JP6482208B2 - Polyurethane foam - Google Patents

Description

  The present invention relates to a polyurethane foam, and more particularly to a polyurethane foam having flame retardancy. More specifically, the present invention relates to a polyurethane foam that can exhibit excellent flame retardancy without using a flame retardant.

  Polyurethane foams used in a wide range of fields such as automobiles, electrical products, furniture, and building materials have their own flame retardant standards in each field and application due to fire-related laws and regulations that are becoming stricter year by year. Therefore, it is necessary to make the polyurethane foam flame retardant according to the field and application.

Therefore, as a technique for making a polyurethane foam flame-retardant, there is a method of adding a flame retardant to the system.
In particular, halogen-containing phosphates are most frequently used as the types of flame retardants used in polyurethane foams. Examples include TCEP (trichloroethyl phosphate) and TDCP (trisdichloropropyl phosphate). These halogen-containing phosphate esters are flame retardants that have a synergistic flame retardant effect by combining the effects of a halogen compound effective in the gas phase and a phosphorus compound effective in the solid phase (for example, Patent Document 1). reference).

  In addition, depending on the application and required performance, halogen (bromine compounds, chlorine compounds, etc.), inorganic (hydrated metal compounds, antimony trioxide, zinc borate, etc.), inorganic phosphorus (red phosphorus, APP, etc.), Flame retardants such as nitrogen-based (triazines, melamine cyanurates, guanidines, etc.) and expandable graphite are also used (see, for example, Patent Document 2 or 3). Recently, a technique for developing flame retardancy using a polyol containing halogen or phosphorus has been developed.

  However, the above-mentioned flame retardant has a large amount of addition for effectively exhibiting the function, and requires an amount of 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin, or about 50 parts by mass in the case of more. It may be necessary (see, for example, Patent Document 4).

JP 2009-29993 A JP 2007-91866 A JP-A-10-218956 Japanese Patent Laid-Open No. 2007-2120

  However, in the polyurethane foam to which these flame retardants are added, the physical property values are deteriorated, in particular, the strength and hardness are reduced or the hardness is increased. Further, when a halogen-based flame retardant is used, gas may be generated, and suppression of such gas generation is desired particularly from the viewpoint of the environment. Furthermore, since many of the above flame retardants are expensive, it is not easy to control costs.

Specifically, the polyurethane containing the halogen-containing phosphate ester described in Patent Document 1 as a flame retardant contains halogen, and thus gas may be generated during combustion.
In addition, when using a powder such as melamine described in Patent Document 2, it is difficult to dissolve in the main raw material due to its low specific gravity, so it must be added in large quantities or used in combination with another flame retardant such as phosphate ester. It is difficult to obtain an effect. Furthermore, when powder is used, the extensibility of polyurethane decreases and the hardness increases. On the other hand, when a phosphoric acid ester is used, flame retardancy of the polyurethane appears, but the hardness of the polyurethane is greatly reduced and the strength is reduced.
In Patent Document 3, antimony trioxide and antimony pentoxide are used as an auxiliary agent for enhancing the flame retardancy of halogen compounds such as bromine compounds. A significant amount of addition is required to combust.

  Therefore, as described above, there has been a demand for a polyurethane foam excellent in flame retardancy without using a flame retardant or the like, rather than using a special additive, a flame retardant or the like to improve the flame retardancy.

  That is, an object of the present invention is to provide a polyurethane foam excellent in flame retardancy.

In order to achieve the above object, the following invention is provided.
<1> A silicone foam stabilizer represented by the following general formula (1) and having a ratio of m / (n1 + n2) of 1 or more and 5 or less;
A polyisocyanate component;
A polyol component;
A blowing agent;
A catalyst,
The mixture containing is a reaction-cured polyurethane foam.

