JP4727462B2 - Deodorant polyurethane foam and method for producing the same - Google Patents

Description

  The present invention relates to a deodorizing polyurethane foam comprising foaming beads foamed by heat generated during reaction of a polyurethane raw material and a deodorant, and a method for producing the same.

  A foamable bead-containing polyurethane foam has been proposed in which foamable beads are contained in a polyurethane raw material, and foamable beads are foamed by heat generated during the reaction of the polyurethane raw material. Since the foamed bead-containing polyurethane foam is excellent in air permeability, sound absorption, heat insulation and high hardness, it can be used as a cushioning material for automobiles, trains, aviation, furniture, etc., or a heat insulating material for building materials. In addition, the foamable bead-containing polyurethane foam may be required to have deodorizing properties depending on the application.

  On the other hand, as a foamed bead molded product having deodorizing properties, a foamed bead with a deodorant coating film made of a metal phthalocyanine derivative formed on the surface is pre-foamed and then shaped by molding Has been.

  However, since the deodorant foaming bead molded product is limited to metal phthalocyanine derivatives, there is little room for selection of the deodorant, and an inexpensive deodorant cannot be used. is there. Moreover, in order to fix the deodorant composed of a metal phthalocyanine derivative on the surface of the expandable bead as a coating film, a mixture in which the metal phthalocyanine derivative is mixed in the adhesive composed of an aqueous acrylic resin or an aqueous urethane resin is used. Therefore, there is a problem that the number of steps increases and the cost increases. Further, the deodorant expandable bead molded product is inferior in breathability because the adjacent expandable beads are in intimate contact with each other, as in the normal expandable bead molded product. Since it is difficult for outside air to enter, there is also a problem that it is difficult to expect the deodorizing effect of the deodorant fixed to the surface of the foamable beads inside the molded product.

JP-A-8-120112 JP 2001-261878 A

  This invention is made | formed in view of the said point, Comprising: It aims at provision of the cheap deodorizing polyurethane foam containing the expandable bead, and its simple manufacturing method.

The invention of claim 1 is a deodorant polyurethane foam comprising a polyurethane foam containing expandable beads and a deodorant , wherein the polyurethane foam is a polyol, polyisocyanate, expandable beads, heat reduction The foamed beads are foamed and cured from a polyurethane raw material containing an agent, a foaming agent and a deodorant, and the foamable beads are foamed by heat generation during the foaming reaction of the polyurethane raw material.

The invention of claim 2 is characterized in that, in claim 1 , the deodorant comprises one or both of catechin and bincho charcoal.

The invention of claim 3 is to foam and cure a polyurethane raw material containing a polyol, polyisocyanate, expandable beads, a heat reducing agent, a foaming agent and a deodorant, and generate the foamable beads by heat generation during the foaming reaction of the polyurethane raw material. The present invention relates to a method for producing a deodorant polyurethane foam characterized by foaming.

Invention of Claim 4 is Claim 3 WHEREIN: The said foamable bead is 10-50 weight part with respect to 100 weight part of polyols in the said polyurethane raw material, and the said deodorizer is 0.5-5 weight part. It is characterized by that.

  According to the deodorant polyurethane foam of the present invention, the deodorant can be exhibited by the deodorant. In addition, since odors generated from raw materials such as expandable beads can be deodorized, the deodorant polyurethane foam itself can have no odor or less. Moreover, according to the deodorant polyurethane foam of the present invention, since the outside air can be infiltrated into the inside of the foam by the breathability of the polyurethane foam, the deodorizing effect is also exhibited by the deodorizer inside the foam. can do. Furthermore, since catechin and Bincho charcoal, which are inexpensive general-purpose deodorants, can be used as the deodorant, the deodorant polyurethane foam can be made inexpensive.

  Further, according to the production method of the present invention, it is not necessary to previously apply a mixture of a deodorant and a fixing agent to the surface of the expandable beads to form a coating film, and it is also necessary to pre-expand the expandable beads. Therefore, the deodorant polyurethane foam can be produced simply and inexpensively.

