JP5042449B2 - Flame retardant filter foam and method for producing the same - Google Patents

Description

The present invention relates to a flame retardant filter foam and a method for producing the same .

  The flexible polyurethane foam that has undergone film removal has excellent air permeability and filterability due to the three-dimensional network structure formed by film removal, so it can be used as a filter material in various fields such as home appliances, automobiles, and railways. Has been.

  In recent years, high flame resistance has been demanded for the materials themselves, regardless of general use or industrial materials, and high flame retardancy is also required for filter materials made of flexible polyurethane foam with film removal. ing. For example, FMVSS302 for automobiles and UL-94 for household appliances have high flame retardant specifications such as HBF, HF-2, and HF-1.

  As a method for imparting flame retardancy to the film-removed flexible polyurethane foam, there are a method in which a flame retardant is added to the blended raw material of urethane foam and the film is removed after foaming, and a method in which the film-removed flexible polyurethane foam is post-treated. is there. As a method for adding a flame retardant to a raw material for urethane foam, (1) a halogen flame retardant or a phosphorus flame retardant is added alone, (2) a halogen flame retardant and a phosphorus flame retardant are added together, (3) There are combined addition of antimony trioxide and halogen flame retardant, and (4) addition of aluminum hydroxide. Moreover, as a method of post-processing the film-removed flexible polyurethane foam, (5) a method of attaching aluminum hydroxide to the foam skeleton by impregnation or the like can be mentioned.

However, in the case of the above (1) to (4), that is, when removing the film after adding a flame retardant to the blended raw material and foaming, or when performing the post-treatment on the foam after film removal (5) The following problems were found to arise: That is, in the case of (1) to (3), the flexible polyurethane foam after film removal has a three-dimensional network skeleton structure and high air permeability, so that external air is easily supplied into the foam at the time of combustion, and flame retardant It becomes difficult to obtain sufficient flame retardancy with the added flame retardant. In the case of (4), a large amount of aluminum hydroxide must be added in order to satisfy the required high flame retardant standard, so that it becomes difficult to foam well and it becomes difficult to obtain a foam. In the case of (5), after the film removal of the flexible polyurethane foam, it is necessary to perform an impregnation process in a later process, so that not only the manufacturing work becomes troublesome but also the aluminum oxide is impregnated and adhered to the filter foam. There is a problem that becomes heavy.
Japanese Patent Laid-Open No. 2002-3713 JP 2002-58930 A

  The present invention has been made in view of the above points, and provides a flame retardant filter foam that is excellent in flame retardancy, light weight, and air permeability and that can be easily manufactured.

The invention of claim 1 is a flame-retardant filter foam comprising a soft polyurethane foam obtained by removing a soft polyurethane foam obtained by a reaction between a polyol and a polyisocyanate and containing expanded graphite, wherein the film-free soft polyurethane A phosphorus flame retardant and a foam stabilizer are contained in the foam, and the amount of the expanded graphite contained in the removed flexible polyurethane foam is 18 to 55 parts by weight per 100 parts by weight of the polyol, and the phosphorus flame retardant The weight ratio of expanded graphite and phosphorus-based flame retardant contained in the film-removed flexible polyurethane foam is not more than 23 parts by weight per 100 parts by weight of the polyol, and the weight ratio of expanded graphite: phosphorous flame retardant = 5: 1 to 1: 1, wherein the foam stabilizer is a silicone compound, the density of the flame retardant filter form 8 0 kg / ^{m 3,} air permeability according to the flame-retardant filter form, characterized in that at 50L / min or more.

According to a second aspect of the present invention, there is provided a flame retardant filter foam in which a blended raw material containing a polyol, a polyisocyanate, and expanded graphite is mixed and stirred to remove a film from a flexible polyurethane foam obtained by the reaction between the polyol and the polysocyanate. In the production method, the blended raw material contains a phosphorus flame retardant and a foam stabilizer made of a silicone compound, and the amount of the expanded graphite is 18 to 55 parts by weight per 100 parts by weight of the polyol. The amount of the flame retardant is 23 parts by weight or less per 100 parts by weight of the polyol, and the weight ratio of the expanded graphite to the phosphorus flame retardant is expanded graphite: phosphorous flame retardant = 5: 1 to 1: 1 and the density of the flame retardant filter foam is 8 to 40 kg / m ³ Further, the present invention relates to a method for producing a flame retardant filter foam, wherein the air permeability is 50 L / min or more.