(In General Formula (1), R ^A1 and R ^A2 each independently represent —CH ₃ or a phenyl group, R ^B1 represents a monovalent organic group having a weight average molecular weight of 400 to 3100, and R ^B2 Represents a divalent organic group having a weight average molecular weight of 400 to 3,100, X represents a substituent having active hydrogen, m represents an integer of 1 or more, and n1 and n2 each independently represents an integer of 0 or more. And at least one of n1 and n2 is 1 or more, wherein a plurality of R ^A1 and R ^A2 when m is 2 or more, a plurality of R ^B1 when n1 is 2 or more, and n2 is 2 In the above case, the plurality of R ^B2 may be the same or different.)

<2> The polyurethane foam according to <1>, wherein n2 in the general formula (1) represents an integer of 1 or more.

<3> The polyurethane foam according to <2>, wherein the silicone foam stabilizer has at least a hydroxyl group as a substituent having an active hydrogen represented by X in the general formula (1).

  According to the invention <1>, a polyurethane foam having excellent flame retardancy is provided.

  According to the invention <2>, a polyurethane foam having excellent water stopping properties is provided.

  According to the invention <3>, a polyurethane foam having excellent water stopping properties is provided.

It is the schematic showing the water-stop test apparatus used for the evaluation test of an Example and a comparative example.

  Hereinafter, the polyurethane foam according to the present invention will be described in detail.

[Polyurethane foam]
The polyurethane foam according to the present invention is obtained by reaction-curing a mixture containing a silicone foam stabilizer, a polyisocyanate component, a polyol component, a foaming agent, and a catalyst.
In addition, the said silicone foam stabilizer is represented by following General formula (1), and ratio of m / (n1 + n2) is 1-5.

(In General Formula (1), R ^A1 and R ^A2 each independently represent —CH ₃ or a phenyl group, R ^B1 represents a monovalent organic group having a weight average molecular weight of 400 to 3100, and R ^B2 Represents a divalent organic group having a weight average molecular weight of 400 to 3,100, X represents a substituent having active hydrogen, m represents an integer of 1 or more, and n1 and n2 each independently represents an integer of 0 or more. And at least one of n1 and n2 is 1 or more, wherein a plurality of R ^A1 and R ^A2 when m is 2 or more, a plurality of R ^B1 when n1 is 2 or more, and n2 is 2 In the above case, the plurality of R ^B2 may be the same or different.)

In the polyurethane foam, flame retardancy suited to the field is required depending on the application, and as a technique for flame retarding the polyurethane foam, there is a method of adding a flame retardant to the system. However, the polyurethane foam to which a flame retardant is added may cause deterioration of physical properties, particularly a decrease in strength and hardness, or an increase in hardness. In particular, when a halogen flame retardant is used, halogen gas may be generated. Furthermore, since many of the above flame retardants are expensive, it is not easy to control costs.
Therefore, a polyurethane foam excellent in flame retardancy without using a flame retardant is desired.

On the other hand, according to the polyurethane foam according to the present invention, m / (n1 + n2) is obtained by including a silicone foam stabilizer represented by the general formula (1) and having a ratio of m / (n1 + n2) of 1 to 5. It has been found that excellent flame retardancy can be exhibited compared to the case where the ratio of) exceeds the above range.
More specifically, by applying the silicone foam stabilizer to the polyurethane foam according to the present invention, the combustibility can be suppressed without using a flame retardant, or at least the combustion rate can be made slower.

In addition, although the mechanism which expresses this function is not necessarily clear, it is guessed as follows.
That is, in the silicone foam stabilizer represented by the general formula (1), the main chain portion of the siloxane structure may be cleaved, and the ends of the cleaved siloxane structure are bonded to generate a cyclic siloxane. Sometimes. This cyclic siloxane has the property of being easily volatilized, and the volatilized cyclic siloxane is easily combusted. Therefore, it is considered that the flame retardant is inferior due to the formation of the cyclic siloxane.
However, the silicone foam stabilizer used in the present invention has a ratio of m / (n1 + n2) of 1 or more and 5 or less, that is, it has a side chain of a polymer organic group having a molecular weight in the above range within a specific range. ing. When the siloxane structure is cleaved, a cyclic siloxane can be generated if there are three or more silicons. However, in the present invention in which the ratio of m / (n1 + n2) is in the above range, the generated cyclic siloxane also has a high molecular weight. It is thought that what has an organic group increases. It is presumed that the cyclic siloxane having a high molecular weight organic group having a molecular weight within the above range is difficult to volatilize, and thus the volatilization of the generated cyclic siloxane is suppressed, and as a result, the polyurethane foam can exhibit flame retardancy. The