  Hereinafter, embodiments of the present invention will be described in detail. The deodorant polyurethane foam in the present invention is a polyurethane foam containing foam beads and a deodorant. The polyurethane foam is foamed and cured from a polyurethane raw material containing polyol, polyisocyanate, foamable beads, heat reducing agent, foaming agent and deodorant, and the foamable beads are subjected to a foaming reaction of the polyurethane raw material. It is foaming due to the heat generated at the time.

  As the polyol used in the present invention, any one or both of known ether polyols and ester polyols used for polyurethane foams can be used. Examples of ether polyols include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sucrose, or polyhydric alcohols thereof. The polyether polyol which added alkylene oxides, such as ethylene oxide and a propylene oxide, can be mentioned. As ester polyols, polycondensation of aliphatic carboxylic acids such as malonic acid, succinic acid and adipic acid and aromatic carboxylic acids such as phthalic acid and aliphatic glycols such as ethylene glycol, diethylene glycol and propylene glycol. The polyester polyol obtained in this way can be mentioned.

  The polyisocyanate may be aromatic, alicyclic or aliphatic, and may be a bifunctional isocyanate having two isocyanate groups in one molecule, or three in one molecule. Trifunctional or higher isocyanates having the above isocyanate groups may be used, and these may be used alone or in combination.

  For example, as the bifunctional isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'- Fragrances such as diphenylmethane diate, 2,2′-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisonate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate Aliphatic ones such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, butane-1,4-diisocyanate Over DOO, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, there may be mentioned aliphatic, such as lysine isocyanate.

  Examples of the tri- or higher functional isocyanate include 1-methylbenzole-2,4,6-triisocyanate, 1,3,5-trimethylbenzole-2,4,6-triisocyanate, biphenyl-2,4,4 ′. -Triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5' tetraisocyanate, triisocyanate Examples thereof include phenylmethane-4,4 ′, 4 ″ -triisocyanate, polymeric MDI, and the like. Other urethane prepolymers can also be used. The polyisocyanate is not limited to one type, but one type. For example, one type of aliphatic isocyanate and The two types of aromatic isocyanates may be used in combination.

  The foamable beads are foamed by reaction heat generated when the polyurethane raw material reacts and foams, and are dispersed in the deodorized polyurethane foam in a state after foaming. The unexpanded foamable beads blended in the polyurethane raw material have a smaller particle size than the foamable beads after foaming, and it is easy to disperse and mix a desired amount in the polyurethane raw material. In general, in the method of manufacturing a molded body of beads, unexpanded expandable beads are pre-expanded and pre-expanded in a spherical state to a particle size of 1 to 5 mm, and the pre-expanded spherical expandable beads are molded. It is made into a molded body by being put in and heat-sealed. However, pre-foamed expandable beads are mixed and dispersed in a polyurethane raw material to form the deodorant polyurethane foam of the present invention. The pre-expanded expandable beads have a too large particle size and a desired amount is mixed. It is not preferable because it cannot be dispersed.

  Examples of the foamable bead material include polycarbonate, methyl methacrylate, polyethylene / polypropylene copolymer, polyethylene / polystyrene copolymer, acrylic / styrene copolymer, and polyuric acid. Among these, as a preferable example of the expandable beads, expandable polystyrene beads can be exemplified. The expandable polystyrene beads are made by impregnating polystyrene or styrene-based copolymer plastic with a foaming agent. As the foaming agent used for the expandable polystyrene beads, pentane, butane, propane or the like, and a polymer having a number average molecular weight of 1000 to 3000 is preferable. The expandable beads preferably have a heat resistant temperature of 80 ° C. or higher and a foaming start temperature of 150 ° C. or lower. When the heat-resistant temperature is lower than 80 ° C., the expandable beads are once foamed and then collapse and easily contract. On the other hand, when the foaming start temperature is higher than 150 ° C., the foamable beads are difficult to foam due to the heat generated when the polyurethane raw material is foamed. The amount of expandable beads is preferably 10 to 50 parts by weight with respect to 100 parts by weight of polyol. When the amount of expandable beads is less than 10 parts by weight, the density of the deodorant polyurethane foam is lowered and the hardness is lowered. On the other hand, if it exceeds 50 parts by weight, the heat generated when the polyurethane raw material is foamed cannot supply the amount of heat for foaming all of the expandable beads, and the expandable beads do not sufficiently expand (expand) and deodorant polyurethane foam. The foamable beads after foaming contained in the body have a small average particle diameter.

