JP2006111788A - Polyurethane foam formulation and polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane foam formulation and polyurethane foam having excellent flame retardancy. <P>SOLUTION: The polyurethane foam formulation contains a polyol component and an isocyanate component as main components. The polyol component is a combination of a polyether polyol and a polymer polyol having a loss on heating (mass%/min) peak temperature of 300-350°C in solid components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyurethane foam composition used for various molded articles such as automobile parts and indoor products, and a polyurethane foam obtained by foaming the composition. More specifically, the present invention relates to a polyurethane foam composition having greatly improved flame retardancy and The present invention relates to a polyurethane foam obtained by foaming the blend.

  Recently, high flame retardancy has been demanded in a wide range of fields such as building materials, automobile parts, and indoor products, and in order to make polyurethane foams widely used in these fields flame retardant. It is known to add various flame retardants. For example, it is known to add vinyl chloride, antimony trioxide, zinc white, halogen flame retardant, organophosphorus flame retardant, etc. to polyurethane foam formulations.

  However, the use of a halogen-based flame retardant is not preferable because there is a risk of deteriorating and destroying the global environment due to harmful halogen substances. In addition, even when various flame retardants such as organic phosphorus flame retardants are used, it may be caused by deterioration of the function of the polyurethane foam, and the flame retardant effect of the polyurethane foam is not yet sufficient, and further flame retardant effect Improvement is expected.

  For example, a polyurethane foam described in JP-A No. 11-226960, that is, a polyurethane foam which is a combination of a polyether polyol and a general-purpose polyol and does not contain a flame retardant, is still not sufficiently flame retardant.

Japanese Patent Laid-Open No. 11-226960

  This invention is made | formed in view of the said situation, and aims at providing the polyurethane foam compound and polyurethane foam excellent in the flame retardance.

  As a result of intensive studies to achieve the above object, the present inventors have, as a main component, a polyol component, an isocyanate, and a polyurethane foam formulation in which various additives such as a foaming agent, a catalyst, and a foam stabilizer are blended. As the above-mentioned polyol component, by using together the polyether polyol and the polymer polyol whose peak temperature of heat loss (mass% / min) in the solid component is in the range of 300 to 350 ° C., surprisingly, the flame retardant effect is obtained. The present inventors have found that it can be greatly improved and have reached the present invention.

Accordingly, the present invention provides the following.
Claim 1:
In the polyurethane foam formulation mainly comprising a polyol component and an isocyanate, the polyether polyol and the peak temperature of heat loss (mass% / min) in the solid component are in the range of 300 to 350 ° C. as the polyol component. A polyurethane foam composition characterized by using a polymer polyol in combination.
Claim 2:
The polyurethane foam formulation according to claim 1, wherein the blending ratio of the polyether polyol and the polymer polyol is 99/1 to 10/90 by mass ratio.
Claim 3:
The polyurethane foam formulation according to claim 1 or 2, wherein the base polyol in the polymer polyol has a number average molecular weight of 1,000 to 10,000.
Claim 4:
The polyurethane foam formulation according to any one of claims 1 to 3, wherein the polymer polyol has a specific gravity of 1.000 to 1.100.
Claim 5:
The polyurethane foam formulation according to any one of claims 1 to 4, wherein 0.1 to 10 parts by mass of a crosslinking agent is blended with respect to 100 parts by mass of the polyol component.
Claim 6:
A polyurethane foam obtained by foaming the blend according to any one of claims 1 to 5.

  According to the polyurethane foam formulation and polyurethane foam of the present invention, flame retardancy is greatly improved.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, the present invention will be described in more detail. The polyurethane foam composition of the present invention is composed mainly of a polyol component and an isocyanate, as in the normal case, and the polyol component includes a heat loss (mass% / min.) In the polyether polyol and the solid component. ) In combination with a polymer polyol having a peak temperature in the range of 300 to 350 ° C.