In addition, according to the present invention, since a flame retardant is not used in polyurethane foam or the use of the flame retardant can be suppressed, the load on the environment and safety can be reduced, and the physical properties (mechanical strength and water stopping performance) due to the flame retardant. Reduction, complexity of production in powder dispersion, and non-uniformity can be suppressed. Moreover, since a flame retardant is not used or use of a flame retardant can be suppressed, it can be provided at low cost.
In particular, by obtaining a polyurethane foam using the silicone foam stabilizer of the present invention, it is possible to obtain a polyurethane foam having excellent water-stopping performance and excellent flame retardancy.

  Next, the structure and physical properties of the silicone foam stabilizer used in the present invention will be described in detail.

-Ratio of m / (n1 + n2) As for the silicone foam stabilizer used for this invention, ratio of m / (n1 + n2) in General formula (1) is 1-5. If it exceeds 5, the flame retardancy superior to polyurethane foam cannot be expressed. On the other hand, if it is less than 1, the side chain of the organic group of the polymer having a molecular weight within the above range will increase too much, and good alignment will be achieved. Foam performance is not obtained.

The ratio m / (n1 + n2) is preferably 1.5 or more and 4.5 or less, and more preferably 2.1 or more and 4.0 or less.
A method for calculating and controlling the ratio m / (n1 + n2) will be described later.

-R ^A1 and R ^A2
In General Formula (1), R ^A1 and R ^A2 each independently represent —CH ₃ or a phenyl group. Among these, —CH ₃ is more preferable.

・ R ^B1 and R ^B2
R ^B1 represents a monovalent organic group having a weight average molecular weight of 400 to 3100, and R ^B2 represents a divalent organic group having a weight average molecular weight of 400 to 3100.
In the case where the molecular weight of R ^B1 and R ^B2 is lower than the above lower limit, it is impossible to express the excellent flame retardancy of the polyurethane foam. This is presumably because the volatilization of the cyclic siloxane produced by cutting the siloxane structure due to the small molecular weight of the side chain is not satisfactorily suppressed.
On the other hand, when the molecular weights of R ^B1 and R ^B2 exceed the above upper limit, the molecular weight is too large, so that good foam regulating performance cannot be obtained.

The weight average molecular weights of R ^B1 and R ^B2 are preferably 1000 or more and 3000 or less from the viewpoint that foam formation is relatively easy and preferable for low foams and elastomers. In view of being preferable, it is preferably 2000 or more and 3000 or less. Moreover, 2000 or more and 3000 or less are preferable also from a viewpoint that stabilization of foam formation can be aimed at and it is preferable for flexible polyurethane foam preparation.
On the other hand, the molecular weight is preferably 500 or more and 1000 or less from the viewpoint that the lower raw material cost can be suppressed and the cost for producing the foam stabilizer is preferable.

The organic group having a molecular weight represented by R ^B1 or R ^B2 within the above range includes at least one of an ethylene oxide group (—C ₂ H ₄ O—) and a propylene oxide group (—C ₃ H ₆ O—). The organic group is preferably an organic group having all the structure other than the terminal composed of only an ethylene oxide group (—C ₂ H ₄ O—) and / or a propylene oxide group (—C ₃ H ₆ O—). It is preferable that

When R ^B1 and R ^B2 have at least one of an ethylene oxide (EO) group and a propylene oxide (PO) group, the PO: EO ratio (molar ratio) in the entire molecule affects the foaming characteristics of the polyurethane foam. From the standpoint of providing a suitable amount, it is appropriately selected according to the compatibility between the polyol component and the polyisocyanate component, that is, an appropriate ratio is used depending on the formulation and composition. The specific PO: EO ratio is not particularly limited, but is preferably in the range of 0: 100 to 55:45, and more preferably in the range of 10:90 to 50:50.