  The heat reducing agent is for preventing the foaming beads once foamed from collapsing and contracting due to heat when the polyurethane raw material is foamed, and the heat generated during foaming of the polyurethane raw material. It consists of a compound that can suppress the maximum exothermic temperature and suppress the. As the heat reducing agent, a compound that releases water when a predetermined temperature is reached and lowers the heat generation temperature when the polyurethane raw material is foamed by the latent heat of vaporization of water is preferable. Specific examples of the heat reducing agent include MW powder (registered trademark, manufactured by Shiraishi Calcium Co., Ltd.) having water in the bubbles of a thermoplastic resin foam composed of granular closed cells and inorganic hydrate. In particular, inorganic hydrates are preferred. Examples of the inorganic hydrate include at least one selected from the group of dihydrate gypsum, magnesium sulfate hydrate, and magnesium phosphate hydrate. The amount of the heat reducing agent is preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polyol. When the amount is less than 10 parts by weight, the heat reducing effect of the heat reducing agent is reduced, and the foamed beads once foamed easily contract due to heat generated when the polyurethane raw material is foamed, and the density of the deodorant polyurethane foam is low. It becomes lower and the hardness becomes lower. On the other hand, when the amount exceeds 30 parts by weight, the deodorant polyurethane foam tends to be a poorly foamed state having a puncture inside.

  As the foaming agent, water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, carbon dioxide gas, or the like is used. When the foaming agent is water, the amount added is determined within a range in which the desired density and good foamed state can be obtained in the deodorant polyurethane foam, and 3 to 5 parts by weight are particularly preferred with respect to 100 parts by weight of the polyol. When the amount is less than 3 parts by weight, the polyurethane foam does not sufficiently foam, and the heat generated during foaming of the polyurethane raw material is reduced, so that the foam beads are not sufficiently expanded (expanded), and the hardness of the deodorant polyurethane foam is low. Become. On the other hand, when the amount exceeds 5 parts by weight, heat generation becomes large when the polyurethane raw material is foamed, and the foamed beads once foamed shrink, and the hardness of the deodorant polyurethane foam is lowered.

  The deodorant may be either organic or inorganic, and is not limited to one type, and two or more types may be used. Examples of the organic deodorant include iron phthalocyanine compounds, cyclodextrins, and plant extracts such as catechin and tannin extracted from tea leaves. Examples of the inorganic deodorant include zinc, silver, magnesium, lead, tin, copper, titanium, aluminum, zirconium and other oxides, phosphates, silicates, and mixtures thereof. In the case of a mixture, it is desirable that the mixture be uniform in an amorphous state. The deodorant may be a porous material. Examples of the deodorant made of a porous material include zeolite, activated carbon, activated clay, and bincho charcoal. Among them, Bincho charcoal is easy to obtain and inexpensive, and is therefore preferable as the deodorant of the present invention. Catechin is an organic compound of polyhydric phenol that exerts a deodorizing action by adsorption of chemical reaction. Therefore, unlike the deodorizing property by physical adsorption, the re-release of the adsorbed substance due to temperature rise is extremely small. Particularly suitable as a deodorant in the present invention. Furthermore, the deodorant is preferably in a state that is easily dispersed in the polyurethane raw material, for example, powder or granular. Further, a suspension in which a powdery deodorant is dispersed in a liquid may be used.

  The addition amount of the deodorant is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyol. When the amount is less than 0.5 parts by weight, the deodorizing effect is lowered. On the other hand, when the amount exceeds 5 parts by weight, foaming of the polyurethane raw material is inhibited, and a deodorant polyurethane foam having a good foamed state cannot be obtained.

  The polyurethane raw material includes a catalyst. As the catalyst, a known catalyst for polyurethane foams can be used. For example, amine catalysts such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, tetramethylguanidine, tin catalysts such as stannous octoate and dibutyltin dilaurate, phenylmercurypropionate or lead octenoate And metal catalysts (also referred to as organometallic catalysts). The general amount of the catalyst is about 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the polyol.

  Furthermore, the said polyurethane raw material contains an additive suitably. Examples of the additive include a foam stabilizer and a pigment. Any foam stabilizer may be used as long as it is used for polyurethane foams, and examples thereof include silicone foam stabilizers, fluorine-containing compound foam stabilizers, and known surfactants. As the pigment, those according to the required color are used.

