表２に示した結果から、比較例１では消臭剤を配合しなかったため、アセトアルデヒドを全く低減させることができなかった。なお、比較例２、３は、金属化合物を担持していない無機多孔質体での例である。比較例２では、吸着剤として活性炭を配合し、比較例７では吸着剤としてモレキュラーシーブを配合したため、アセトアルデヒドをある程度吸着させることはでき、一定の消臭効果は有するが、加熱後のアルデヒド類の再放出が確認される。したがって、継続的な消臭効果を期待できず、長期にわたって消臭性能を発揮しえないものと思われる。また、比較例４、５は、各実施例１、２、実施例３、４に対し、粒子径が細かい消臭剤を配合したものであるが、消臭速度、消臭効果ともに相対的に劣っていることが確認できる。

On the other hand, from the results shown in Table 2, since no deodorant was blended in Comparative Example 1, acetaldehyde could not be reduced at all. Comparative Examples 2 and 3 are examples of an inorganic porous body that does not carry a metal compound. In Comparative Example 2, activated carbon was blended as the adsorbent, and in Comparative Example 7, molecular sieve was blended as the adsorbent. Therefore, acetaldehyde can be adsorbed to some extent and has a certain deodorizing effect. Re-release is confirmed. Therefore, it seems that a continuous deodorizing effect cannot be expected and the deodorizing performance cannot be exhibited over a long period of time. Further, Comparative Examples 4 and 5 were prepared by blending a deodorant having a fine particle size with respect to each of Examples 1, 2, and Examples 3 and 4, but both the deodorizing speed and the deodorizing effect were relatively high. It can be confirmed that it is inferior.

また表２に示した結果から、実施例７、８、９は、実施例１の消臭剤の添加量を変量させたものである。消臭剤をポリオール１００質量部当たり５〜４０質量部配合したことから、アセトアルデヒドの濃度を十分に抑えることができたと同時に、硬さ、引張強さ及び伸びを良好に保持することができた。消臭剤の添加量を同じにした実施例９と比較例６とを比較すると、セル骨格の幅より粒子径が大きい消臭剤を使用した実施例９は、消臭速度、消臭効果においても、優れていることが確認できる。

Further, from the results shown in Table 2, Examples 7, 8, and 9 are obtained by varying the amount of the deodorant added in Example 1. Since the deodorizer was blended in an amount of 5 to 40 parts by mass per 100 parts by mass of the polyol, the concentration of acetaldehyde could be sufficiently suppressed, and at the same time, the hardness, tensile strength and elongation could be maintained well. Comparing Example 9 and Comparative Example 6 with the same amount of deodorant added, Example 9 using a deodorant having a particle size larger than the width of the cell skeleton was effective in deodorizing speed and deodorizing effect. Can also be confirmed.

In addition, the said embodiment can also be changed and actualized as follows. A plurality of metal compounds or inorganic porous materials can be used in appropriate combination as the deodorant.

Further, the technical idea that can be grasped from the embodiment will be described below.

-The polyurethane foam for deodorization according to any one of claims 1 to 4, wherein the raw material of the polyurethane foam contains a chelating agent. In this case, in addition to the effects of the invention according to any one of claims 1 to 3, the deodorant can be stabilized.

The deodorizing polyurethane foam according to claim 4, wherein the aldehyde is acetaldehyde. In this case, in addition to the effect of the invention according to claim 4, acetaldehyde is oxidatively decomposed to acetic acid, and the acetic acid is oxidatively decomposed to carbon dioxide and water to make odorless and harmless. it can.

A method for producing a deodorant polyurethane foam obtained by reacting and foaming a raw material of a polyurethane foam containing a polyol, a polyisocyanate, a catalyst, a foaming agent and a deodorizer, wherein the deodorizer is a metal It is an inorganic porous material carrying a compound, and the metal compound oxidizes and decomposes a volatile organic compound and also oxidizes itself. After the oxidation and decomposition, the metal compound returns to the original metal compound by being reduced by moisture. A method for producing a deodorant polyurethane foam, which is a compound and the content of the deodorizer is 5 to 40 parts by mass per 100 parts by mass of polyols. According to this manufacturing method, VOCs contained in raw materials, VOCs generated by reaction and foaming, and VOCs in use can be rapidly oxidized and decomposed to be harmless, and the performance can be improved for a long time. It is possible to easily obtain a deodorant polyurethane foam that can be exhibited over a wide range.

Claims (4)

A deodorant polyurethane foam obtained by reacting and foaming a polyurethane foam raw material containing polyols, polyisocyanates, catalyst, foaming agent and deodorant,
The deodorant is an inorganic porous material supporting a metal compound, and the metal compound oxidizes and decomposes a volatile organic compound and is also oxidized. After the oxidation and decomposition, the metal compound is reduced by moisture. The deodorant polyurethane foam, wherein the deodorizer has a particle size larger than the width of the cell skeleton constituting the cells of the polyurethane foam.   The deodorant polyurethane foam according to claim 1, wherein the content of the deodorant is 5 to 40 parts by mass per 100 parts by mass of polyols. The deodorant polyurethane foam according to claim 2, wherein the metal compound of the deodorant is an iron compound or a silver compound. The deodorizing polyurethane foam according to any one of claims 1 to 3, wherein the volatile organic compound is an aldehyde.