Examples of the substituent having an active hydrogen represented by X that is substituted at the terminal of R ^B2 include —OH, —SH, —NH ₂ , and among these, —OH is more preferable.

The structure of “R ^B1 ” is not particularly limited, but preferably has the following group (B1) structure. Further, the structure of “—R ^B2 —X” is not particularly limited, but preferably has the structure of the following group (B2).

In (group (B1), represents an integer of 0 or more each independently a1 and b1, there is no possibility a1 and b1 are simultaneously 0 .X ¹ is an alkyl group such as a methyl group (-CH ₃₎ or, Represents an acetyl group (—COCH ₃ ).
In the group (B2), a2 and b2 each independently represent an integer of 0 or more, but a2 and b2 are not 0 at the same time. X ² represents a -H. )

PO in the case where R ^B1 is the structure of the group (B1) and -R ^B2 -X is the structure of the group (B2) and does not have an EO group and a PO group other than R ^B1 and R ^B2 : The EO ratio represents “(b1 + b2) :( a1 + a2)”.

As the ^{X 1} in group (B1), -CH ₃ or -COCH ₃ Among the preferred.

Active hydrogen The silicone foam stabilizer represented by the general formula (1) preferably has one or more substituents having active hydrogen in the molecule. That is, n2 in the general formula (1) is an integer of 1 or more, and preferably has at least one “X”. By having a substituent having active hydrogen, the reactivity with the resin can be imparted by selecting the partner resin, and the reactivity with the isocyanate group can be imparted when forming a polyurethane foam. Thereby, a water stop can be raised more in the polyurethane foam obtained.

The number of substituents having active hydrogen in the molecule is more preferably 1 or more and 3 or less. By being 3 or less, favorable foam regulating performance can be maintained.
From that viewpoint, n2 in the general formula (1) is more preferably 1 or more and 3 or less.

-About specification of the structure of a foam stabilizer First, the weight average molecular weight of the whole foam stabilizer can be measured by gas chromatography (GPC). The molecular weights of R ^B1 and R ^B2 can also be measured by gas chromatography (GPC) after being decomposed by a chemical reaction. In addition, the strength ratio of the end of the side chain represented by the general formula (1), that is, “X” and “R ^B1 terminal group”, the ratio of PO and EO of R ^B1 and R ^B2 of the general formula (1) Etc. can be measured and analyzed by NMR.
Further, the ratio of m, n1, and n2 in the general formula (1) can also be calculated from the overall molecular weight obtained from the above, the intensity ratio, the PO: EO ratio, and the like.

  In addition, the silicone foam stabilizer used by this invention can be manufactured by a conventionally well-known method.

Next, materials other than the silicone foam stabilizer in the polyurethane foam according to the present invention will be described.
Polyurethane foam, for example, as a urethane raw material, a method of pouring a mixed stock solution containing a polyol, polyisocyanate, and, if necessary, a chain extender into a mold, molding the mixed stock solution on a release paper, and after heat curing, It can be formed by a method of punching into a predetermined shape. The mixed stock solution containing the urethane raw material contains at least the silicone foam stabilizer, the foaming agent and the catalyst according to the present invention, and may further contain other additives.

-Polyol-
As the polyol, for example, a polyether-based polyol such as polyoxypropylene polyol (PPG), polyoxyethylene polyol (PEG), a copolymer of PPG and PEG, or polyoxytetramethylene polyol (PTMG) is preferably used. Polyether-based polyols (particularly PPG and PTMG) are excellent in hydrolysis resistance as well as reactivity, so that durability and resilience of the polyurethane foam are likely to increase. In addition, polyether polyols have the advantage of low viscosity and high handleability.