  Here, as the polyether polyol, a general-purpose polyether polyol can be used for a polyurethane foam molded article. For example, an ether skeleton composed of alkylene oxide is only propylene oxide (PO) or ethylene oxide. Polyether polyols composed of (EO) and propylene oxide are exemplified, and those in which the alkylene oxide portion is composed of propylene oxide and ethylene oxide are particularly preferred, and the ratio thereof is EO / PO = 8/92 to 18/82 ( The molar ratio) is particularly preferred. Moreover, the said polyether polyol may have functional groups other than hydroxyl groups, such as an amino group, as a functional group. Further, those having 2 to 4 functional groups, particularly those having 3 functional groups are preferred. As such a thing, the polyether polyol obtained using glycerol as an initiator is mentioned, for example. In addition, it is preferable that the average molecular weight of polyether polyol is 1,000-10,000.

  Moreover, as a commercial item of the above-mentioned various polyols, E-3030 (molecular weight 3000, f = 3, polyether polyol manufactured by Asahi Glass Co., Ltd.), V3943A (base polyol molecular weight 3000, f = 3, Dow Polyurethane Japan Co., Ltd.) Acrylonitrile / styrene 43% graft copolymer polyol), 3P56B (molecular weight 3000, f = 3, polyester polyether polyol manufactured by Takeda Pharmaceutical Co., Ltd.), and the like.

  In the present invention, in addition to the polyether-based polyol, a polymer polyol having a peak temperature of heat loss (mass% / min) in the solid component in the range of 300 to 350 ° C. is used in combination. Thereby, a flame retardance can be improved, maintaining the various characteristics of a polyurethane.

  The peak temperature of the heat loss (mass% / min) in the solid component of the above polymer polyol is in the range of 300 to 350 ° C. as described above, but it is particularly preferable to use one having a temperature of 330 to 350 ° C. . The heat loss means the mass reduction rate per unit time, and the measurement method is based on the thermogravimetric method. Further, the temperature rising rate is 1 ° C./min and is a constant condition. Within the range of the melting temperature of the above polymer polyol, the peak temperature is relatively low, melting (melt drop) occurs at a stretch on the low temperature side, and it is difficult to store heat because it drops outside the system, thus improving the flame retardant effect It is assumed that

  Specifically, the polymer polyol is a polymer made of polyalkylene oxide, preferably a base polyol having an average molecular weight of 3,000 to 8,000 and graft copolymerized with polyacrylonitrile, acrylonitrile-styrene copolymer or the like. Polyols are preferred. The alkylene oxide constituting the polyalkylene oxide preferably contains propylene oxide, and particularly preferably contains propylene oxide alone or contains both propylene oxide and ethylene oxide. Moreover, the thing whose density | concentration of the polymer component in a polymer polyol is 25 to 50% is preferable. Furthermore, the polymer polyol may have a functional group other than a hydroxyl group such as an amino group as a functional group. Further, those having 2 to 4 functional groups, particularly those having 3 functional groups are preferred. As such a thing, the polymer polyol obtained using glycerol as an initiator is mentioned, for example. In addition, it is preferable that the number average molecular weights of the base polyol in the said polymer polyol are 1000-10000. The blending amount of the polymer polyol is 5 to 80 parts by mass, more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the total polyol.

  As said isocyanate, well-known isocyanate can be mentioned, For example, tolylene diisocyanate, diphenylmethane diisocyanate, triphenyl diisocyanate, xylene diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. are mentioned.

  Although the compounding amount of the isocyanate is not particularly limited, it is usually recommended that the amount is 20 to 100 parts by mass with respect to 100 parts by mass of the total polyol. If it becomes closed cells and the amount is less than 20 parts by mass, the resin reaction of polyurethane foam may not proceed.