  The production of the deodorant polyurethane foam is preferably carried out by known slab foaming in which a polyurethane raw material is reacted at room temperature and atmospheric pressure after preparing the polyurethane raw material. Specifically, a polyol, a heat reducing agent, a foaming agent, a deodorant, a catalyst, and appropriate additives are mixed, then unfoamed foam beads are added and mixed, and polyisocyanate is injected into this mixture by a known polyurethane. The polyurethane raw material obtained by mixing in a machine is discharged onto a belt conveyor, and while the belt conveyor moves, the polyurethane raw material reacts under normal temperature and atmospheric pressure to cause natural foaming and curing, thereby deodorizing polyurethane Foam can be produced continuously. In addition, about the said deodorizer, in order to make dispersion | distribution in a polyol raw material favorable, it is preferable to mix with a polyol previously.

  Examples of the present invention will be specifically described below together with comparative examples. A polyurethane raw material is prepared by blending the components shown in Tables 1 to 4 in the ratios in the same table, slab foamed using the polyurethane raw material obtained by this preparation, and the resulting slab foam is 150 × 100. Cut to 50 mm to obtain deodorant polyurethane foams of Examples and Comparative Examples. Preparation of the polyurethane raw material involves first mixing a polyol with a heat reducing agent, foaming agent, deodorant, catalyst, and appropriate additives, and then adding and mixing unfoamed expandable beads, and adding polyisocyanate to the mixture. This was done by mixing. Table 1 shows the case where the type and amount of the deodorant is changed, Table 2 shows the case where the amount of the expandable beads is changed, Table 3 shows the case where the amount of the heat reducing agent is changed, Table 4 shows the case where the amount of the foaming agent ( This is a case where the amount of water) is changed.

  Polyols in Tables 1 to 4 are polyether polyols, product numbers: Sannix GP3050F, MW3000, functional group number f = 3, OH number = 33, manufactured by Sanyo Chemical Industries, Ltd., deodorant (Bincho charcoal), for deodorization, Powdered, manufactured by Kyodo Kyodo Latest, deodorant (catechin) is powder, manufactured by Sanyo Dye Co., Ltd. . 25, manufactured by Kao Corporation, metal catalyst is stannous octylate, product number: MRH110, manufactured by Johoku Chemical Industry Co., Ltd., foam stabilizer is silicone foam stabilizer, product number: F650A, manufactured by Shin-Etsu Chemical Co., Ltd., expandable beads Is expandable polystyrene beads, product number: NEWRS, heat-resistant temperature 120 to 130 ° C., unfoamed average particle size 0.8 mm, average particle size after foaming 1.2 mm, manufactured by Hitachi Chemical Co., Ltd., polyisocyanate is tolylene diisocyanate, product number : T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.

  For the deodorant polyurethane foams of Examples and Comparative Examples thus obtained, the state of the foam, the appearance of the expandable beads, the average particle diameter of the expandable beads, and the density (JIS K7222- 2004), and deodorant properties for ammonia were measured. The results are as shown at the bottom of Tables 1-4.

  The state of the foam was determined by cutting the deodorant polyurethane foam and determining whether or not there was a puncture (cavity) inside. Further, in the foam state column of Tables 1 to 4, “◯” indicates a case where there is no puncture and a good foamed state, and “puncture” indicates a case where puncture (cavity) is present inside.

  The appearance of the expandable beads and the average particle size of the expandable beads are determined by cutting the deodorant polyurethane foam and judging the appearance (size and presence / absence of shrinkage) of the expandable beads visually and averaging the expandable beads. This was done by measuring the particle size visually. In the bead appearance column of Tables 1 to 4, “◯” indicates that the expandable bead has a predetermined size, “small” indicates a small size, and “shrinkage” indicates a case where the foaming is once contracted after expansion.

  The deodorizing property was measured by storing a deodorant polyurethane foam test piece (150 × 100 × 50 mm) in a 2000 ml wide-mouth glass bottle, and injecting ammonia (2.8% aqueous solution, 100 μl) with a syringe. Was kept at room temperature for 24 hours, and then the residual ammonia in the wide-mouth glass bottle was measured by glass chromatography. The residual ammonia after 24 hours was measured in the same manner without accommodating a test piece of deodorant polyurethane foam in a wide-mouth glass bottle, and it was 100 ppm.