  In addition to polyether polyols, polyols include dicarboxylic acids (adipic acid, sebacic acid, phthalic acid, dimer acid, etc.) and glycols (ethylene glycol, propylene glycol, 1.4-butanediol, 1.6-hexanediol, 2 Polyester polyol (PES), polycaprolactone polyol (PCL), polycarbonate polyol (PCA), (hydrogenated) polybutadiene-based polyol, (hydrogenated) polyisoprene condensed with -methylpropanediol, 3-methylpentanediol, etc. A system polyol or the like may also be used.

  In addition, it is preferable that the polyol is reacted with an excess equivalent of an isocyanate in advance and used as a prepolymer of a terminal NCO group because the resilience and toughness of the polyurethane foam are enhanced.

-Polyisocyanate-
As the polyisocyanate, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), crude MDI (cr-MDI), or the like is preferably used. In particular, it is preferable to use diphenylmethane diisocyanate (MDI) -based isocyanate because the reactivity is high and the durability and resilience of the polyurethane foam are easily increased.

-Chain extender-
Examples of the chain extender include aromatic diamines (for example, 4,4′-diamino-3,3′-dichlorodiphenylmethane (MOCA)), glycols having a molecular weight of 500 or less, or polyfunctional alcohols (for example, ethylene glycol, 1,4- Butanediol, 1,6-hexanediol, trimethylolpropane, glycerin, trimethylolpropane, etc.) and their ethylene oxide adducts or propylene oxide adducts, ethylene oxide adducts or propylene oxide adducts of bisphenol A, ethylene of hydroquinone It is preferable to use an oxide adduct or an ethylene oxide adduct of resorcinol.

  Among these, the chain extender is a low molecular polyol of a primary alcohol having a molecular weight of 200 or less, and ethylene oxide addition of ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, hydroquinone, resorcin. A thing etc. are the most preferable.

-Catalyst-
Examples of the catalyst include an organometallic compound catalyst and an amine catalyst.
Examples of the organometallic compound-based catalyst include tin-based, titanium-based, bismuth-based and nickel-based organometallic catalysts such as organotin compounds such as stannous octenoate and stannic dibutyllaurate. It is done.
Examples of amine-based catalysts include amine-based catalysts such as monoamines, diamines, triamines, cyclic amines, alcohol amines, ether amines, and the like, for example, triethylenediamine, triethylamine, n-methylmorpholine, n-ethylformomo. Phosphorus, N, N, N ′, N′-tetramethylbutanediamine and the like.
The addition amount of the catalyst is appropriately used in an appropriate ratio depending on the formulation.

-Foaming agent-
Examples of the foaming agent include water, halogenated alkanes such as monofluorotrichloromethane and dichloromethane, low-boiling alkanes such as butane and pentane, and azobisisobutyronitrile that generates cracked nitrogen. However, halogenated alkanes such as monofluorinated trichloromethane and dichloride methane are not preferred because of environmental problems.
The addition amount of the foaming agent is appropriately used in an appropriate ratio depending on the required density of the polyurethane foam.

-Waterproofing agent-
In the present invention, a hydrocarbon compound may be added as a waterproofness-imparting agent in order to increase the water-stopping property. The water-stopping property can be further improved by mixing a waterproofing agent. As the waterproofing agent, those which are solid at room temperature and excellent in compatibility with urethane resins are preferable, and as a hydrocarbon compound, a melting point of about 100 ° C. which is said to be a petroleum resin obtained by polymerizing C5 to C9 fractions. Examples thereof include solid resins and petroleum waxes.

  However, if the waterproofness-imparting agent is simply mixed, the flame retardancy is lowered and the compressive strain is deteriorated. Therefore, the amount of the waterproofness-imparting agent added is 10 parts by mass with respect to 100 parts by mass of the polyurethane foam. The amount is preferably 30 parts by mass or less and more preferably 15 parts by mass or more and 25 parts by mass or less.

-Other additives-
Examples of other additives include colorants such as pigments for making polyurethane foam a specific hue, fillers such as calcium carbonate, antioxidants, conductive materials such as carbon black, and the like. It may be added accordingly.