  According to the flame retardant filter foam of claim 1, since the expanded graphite expands during combustion and the cell after film removal is blocked, the inside of the foam is blocked from outside air and exhibits high flame retardancy. Can do. In addition, the weight increase is small compared to the case where a large amount of aluminum hydroxide is contained, the weight is light, and the post-treatment for impregnation is unnecessary, so that the manufacturing operation is easy.

  According to the flame retardant filter foam of the first aspect, since the phosphorus-based flame retardant is contained in addition to the expanded graphite, the flame retardancy is further improved.

According to the flame retardant filter foam of claim 1, since the density of the filter foam is 8 to 40 kg / m ³ , the filter foam is lightweight, and since the air permeability is 50 L / min or more, the air permeability is excellent. The excellent air permeability reduces the filtration resistance and improves the filtration performance.

Embodiments of the present invention will be described below. The flame-retardant filter foam of the present invention comprises a film-extracted soft polyurethane foam containing expanded graphite. Density of the flame retardant filter form (JIS K 6400-compliant) is preferably 8~40kg / ^{m 3,} more preferably from 12~50kg / ^{m 3.} When the density is lower than 8 kg / m ³ , the density of the cell skeleton becomes too small and the combustibility becomes high. On the other hand, when the density is higher than 40 kg / m ³ , the lightness is impaired. Further, the air permeability (according to ASTM D 3574 test D) of the flame retardant filter foam is preferably 50 L / min or more. When the air permeability is lower than 50 L / min, the filtration resistance becomes too large and the filtration efficiency is deteriorated. The upper limit value of the air permeability is not limited, but a particularly preferable upper limit value is 280 L / min.

  The film-removed flexible polyurethane foam is obtained by removing a cell film (bubble film) of the flexible polyurethane foam by a known film removal treatment. Examples of the film removal treatment include post-treatment with heat, ozone, alkali and the like. By the film removal treatment, most of the cell membrane is removed from the flexible polyurethane foam to form a three-dimensional network skeleton structure.

  The flexible polyurethane foam before film removal is made of a soft polyurethane foam obtained by a reaction between a polyol and a polyisocyanate, and the soft polyurethane foam contains expanded graphite and preferably a phosphorus-based flame retardant.

  As the polyol, ether-based polyols or ester-based polyols known for flexible polyurethane foams can be used alone or in combination.

  Examples of ether polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, sucrose, and other polyhydric alcohols such as ethylene oxide and propylene oxide. The polyether polyol which added the alkylene oxide of this 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, etc. The obtained polyester polyol can also be used. In addition, a polymer polyol obtained by polymerizing an ethylenically unsaturated compound in a polyether polyol can also be used.

  As the polyisocyanate, aliphatic or aromatic polyisocyanates having two or more isocyanate groups, mixtures thereof, and modified polyisocyanates obtained by modifying them can be used.

  Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexamethane diisocyanate. Examples of the aromatic polyisocyanate include toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, polymeric polyisocyanate (crude MDI), and the like. Other prepolymers can also be used.

  As the expanded graphite, a known one can be used, and the raw material graphite is not particularly limited, but graphite having highly developed crystals such as natural graphite, quiche graphite, and pyrolytic graphite is preferable. Furthermore, natural graphite is preferable in consideration of the balance between the obtained characteristics and the economical efficiency. There is no restriction | limiting in particular as natural graphite to be used, Commercial products, such as SS-3N (made by Sumikin Chemical Co., Ltd.) and GREP-EG (made by Tosoh Corp.), can be used. There is no particular limitation on the average particle diameter of expanded graphite, but considering the mixing with polyol and the like, a powder of +50 mesh 80% or more is preferable.

  In the present invention, the amount of the expanded graphite is preferably contained in the flexible polyurethane foam at a ratio of 18 to 55 parts by weight, particularly 25 to 35 parts by weight, per 100 parts by weight of polyol. If the expanded graphite exceeds the upper limit of 55 parts by weight, the fluidity of the resin tends to be impaired when the flexible polyurethane foam is foamed. On the other hand, if the expanded graphite is less than 18 parts by weight, the amount of expanded graphite in the flexible polyurethane foam is small. Thus, the action of blocking the cell after film removal and blocking from the outside air at the time of combustion is lowered, and good flame retardancy cannot be obtained.