  From the results of Table 1, Examples 1A to 1D containing 0.5 to 5 parts by weight of Bincho charcoal and catechin as deodorizers with respect to 100 parts by weight of polyol can foam the polyurethane foam well, and In the case of Comparative Examples 1A and 1C containing less than 0.5 parts by weight of Bincho charcoal or catechin as a deodorant with respect to 100 parts by weight of the polyol, the deodorant was lowered while good deodorant was obtained. On the other hand, in Comparative Examples 1B and 1D containing more than 5 parts by weight, it can be seen that the polyurethane foam is punctured and cannot be foamed well. From this, it is understood that the amount of the deodorant is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyol.

  From the results of Table 2, Examples 2A to 2D, in which the amount of expandable beads is 10 to 50 parts by weight with respect to 100 parts by weight of polyol, the appearance of expandable beads is good and sufficiently foamed In Comparative Example 2B, in which the expandable beads are less than 10 parts by weight, the density of the deodorant polyurethane foam is low, whereas in Comparative Example 2A, in which the expandable beads exceeds 50 parts by weight, the expandable beads are sufficiently foamed. It can be seen that the average particle size of the expandable beads is less than 1.2 mm. From this, it is understood that the amount of expandable beads is preferably 10 to 50 parts by weight with respect to 100 parts by weight of polyol.

  From the results of Table 3, Examples 3A to 3C in which the amount of the heat reducing agent is 10 to 30 parts by weight are good in the state of the foam and the appearance of the expandable beads, whereas the amount of the heat reducing agent is 10 parts by weight. In Comparative Example 3B below, heat generation at the time of foaming is high, so that the foamed beads once foamed shrink, whereas in Comparative Example 3A in which the amount of the heat reducing agent exceeds 30 parts by weight, the foam has a cavity inside It turns out that it becomes a punk state. From this, it is understood that the amount of the heat reducing agent is preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polyol.

  From the results of Table 4, in Examples 4A to 4C in which the amount of the foaming agent (water) is 3 to 5 parts by weight, the foamed state is good and the appearance of the expandable beads is also good. In Comparative Example 4A having less than parts by weight, the expandable beads do not sufficiently foam, whereas in Comparative Example 4B exceeding 5 parts by weight, the once expanded foam beads are contracted. It can be seen that the average particle size is less than 1.2 mm and the hardness of the foam cannot be increased. From this, it is understood that the amount of the blowing agent (water) is preferably 3 to 5 parts by weight with respect to 100 parts by weight of the polyol.

  As described above, the deodorant polyurethane foam of the present invention is excellent in deodorizing properties, and can be used at low cost because catechin and bincho charcoal, which are general-purpose deodorants, can be used. Furthermore, since the deodorant polyurethane foam of the present invention can exhibit the breathability of the polyurethane foam, the deodorant in the foam can also exert a deodorizing action, and bedding, sofas, building materials It is suitable as a wall material series. Moreover, according to the manufacturing method of this invention, a deodorant polyurethane foam can be obtained easily and cheaply.

Claims (4)

A deodorant polyurethane foam comprising a polyurethane foam containing expandable beads and a deodorant ,
The polyurethane foam is foamed and cured from a polyurethane raw material containing a polyol, polyisocyanate, expandable beads, heat reducing agent, foaming agent and deodorant,
The deodorant polyurethane foam, wherein the foamable beads are foamed by heat generation during the foaming reaction of the polyurethane raw material. The deodorant polyurethane foam according to claim 1 , wherein the deodorizer comprises one or both of catechin and Bincho charcoal.   A polyurethane raw material containing a polyol, a polyisocyanate, an expandable bead, a heat reducing agent, a foaming agent and a deodorant is foamed and cured, and the expandable bead is foamed by heat generated during the foaming reaction of the polyurethane raw material. A method for producing a deodorant polyurethane foam. The extinction according to claim 3 , wherein the foamable beads are 10 to 50 parts by weight and the deodorizer is 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyol in the polyurethane raw material. Method for producing odorous polyurethane foam.