The thickness of the polyurethane foam of the present invention can be arbitrarily selected according to the purpose, but considering the molding conditions, the thickness can be 10 mm or less, and even if it is flexible, it has excellent mechanical strength. It can be formed to a thickness of 0.1 mm to 1.0 mm.
In addition, in this specification, the value measured based on JIS-K6400 is used for the thickness of a sheet | seat. That is, a test piece of polyurethane foam was punched 100 × 100 mm wide, 9 points were measured with a dial gauge having a precision of 1/100 mm in the foaming direction, and the average value was taken as the sheet thickness.

(Foaming method)
The polyurethane foam production method includes a slabstock method, a casting method such as spray coating or roll coating, a mold method for molding in a mold, a dispenser method for casting from a thin nozzle, etc., and the production of the polyurethane foam according to the present invention Any method can be used as the method.

  In addition, when manufacturing the polyurethane foam according to the present invention, the amount of the silicone foam stabilizer described above is preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the polyurethane foam. The range of 0.7 parts by mass or more and 2.0 parts by mass or less is more preferable.

(Use)
The polyurethane foam according to the present invention is used, for example, for water-stopping purposes of various products such as automobile air conditioners, refrigerators, prefabricated houses, unit baths and the like.

Examples will be described below, but the present invention is not limited to these examples. In the following examples and comparative examples, “part” is based on mass unless otherwise specified. Moreover, Examples 1-4, 7-12, 14-21, 23-26, and 28 shown below are shown as reference examples for the present invention.

(Production method of polyurethane foam sheet)
In the resin cup, components other than isocyanate among the components described in Tables 1 and 2 described below are added and stirred with a mixer. The isocyanates listed in Tables 1 and 2 are added to the stirred mixture, and further stirred with a mixer. The agitated material is applied to a peelable process paper with a constant thickness (500 μm), and the peelable process paper is further covered so that air does not enter from above. After placing in an oven at 70 ° C. for 5 minutes, it was further placed in an oven at 110 ° C. for 5 minutes. After completion of foaming, it was left at room temperature for 7 days, and the two process papers were peeled to obtain a sheet.

(Production method of polyurethane foam slab)
In the resin cup, components other than isocyanate among the components shown in Tables 3 to 5 described later are added and stirred with a mixer. The isocyanates listed in Tables 3 to 5 are added to the stirred product, and the mixture is further stirred with a mixer. The agitated material was placed in a box-shaped container, cured after completion of foaming at 100 ° C. for 24 hours, and further allowed to stand at room temperature for 7 days to obtain a slab.

  In addition, the foam stabilizer of Table 1 thru | or Table 5 has a structure of the following general formula (A).

In Tables 1 to 5, “PO ratio” represents “(b1 + b2) / (a1 + a2 + b1 + b2) × 100”, and “EO ratio” represents “(a1 + a2) / (a1 + a2 + b1 + b2) × 100”.
In Tables 1 to 5, there are some numbers that are not integers as numerical values of “m”, “n1”, and “n2”, and this represents an average value in the used foam stabilizer.
“R ^B1 portion Mw” and “R ^B2 portion Mw” described in Tables 1 to 5 represent the weight average molecular weight Mw of the portion corresponding to R ^B1 and R ^B2 in the general formula (1).

In addition, the detail of each component of the said Table 1-Table 5 is as follows.
Polyol 1: Actcol EP-240 (Mitsui Chemicals)
Polyol 2: EXCENOL 4030 (Asahi Glass Co., Ltd.)
Polyol 3: Actol 3P-56M (Mitsui Chemicals)
Cross-linking agent: 1,4-butanediol (BASF Idemitsu Co., Ltd.)
Isocyanate 1: Coronate T-65 (Nippon Polyurethane Industry Co., Ltd.)
Isocyanate 2: DC-6974 (manufactured by Nippon Polyurethane Industry Co., Ltd.)
Metal catalyst: Stanocto (manufactured by API Corporation)
Amine catalyst 1: Dabco 33Lv (manufactured by Air Products Japan)
Amine catalyst 2: u-cat SA 102 (manufactured by San Apro Co., Ltd.)
Additive 1: Made by Mitsui Chemicals, FTR, high purity aromatic resin

-Evaluation-
With respect to the foams obtained in the above Examples and Comparative Examples, each characteristic value was measured by the following method.
-Foam density The foam density was measured according to JIS K 6400-1 (soft urethane foam test method).

