JPS5938247B2 - Method of manufacturing flame retardant foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a flame-retardant foam, and more particularly to a method for producing a flame-retardant foam obtained by applying the reactivity of isocyanates.

Conventional foams obtained by applying the reactivity of isocyanate include polyurethane foam obtained in the process of polyurethane bond formation through the reaction of polyisocyanate and polyol, and polyurethane foam obtained in the process of polyurethane bond formation and isocyanate trimerization reaction. In addition to the polyurethane-modified isocyanurate foam obtained by this method and the polyisocyanurate foam obtained only by trimerization of isocyanate, these foams can be combined with polyimide, polyamide, polycarbodiimide, polyurea, and polyoxazolidone bonds. A variety of foams are known, either by reaction during production or by introduction prior to foam production.

Typically, the production of these foams involves the presence of an isocyanate and a blowing agent, optionally one or more compounds capable of reacting with the isocyanate, such as polyols, epoxy compounds, polycarboxylic acids, acid anhydrides, etc. However, all of these foams can be made flame retardant to a certain extent depending on the type of material used.

In particular, isocyanurate foams that involve a trimerization reaction of isocyanate during foam production have good flame retardancy. In addition, halogen compounds,
There are known methods of adding phosphorus compounds, antimony compounds, titanium compounds, or crystal water-containing compounds during foam production to make it flame retardant, but none of these methods can achieve a high degree of flame retardancy, and When exposed to water, they often emit large amounts of toxic gas, making them unsuitable for use as building materials. As a result of continuing research aimed at further improving the flame retardance of various foams obtained by utilizing the reactivity of isocyanates, the present inventor added a soluble iron compound to the foaming stock solution during the production of these foams. It was discovered that the obtained foam has high flame retardancy, and the present invention was achieved.

That is, the present invention provides a polyisocyanate and a blowing agent,
In some cases, at least one of polyols, epoxy compounds, polycarboxylic acids, acid anhydrides, and other compounds capable of reacting with isocyanates is present (however, when a polyol is present, NCO/0H (equivalent ratio)
〉1.5) When manufacturing foam, the iron compound soluble in the foam manufacturing stock solution is calculated as 0 in terms of the amount of iron element.
．． A method for producing a flame retardant foam characterized in that the amount of the flame retardant foam is added in the range of 0.05 to 10% by weight.

The present invention will be explained in detail below.

In the present invention, the iron compound soluble in the production stock solution means that the iron compound added to the stock solution before foaming by mixing the raw material and the blowing agent is at least 0.05% by weight in terms of iron in the stock solution.
It means something that dissolves, but it is more efficient if all of the added amount is dissolved.

Iron compounds soluble in the production stock solution include synchropentanenyl iron (ferrocene), mono- and di-lower alkyl (C1-8) synchropentanenyl iron; for example, ethyldicyclopentadienyl iron, n- Synchropentanenyl iron compounds such as butyldicyclopentadienyl iron, diethyldicyclopentadienyl iron, di-n-butyldicyclopentadienyl iron, acetylacetone iron, iron chloride, and the like can be mentioned.

If the amount of iron compound added is too large, there is a problem that the inside of the foam will be burnt immediately after foaming (scorch occurs), and if it is too small, the flame retardant effect will be small.

Therefore, the range of the addition amount of the iron compound is 0.000000000 in terms of iron element, based on the total amount of the foam manufacturing stock solution, the third component such as polyincyanate and polyol reactive therewith, and the iron compound. 0.05 to 10% by weight (hereinafter, % indicates weight % unless otherwise specified), preferably 0.05 to 10% by weight.
It is in the range of 35 to 7%, more preferably 0.5 to 5%. The foam obtained by adding an iron compound by the method of the present invention rapidly oxidizes the side chains of the resin when it is exposed to flame due to the action of the iron compound, which has a strong oxidizing effect, and converts the main chain into a carbon polymer. It is believed that by guiding the polymer, it increases its heat resistance, slows down the potassium burning rate, and exhibits flame retardancy.

As for the resin used, the Q effect of the present invention increases as the resin itself has a larger thermal stability range. For example, in a urethane-modified isocyanurate foam, the GζNCO/0H equivalent ratio (hereinafter all NCO/0H refers to the equivalent ratio) is The higher the temperature, the more the carbonization yield increases due to the action of the iron compound when the flame is applied, and the amount of decomposed gas decreases, so the heat resistance and flame retardance of the foam improves. However, when iron compounds are added to polyurethane foams such as NCO/0H Ki1,
When exposed to flame, the amount of smoke generated decreases with the amount of ferrocene, but the flame retardancy actually decreases.