  Moreover, in this invention, in order to adjust hardness suitably, a crosslinking agent can also be mix | blended. Specific examples of the crosslinking agent include trimethylolpropane, diethylene glycol, sucrose (sugar), pentaerythritol, 1,4-butanediol, dipropylene glycol, ethylenediamine, glycerin, and the like, and propylene oxide or ethylene oxide is added thereto. And the like. Examples of such commercially available products include T-880 manufactured by Takeda Pharmaceutical Co., Ltd., GR-04 manufactured by the same company, XQ8221 manufactured by Dow Polyurethane Japan Co., Ltd., and the like. The blending amount of the crosslinking agent is appropriately adjusted with respect to each blending component, but is usually 0.1 to 10 parts by weight, particularly 1 to 5 parts by weight with respect to 100 parts by weight of the total polyol.

  In the polyurethane foam composition of the present invention, other non-halogen flame retardants such as clay, aluminum hydroxide, antimony trioxide, zinc white, calcium carbonate, ammonium polyphosphate, condensed phosphate ester are used as the flame retardant. Etc. can be used together. The blending amount is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyol component.

  In the polyurethane foam formulation, a foaming agent, a catalyst, a foam stabilizer and the like can be blended as necessary in the same manner as in a normal polyurethane foam formulation.

  Here, the foaming agent can be appropriately blended as necessary. For example, water can be preferably used, but a compound having a low boiling point such as methylene chloride or monofluorotrichloromethane can also be used. The blending amount of the foaming agent is appropriately adjusted, and is usually 0 to 15 parts by mass, particularly 0 to 5 parts by mass with respect to 100 parts by mass of the total polyol.

  As the catalyst, both amine-based and tin-based catalysts can be suitably used. As the amine-based catalyst, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, bis- (dimethylaminoethyl) ether. Examples of tin-based catalysts such as tetramethylpropylenediamine, trimethylaminoethylpiperazine, tetramethylethylenediamine, dimethylbenzylamine, methylmorpholine, ethylmorpholine, and triethylenediamine include stannous octate and dibutyltin dilaurate. These catalysts may be used alone or in combination of two or more. The compounding quantity of a catalyst can be 0-5 mass parts with respect to 100 mass parts of all the polyols, especially 0.1-1 mass part especially.

  Examples of the foam stabilizer include organopolysiloxanes, alkyl carboxylates, and alkylbenzene sulfonates. The blending amount of the foam stabilizer may be 0 to 5 parts by mass, particularly 0.5 to 2 parts by mass with respect to 100 parts by mass of the total polyol.

  Furthermore, various additives can be added to the polyurethane foam formulation of the present invention as necessary. For example, a colorant such as a pigment, a filler such as calcium carbonate, an antioxidant, and an ultraviolet absorber. , A light stabilizer, a conductive substance such as carbon black, an antibacterial agent, and the like can be blended.

  The polyurethane foam of the present invention is obtained by foaming the above polyurethane foam composition. As the foaming method, for example, a one-shot method or a prepolymer method can be employed. The foaming temperature can be 0 to 40 ° C, particularly 15 to 25 ° C. In this case, the compression rate in the container is not particularly limited and may not be compressed. However, the compression rate is usually 1/1 to 1/5.

The polyurethane foam of the present invention can be used for various molded products such as seat cushions for automobiles and transport vehicles, and soft slab foams such as sofas and mattresses. The density and tensile strength required for the intended molded products. Various characteristics such as compression residual strain, impact resilience, and elongation can be appropriately adjusted within a predetermined numerical range. For example, in the case of a seat cushion, the density (core) is adjusted to 25 to 80 kg / m ³ , tensile strength 75 kPa or more, compression residual strain 20% or less, impact resilience 30% or more, and elongation 90% or more. Is preferred.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Examples 1 and 2, Comparative Examples 1 and 2]
A polyurethane foam molded material (liquid temperature: 25 ° C.) shown in Table 1 was prepared, poured into a cavity space in a mold (mold temperature: 60 ° C.), foamed, and 100 mm high × 400 mm wide × A sheet-like polyurethane foam molded article having a length of 400 mm was obtained.