  The phosphorus-based flame retardant is not particularly limited, and compounds such as triphenyl phosphate, tricresyl phosphate, bis (1,3-phenylenediphenyl) phosphate, triaryl phosphate, trialkyl phosphate, alkyl phosphate Examples include compounds such as aryl, red phosphorus, ammonium polyphosphate, phosphate ester, melamine phosphate, melamine polyphosphate, guanidine phosphate, and ethylenediamine phosphate. It is preferably 23 parts by weight or less per 100 parts by weight of polyol, and the weight ratio of expanded graphite: phosphorous flame retardant is preferably 5: 1 to 1: 1, particularly 4: 1 to 2: 1. When the ratio of the phosphorus-based flame retardant is lower than the weight ratio of the expanded graphite: phosphorus-based flame retardant of 5: 1, the flame-retardant effect due to the addition of the phosphorus-based flame retardant tends to be difficult to obtain. When the ratio of the phosphorus-based flame retardant is higher than the weight ratio of the phosphorus-based flame retardant 1: 1, the flame retardant effect due to the expanded graphite is lowered when the filter foam is burned.

  In the flexible polyurethane foam, a foam stabilizer and a catalyst are added to improve the foaming reaction in the reaction between the polyol and the polyisocyanate, and an appropriate amount of water is added for the foaming reaction and hardness adjustment. The

  As a foam stabilizer, what consists of a silicone compound is preferable. In particular, a silicone compound having a polydimethylsiloxane chain number (N) of 25 to 100 is preferable. The foam stabilizer made of the silicone compound, particularly the foam stabilizer having a polydimethylsiloxane chain number (N) of 25 to 100 is effective not only as a foam regulating effect but also as a flame retardant aid. Specific examples of foam stabilizers having a polydimethylsiloxane chain number (N) of 25 to 100 include product number: F-650, manufactured by Shin-Etsu Chemical Co., Ltd., product number: SZ-1136, manufactured by Nippon Unicar Co., Ltd. It is done. The amount of the foam stabilizer made of the silicone compound is preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the polyol. When the addition amount is larger than the above range, the foamed flexible polyurethane foam has a large number of closed cells (closed cells), and the foam shrinks and deforms before film removal treatment due to cooling after foaming.

  As the catalyst, known ones for flexible polyurethane foams are used. For example, amine catalysts such as triethylamine, triethylenediamine, and tetramethylguanidine, tin catalysts such as dibutyltin dilaurate and stannous octoate, metal catalysts such as phenylmercurypropionate and lead octenoate (also referred to as organometallic catalysts) ).

  In addition, manufacture of the said flexible polyurethane foam is performed by the manufacturing method of the well-known polyurethane foam which mix | blends the said raw material, mixes and stirs the mixing | blending raw material with a stirrer, discharges and foams. Moreover, the film removal process is performed with respect to the flexible polyurethane foam manufactured in this way, and the flame-retardant filter foam of this invention is obtained.

Examples and comparative examples will be described below. The raw materials used are as follows.
Polyol: molecular weight 3000, OH number 56, product number GP3000, manufactured by Sanyo Chemical Industries, Ltd. Amine catalyst: product number LV-33, manufactured by Chukyo Yushi Co., Ltd. Tin catalyst: product number MRH-110, Johoku Chemical Industry Co., Ltd. -Foam stabilizer made of silicone compound: Part number F-650, manufactured by Shin-Etsu Chemical Co., Ltd.-Expanded graphite: Particle size +50 mesh 80% or more, Part number SS-3N, manufactured by Sumikin Chemical Co., Ltd. Flame retardant: Part number CR-504, manufactured by Daihachi Chemical Industry Co., Ltd., PVC (polyvinyl chloride): Part number PVC paste, manufactured by Shin Daiichi PVC Co., Ltd., Antimony trioxide: Part number PATOX, manufactured by Nippon Seiko Co., Ltd. -Polyisocyanate: Product number Coronate T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.