This means that U. S. P. 334l3ll and U. S. P
．． As seen in No. 3,294,685, the iron compound acts as a combustion catalyst, reducing incomplete combustion and thus reducing the amount of smoke, but conversely it is thought that the flame retardancy decreases. Therefore, the reaction of isocyanate is substantially achieved by polyurethane foam (NC) obtained only by polyol.
Q/0H+1), it is difficult to expect the effect of the present invention.

Among the foams used in the present invention, in the case of foams having a urethane skeleton, the mixing ratio of isocyanate and polyol during foam production is poor, resulting in an NCO/OH of 1.
．． It needs to be 5 or more, preferably 2.5 or more, and more preferably 4.0 or more.

When an iron compound is added to such a urethane-modified isocyanurate foam with a high NCO/0H, there is less weight loss even when heated at high temperature for a long time, and even when the foam is exposed to flame, compared to when no iron compound is added. , there is almost no deformation of the back side of the foam or the surrounding areas that are hit by the flame.

When an iron compound is added to a stock solution during foaming, if the compound is a powder, it is preferably used after being dissolved in a polyisocyanate component or a foaming stock solution other than polyisocyanate. Furthermore, when the iron compound is in liquid form, it may be added directly. In short, most of the iron compound, preferably all of the added iron compound, needs to be uniformly dissolved in the stock solution. A product that reacts with the reaction is obtained.

In addition to the iron compound used in the present invention, the heat resistance and flame retardance are further improved when the foam is manufactured by adding the ethylenediamine metal chelate compound previously filed (Japanese Patent Application No. 103,850/1982).

What is the ethylenediamine metal chelate compound used in combination?
General formula M(H2NCH2CH2NH2)RrlRn(
In the formula, M is a transition metal such as aluminum, copper, zinc, zirconium, cobalt, titanium, nickel, or manganese;
is an inorganic or organic ion, m and n are integers from 1 to 3. ) is a compound represented by In the above formula, n is metal M
It is related to the specific coordination number, and as a specific example of R, CH
3COO〈●〉-COO first class organic anion, Cl-S
Examples include inorganic anions such as O4-.

The metal chelate compound must be soluble in the foaming stock solution. Representative examples of such compounds include the following.

Ethylenediamine copper acetate, ethylenediamine copper octanoate, ethylenediamine copper benzoate, ethylenediamine cobalt acetate, ethylenediamine zinc acetate, ethylenediamine manganese acetate,
Ethylenediamine nickel chloride, ethylenediamine nickel acetate.

However, in the method of the present invention, one type or two or more types of ethylenediamine metal chelate compounds are used. - Shifumi 1t>1 The amount of ethylenediamine chelate compound added is
0.1 to 2 based on the total amount of polyisocyanate, polyols reactive therewith, and this chelate compound
0% (weight %, same below), preferably 0.5 to 10%
, more preferably in the range of 0.5 to 5%.

As mentioned above, this chelate compound needs to be soluble in the foam stock solution, and preferably 0.1% or more of the chelate compound added to the foam production stock solution is preferably completely dissolved.

Ethylenediamine metal compound insoluble in foam stock solution,
For example, even if 1 to 5% of ethylenediamine copper dichloride, ethylenediamine copper sulfate, ethylenediamine iron chloride, or ethylenediamine iron acetate is added, no synergistic effect with the iron compound on flame retardancy can be obtained. J
ISA-1321 difficulty? When attempting to manufacture a foam that passes the Class 2 test, that is, can be used as a quasi-incombustible enclosure material, the addition of an iron compound will eliminate both deformation and cracks, and will also eliminate the problems that occur during forced combustion. The amount of poisonous gas is extremely reduced and a product that passes the flame retardant class 2 test can be obtained, but when used in combination with an ethylenediamine metal chelate compound, the exhaust temperature, which is one of the standard values, can be lowered and deformation and cracking during combustion can be prevented. Therefore, it is possible to obtain products that have more effective action and pass specifications in a wider range of formulations.

Until now, such a flame-retardant and heat-resistant foam has not been found.
Commonly known flame retardants, such as halogen compounds, phosphorus compounds, and antimony compounds? Even with just adding additives, it was far from meeting the standards for passing the above flame retardant test.

Isocyanates that can be used in the present invention include diphenylmethane diisocyanate, polyphenylenepolymethylene polyisocyanate, 2,4-tolylene diisocyanate (
2,4-TD[), 2,6-tolylene diisocyanate (2,6-TDI), xylylene diisocyanate (X
Aromatic polyisocyanates such as D), aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isoborone diisocyanate, and organic polyisocyanates used in ordinary urethanization reactions. Isocyanates can be used alone or in combination of two or more.