-Combustion test In the obtained polyurethane foam slab or sheet, a sample having a length of 100 mm was prepared. About this sample, the combustion test was implemented by the method based on US automobile safety standard FMVSS S302, and the burned length was measured.
In addition, the thing which 100 mm burned was evaluated as "complete combustion", and the thing which all did not burn out was evaluated as "self-extinguishing".
In addition, the burn rate was measured for those that burned completely. The results are shown in Tables 1 to 5.

-Water-stopping For water-stopping, a U-shaped water-stopping tester as shown in FIG. 1 is used, and a U-shaped test piece 1 having a thickness of 10 mm and a width of 15 mm is placed between two acrylic resin plates 3. In order to obtain a compression rate of 50% of the product thickness, water was injected into the U-shape from above to achieve a predetermined water pressure. The water stoppage was expressed as a water pressure height of 2 (cm) that does not leak for 24 hours.
The water stoppage is determined to be good when the waterstop pressure is 50 mm or more with a waterstop holding time of 24 hours.

As shown in Table 1 and Table 2, in Examples 1 to 10 in which the ratio of m / (n1 + n2) is in the range of 1 to 5, self-extinguishing results are obtained, and the ratio exceeds 5 Excellent flame retardancy is obtained as compared with Comparative Examples 1 to 9.
Moreover, as shown in Table 3, in Examples 11 to 16 in which the ratio of m / (n1 + n2) is in the range of 1 to 5, the ratio is more than 5 in Comparative Examples 10 to 12. In comparison, the burning rate is suppressed, and excellent flame retardancy is obtained.
Further, unlike the above examples and comparative examples using ether-based polyols, in Examples 17 to 28 shown in Tables 4 and 5 using ester-based polyols, the ratio of m / (n1 + n2) is 1. As a result of being in the range of 5 or less, a self-extinguishing result is obtained, and excellent flame retardancy is obtained as compared with Comparative Examples 13 to 23 in which the above ratio exceeds 5.

1 Test piece 2 Hydraulic height 3 Acrylic resin plate

Claims (2)

A silicone foam stabilizer represented by the following general formula (1) and having a ratio of m / (n1 + n2) of 1 or more and 5 or less;
A polyisocyanate component;
A polyol component;
Only water as a blowing agent,
A catalyst,
A polyurethane foam in which a mixture containing is reactively cured.


(In General Formula (1), R ^A1 and R ^A2 each independently represent —CH ₃ or a phenyl group, and R ^B1 represents a weight average molecular weight of 2000 to 3100 having a structure represented by the following group (B1): represent the following monovalent organic ^radicals, (the above X represents a -OH) group represented by ^-R B2 -X is part of the ^{R B2} has a structure represented by the following groups (B2) Represents a monovalent organic group having a weight average molecular weight of 2000 to 3100. m represents an integer of 1 or more, n1 and n2 each independently represents an integer of 0 or more, and at least one of n1 and n2 is 1 or more. In addition, a plurality of R ^A1 and R ^A2 when m is 2 or more, a plurality of R ^B1 when n1 is 2 or more, and a plurality of R ^B2 when n2 is 2 or more are the same. Whether or not It has.)


In (group (B1), it represents an integer of 0 or more in each of a1 and b1 independently never a1 and b1 are simultaneously 0 .X ¹ represents an alkyl group or an acetyl group.
In the group (B2), a2 and b2 each independently represent an integer of 0 or more, but a2 and b2 are not 0 at the same time. X ² represents a -H. )   The polyurethane foam according to claim 1, wherein n2 in the general formula (1) represents an integer of 1 or more.