  The said raw material was mixed by the mixing | blending of Table 1, and the flexible polyurethane foam was foamed according to the manufacturing method of the well-known polyurethane foam slab. Briefly describing the procedure, raw materials other than the polyisocyanate were added to the polyol at a ratio shown in Table 1, and mixed by a known stirring method using a mixer to obtain a mixture. The obtained mixture is put into a tank of an injector, and the polyisocyanate is put into another tank of the injector, and the mixture and polyisocyanate are mixed, stirred and discharged in a mixing chamber of a high-pressure injector. A polyurethane foam slab was obtained, and a foam having a required dimension was cut from a portion other than the skin of the polyurethane foam slab. The foams thus obtained were subjected to film removal treatment for Examples 1 to 5, Reference Example 6 and Comparative Example 4 to obtain filter foams, whereas for Comparative Examples 1 to 3 and Comparative Example 5, film removal was performed. A filter foam was obtained without any treatment.

The air permeability (according to ASTM D 3574 test D) and density (according to JIS K 6400) were measured for the example product, the reference example product and the comparative example product obtained as described above. Furthermore, it was investigated whether it passed the flame retardance standard HF-1. The measurement results are as shown in the lower part of Table 1. In Examples 1 to 5 and Reference Example 6, the air permeability was good and the weight was light, and the flame retardant standard HF-1 was passed. On the other hand, for Comparative Examples 1 to 3 and Comparative Example 5 where the film removal treatment is not performed, the air permeability is lower than those of Examples 1 to 5 and Reference Example 6, and when used as a filter, the filtration resistance is increased. Filtration efficiency deteriorates and is not preferable. Furthermore, in Comparative Examples 1 to 3 and Comparative Example 5 that have not been subjected to film removal treatment, the structurally unstable cell film formed by the gas generated during the foaming reaction of the polyurethane foam remains. In addition, it is difficult to stably control the air permeability structurally, which is not preferable as a filter. In addition, Comparative Example 4 containing PVC and antimony trioxide instead of expanded graphite and phosphorus-based flame retardant, and Comparative Example 5 including phosphorus-based flame retardant and not containing expanded graphite fail flammability standard HF-1. It was inferior in flame retardancy. Comparative Example 6 in Table 1 is composed of a flame retardant foam (Part No. UN-2, manufactured by Inoac Corporation), which is made by impregnating a polyurethane foam having a density of 18 kg / m ³ with aluminum hydroxide or the like as a flame retardant. Comparative Example 7 is composed of a flame retardant foam (part number UN-3, manufactured by Inoac Corporation), which is made by impregnating a polyurethane foam having a density of 18 kg / m ³ with aluminum hydroxide or the like as a flame retardant. As in the comparative example, the air permeability, density, and flame retardancy were also measured for comparative examples 6 and 7. As is apparent from the measurement results shown in Table 1, Comparative Examples 6 and 7 were high in density and inferior in lightness.

Claims (2)

A flame retardant filter foam comprising expanded graphite contained in a soft polyurethane foam obtained by removing a flexible polyurethane foam obtained by a reaction between a polyol and a polyisocyanate ,
A phosphorus-based flame retardant and a foam stabilizer are included in the film-free flexible polyurethane foam,
The amount of the expanded graphite contained in the film-removed flexible polyurethane foam is 18 to 55 parts by weight per 100 parts by weight of the polyol, and the amount of the phosphorus flame retardant is 23 parts by weight or less per 100 parts by weight of the polyol. And the weight ratio of expanded graphite contained in the film-removed flexible polyurethane foam to the phosphorus flame retardant is expanded graphite: phosphorous flame retardant = 5: 1 to 1: 1.
The foam stabilizer comprises a silicone compound ;
A flame retardant filter foam, wherein the flame retardant filter foam has a density of 8 to 40 kg / m ³ and an air permeability of 50 L / min or more. A method for producing a flame retardant filter foam in which a mixing raw material containing a polyol, a polyisocyanate, and expanded graphite is mixed and stirred to remove a film from a soft polyurethane foam obtained by a reaction between the polyol and the polysocyanate,
  The blending material includes a phosphorus flame retardant and a foam stabilizer made of a silicone compound,
  The amount of the expanded graphite is 18 to 55 parts by weight per 100 parts by weight of the polyol, the amount of the phosphorus flame retardant is 23 parts by weight or less per 100 parts by weight of the polyol, and the expanded graphite and the The weight ratio of the phosphorus flame retardant is expanded graphite: phosphorus flame retardant = 5: 1 to 1: 1,
  The density of the flame retardant filter foam is 8 to 40 kg / m. ³ A method for producing a flame-retardant filter foam, wherein the air permeability is 50 L / min or more.