In this case, the effect of the present invention is greater as the aromatic component increases. Polyols that can be used in urethane-modified isocyanurate foams, urethane-modified carbodiimide foams, etc. may have any range of hydroxyl groups as long as they are normally used in the production of polyurethane, and particularly preferred are those used in the production of general rigid polyurethane foams. polyether polyol, polyester polyol, or a mixture thereof, having a hydroxyl value within the range of 300 to 800.

Typical examples of polyether polyols include polypropylene ether glycol, polyethylene polypropylene ether glycol, polytetramethylene ether glycol, polypentamethylene ether glycol, polyhexamethylene ether glycol, poly-1,6-octamethylene ether glycol, and bisphenol A. Polyether glycols such as glycols having an aromatic ring obtained by adding propylene oxide or ethylene oxide to Polymers obtained by reaction with substances such as hexanetriol, pentaerythritol, glycerin, trimethylolphenol, trimethylolpropane, 1,4-butanediol, ethylenediamine or similar compounds thereof in the presence of a suitable catalyst. There are branched polyether polyols.

Further, a typical example of polyester polyol is one made from dibasic carboxylic acid and polyhydric alcohol.

Dibasic carboxylic acids useful for making this polyester are those that do not have any active hydrogen-containing functional groups other than their carboxyl groups; specific examples include phthalic acid, terephthalic acid, isophthalic acid, succinic acid, and glutaric acid. Acids such as , adipic acid, pimelic acid are suitable. These acid anhydrides can also be used. The carboxyl group-containing compound used in the production of the amide-modified or amide-urethane-modified isocyanurate foam is obtained by reacting the dibasic acid and the dibasic acid with a polyhydric alcohol. polyester having a group.

To produce the foam, these dibasic carboxylic acids are reacted with isocyanate, which is the main raw material, to synthesize an amide prepolymer having isocyanate groups at the terminals, and this is then combined with the isocyanate component. A method of preparing a foam in the presence of an iron compound, an ethylenediamine metal chelate compound, a trimerization catalyst, a blowing agent, a surfactant, and optionally a polyol, and a dibasic carboxylic acid. There is a method of adding directly to the foam manufacturing stock solution, ie, a one-step method.

When using the one-stage method, if the dibasic carboxylic acid used is a solid, it is preferably used after being dissolved in a polyol or the like. The production of polyimide-modified or polyimide-urethane-modified isocyanurate foams involves the reaction of isocyanates with acid anhydrides, and typical acid anhydrides used here include trimellitic anhydride, pyromellitic anhydride, Examples include acids, benzophenonetetracarboxylic anhydride, etc.

To produce foam using these, these acid anhydrides are reacted with isocyanate in advance to synthesize a prepolymer containing imide bonds and having isocyanate groups at the terminals, and this is used as the isocyanate component. It can be produced in the same manner as the amide-modified or amide-urethane-modified isocyanurate.

Various modified isocyanurate foams such as urethane-modified isocyanurate foams, amide-modified isocyanurate foams, etc. used when producing foams according to the method of the present invention, and in the case of producing pure isocyanurate foams, polypropylene glycol Alkali alcoholades such as polypropylene glycol sodium salt synthesized from; potassium benzoate;
Alkali metal salts such as potassium acetate, potassium oleate, potassium salts of polymerized linseed oil fatty acids, and N. N
5.Matris(dialkylaminoalkyno(c)-S
ym-hexahydrotriazine; 2,4,6-tris(
All known isocyanate trimerization catalysts such as dimethylaminoalkyl)phenol and tertiary amines such as triethylenediamine are effective, and these may be used alone or in mixtures.

Further, it is more effective to use an epoxy compound in combination with the above-mentioned trimerization catalyst. Epoxy compounds include substituted monooxides such as epichlorohydrin, allyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, styrene oxide, propylene oxide, butadiene monoxide, and glycidyl ethers such as diglycidyl ether and bisphenol A diglycidyl ether. etc. When producing various modified urethane foams with relatively low NCO/OH (but not less than 1.5), such as epoxy-modified urethane foams and amide-modified urethane foams, some of the trimerization catalysts can be used. Common urethanization catalysts, such as organotin compounds, phosphine, and tertiary amines, may be used in combination with the trimerization catalyst, or in some cases, a catalyst other than the trimerization catalyst that is compatible with the reaction with the isocyanate modifier.