The contents of the above components are as follows.
Polyether polyol average molecular weight 4800
Functional group number 3
16% by mass of ethylene oxide (EO), 84% by mass of propylene oxide (PO)
Polymer polyol 1
Base polyol average molecular weight 4800
Base polyol functional group number 3
EO 15% by mass, PO 85% by mass
Styrene / acrylonitrile = 65/35 (mass ratio)
Peak temperature of heat loss (mass% / min) 330-340 ° C
Polymer polyol 2
Base polyol average molecular weight 4800
Base polyol functional group number 3
EO15% by mass, PO85% by mass
Styrene / acrylonitrile = 65/35 (mass ratio)
Peak temperature of heat loss (mass% / min) 380-390 ° C
Isocyanate 1
Product name “SBU Isocyanate J296” manufactured by Sumika Bayer Urethane Co., Ltd. (isocyanate equivalent 100, TDI / MDI mass ratio = 80/20
Catalyst A
Product name “Kaorraiser No. 31” manufactured by Kao Corporation
Catalyst B
Product name “Kaorraiser No. 12” manufactured by Kao Corporation
Foam stabilizer A
Product name “BY10-304” manufactured by Toray Dow Corning Silicone Co., Ltd.

Various physical properties of the obtained polyurethane foam were evaluated by the following evaluation methods. The results are shown in Table 2.
[Rebound resilience (%)]
It measured based on the specification of JIS K 6400-3 (2004 edition).
〔Growth rate(%)〕
It measured based on the specification of JIS K 6400-5 (2004 edition).
[Compressive residual strain]
The measurement was made based on the standard of JIS K 6400-4 (2004 edition).
[Flame Retardancy Test]
A combustion test was performed based on the standard of JIS D 1201 (1998 edition). If the test piece does not ignite or does not continue to burn after extinguishing the burner, or if the flame is extinguished before reaching the first mark, the burning time is not measured and the burning rate is 0 mm / min. It is described in the table below as “incombustibility”.

[Examples 3-5, Comparative Examples 3-5]
A polyurethane foam molding material (liquid temperature 25 ° C.) shown in Table 3 was prepared, poured into a cavity space in a mold (mold temperature 60 ° C.), foamed, and 100 mm high × 400 mm wide × A sheet-like polyurethane foam molded article having a length of 400 mm was obtained.

整泡剤Ｂ
商品名「ＳＲＸ ２７４Ｃ」東レ・ダウコーニング・シリコーン（株）製
架橋剤
商品名「ＥＬ５５５」旭硝子（株）製
イソシアネート２
商品名「コロネート１０２５」日本ポリウレタン工業（株）製

Foam stabilizer B
Product name “SRX 274C” manufactured by Toray Dow Corning Silicone Co., Ltd.
Crosslinker trade name “EL555” manufactured by Asahi Glass Co., Ltd.
Isocyanate 2
Product name “Coronate 1025” manufactured by Nippon Polyurethane Industry Co., Ltd.

  Various physical properties of the obtained polyurethane foam were evaluated by the same evaluation methods as described above. The results are shown in Table 4.

Claims (6)

In the polyurethane foam formulation having a polyol component and an isocyanate as main components, the polyether polyol and the peak temperature of heat loss (mass% / min) in the solid component are in the range of 300 to 350 ° C. as the polyol component. A polyurethane foam composition characterized by using a polymer polyol in combination. The polyurethane foam formulation according to claim 1, wherein the blending ratio of the polyether polyol and the polymer polyol is 99/1 to 10/90 by mass ratio. The polyurethane foam formulation according to claim 1 or 2, wherein the base polyol in the polymer polyol has a number average molecular weight of 1,000 to 10,000. The polyurethane foam formulation according to any one of claims 1 to 3, wherein the polymer polyol has a specific gravity of 1.000 to 1.100. The polyurethane foam formulation according to any one of claims 1 to 4, wherein 0.1 to 10 parts by mass of a crosslinking agent is blended with respect to 100 parts by mass of the polyol component. A polyurethane foam obtained by foaming the blend according to any one of claims 1 to 5.