In some cases, a foam may be obtained using only the urethanization catalyst. In addition, in a modified urethane foam in which both an iron compound and an ethylenediamine metal chelate compound are added, the ethylenediamine metal chelate compound exhibits a catalytic effect and the foam can be obtained even without using the above catalyst in some cases.

As with conventional foams based on isocyanates, the present invention may include the addition of surfactants to aid in the homogenization of the components of the reaction mixture during foam production and to adjust the cellular structure of the resulting foam. Surfactants include silicon-containing compounds such as polysiloxane-polyoxyalkylene copolymers and other organopolysiloxanes.

Also effective as surfactants are oxyethylated alkylphenols, oxyethylated aliphatic alcohols, and block copolymers of ethylene oxide and propylene oxide. The blowing agent used in the method of the invention is CO, which is produced by adding water to the foam mixture.
It also includes externally introduced gaseous substances such as 2 or CO2, nitrogen, etc., and mixtures thereof.

Another preferred blowing agent is a low boiling liquid that evaporates due to the heat of reaction generated during foam formation. Boiling point approximately -50℃
Fluorinated and chlorinated hydrocarbons at ~+110°C are well-compatible blowing agents; examples of such are methylene chloride, trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, monochloro Examples include difluoromethane, dichlorotetrafluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, dibromofluoromethane, and monobromotrifluoroethane. In addition, benzene,
There are also toluene, hexane, etc. These blowing agents can be used alone or in combination. The amount of the blowing agent is preferably adjusted so that the foam density is 0.015y/CTiL or more. In particular, when the foam is not used as a composite with a heat-resistant material (such as asbestos) and is used as a semi-noncombustible material, the density of the foam is preferably in the range of 0.027/(-FL to 0.37/d). When used as a composite, it can be a quasi-nonflammable material even if it is 0.3y/d or more.Therefore, depending on the intended use of the foam, those skilled in the art can appropriately It is only a matter of selection. In the present invention, a flame retardant may be added depending on the case.

As flame retardants, all those used for ordinary polyurethane foams and urethane-modified isocyanurate foams are effective. Typical examples thereof include tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(dibromopropyl) phosphate, etc., rogogenated organic phosphorus compounds, and inorganic flame retardants such as antimony oxide. As detailed above, according to the present invention, a foam can be obtained that has excellent flame resistance when exposed to flame, has little deformation and cracking even when forced combustion, and has excellent flame retardancy and heat resistance. In particular, when an iron compound and ethylenediamine metal chelate are contained, a foam that is effective as a quasi-nonflammable building material can be produced with a wider range of formulations. Various measured values were obtained using the following methods.

Dimensional change rate The foam sample was cut into 5 x 5 x 5 (?) cubes, and the dimensional change rate after continuous heating at 150°C for 3 days was measured in the direction perpendicular to the foaming direction (+) and in the direction parallel to the foaming direction ('
).

Surface flammability test JournalOfCellularP
But described in Journal of Cellular Plastics, November 1967 issue, page 479.
larChimneyTest (Battle 1, Chimney 1,
Test) method.

[Production example of ethylenediamine copper acetate] Dissolve 1 mol (60y) of anhydrous ethylenediamine in 700ml methanol, add 0.5 mol (90.7y) cuprous acetate while stirring with a stirrer, and stir for a while to form a deep blue color. A homogeneous solution is obtained.

When this material is filtered and the filtrate is concentrated, ethylenediamine copper acetate is obtained. Other chelates were also produced using similar formulations.

Example 11 SOnate58O (polymethylene-polyphenylene-polyisocyanate, NCO equivalent) 40,
20.9** R-11 trichloromonofluoromethane (manufactured by Asahi Glass Co., Ltd.) to 1407
7, and this was used as solution A, while GP-250 (propylene oxide added to glycerin, 0H value 67)
6. Ferrous chloride (Fe manufactured by Sanyo Chemical Co., Ltd.) 41.7y
Cl2.4H20) 2.5y was dissolved, and HHT{N-Mamartris(dimethylaminopropyl)-Sym-hexahydrotriazine}3y and SH-
193 (silicone surfactant, manufactured by Toray Industries, Inc.) 2.
9y was added and mixed well to prepare solution B. Solution B was added to solution A and stirred well with an electric drill to foam.

In the same way, when water is added in the amount of crystallized water contained in ferrous chloride without adding iron compounds (Experiment.46.2)
Table 1 shows the foaming recipe, foaming properties, and notes.

From Table 1, it can be seen that the dimensional change at high temperatures of the foam containing FeCl2.4H is significantly smaller than that of the foam containing water or ordinary urethane-modified isocyanurate foam. Example 2 Ferrocene 6.4f7 was heated and dissolved in 178.1y of PAPI-135 (polymethylene-polyphenylene-polyisocyanate, NCO equivalent: 135, manufactured by Upsilon, USA), and R-1129t was added, and this was used as A liquid. , while GP
-250227 to HHT4'F7, SH-1936.1
Add 7 and Rll6t and stir to make solution B.
A urethane-modified isocyanurate foam of NCO/0H-5 was prepared by mixing liquids A and B with an electric drill (Experiment Taki 4).

For comparison, a foam was also created using a method in which ferrocene was not added (Experiment 5). The formulation and physical properties of the finished foam are shown in Table 2, Jikkenya 4 and 5. The ferrocene-added foam has a small weight loss after heating at high temperatures. Also in the surface flammability test, the addition of ferrocene increases the residual weight and shortens the afterflame time.
Furthermore, by adding ferrocene, there is almost no change in the external shape after surface combustion. Next, a urethane foam was made using the same materials as in Experiment 4, with a charging ratio of PAPI135 and GP-250, and NCO/0H=1.05, and the effect of adding ferrocene in this case was examined.

The formulation and physical properties are shown in Experimental Waterfalls 6 and 7 in Table 2.

Looking at the physical properties of the experimental F66 foam in which ferrocene was added and the foam of Jikkenya 7 in which ferrocene was not added, the effect of ferrocene was not seen at all in terms of heat resistance. Regarding surface flammability, when ferrocene is added, the residual weight becomes smaller and the afterflame time becomes longer. From the above, it can be seen that adding ferrocene to urethane-modified isocyanurate foam improves flame retardancy, but adding ferrocene to urethane foam lowers flame retardancy.

Example 3 25.9 parts of ferrocene and R-
Solution A was prepared by dissolving 1195 parts of the liquid and adding 17 parts of Epicoat 819 (epoxy resin, manufactured by Mitsubishi Yuka Co., Ltd.), while 1 part of GP-2505, 33.6 parts of HHT, and 33.6 parts of SH.
-19330 parts and R-1180 parts are added to B.
A foam was made by mixing liquids A and B (
NCO/0H=9,0).

Is this form 2.5x22x22? Cut into pieces of size,
A JISA Al32l flame retardant class 2 test was conducted.

As a result, a smoke generation coefficient CA of 40, an exhaust temperature Tdθ of 85, and an afterflame time of 5 seconds or less were obtained. On the other hand, the foam made without adding ferrocene has large deformation.
The exhaust gas temperature Tdθ was 160, and no product was obtained that passed the standard value. Example 4 R-1191.5 to Is0nate580556.3 parts
and 18.5 parts of ferrocene were dissolved, and this was used as liquid A.
On the other hand, 10 parts of ethylenediamine chelate of copper acetate, 2 parts of HHTl, 19.7 parts of SH-193, and 1130 parts of R-1 were dissolved in 26 parts of GP-25 to prepare solution B, and solutions A and B were mixed with an electric drill to form a foam. Tsukutsuta (NC
O/0H=12.7).

This form is 2.5X22X22C77! It was cut into pieces of size and subjected to a JISA-1321 flame retardant class 2 test. As a result, a product was obtained that passed the standard values with a smoke generation coefficient CA32, an exhaust temperature Tdθ20, and an afterflame time of less than 1 second, without any deformation or cracks. On the other hand, a foam made by a known method without the addition of ferrocene and ethylenediamine chelate of copper acetate has a smoke emission coefficient of CA7O, exhaust temperature Tdθ of 110, and large deformation, making it impossible to obtain a foam that passes the standard values. Example 5 Solution A was prepared by dissolving 1193 parts of R-1 and 16 parts of ferrocene in 5801100 parts of PAPI, and adding 81950 parts of Epicote to this solution, while 16.5 parts of ethylenediamine chelate of copper acetate and 22 parts of HHT were added to 25033.5 parts of GP1. , SH-19365 parts and R-11174 parts were dissolved as liquid B, and liquid A and liquid B were mixed to form a foam (NCO/OH=19.5).

This foam was cut into a size of 2.5 x 22 x 22 CfL and tested for JIS Al32l flame retardant class 2. As a result, a test piece was obtained with a smoke generation coefficient CA4O, an exhaust temperature Tdθ50, an afterflame time of less than 1 second, and no deformation or cracks in the test piece itself, which passed the standard values. On the other hand, foamed products other than ferrocene and copper acetate ethylenediamine chelate undergo severe deformation after combustion, and the exhaust temperature Tdθ is 15
0, the flame retardant and heat resistance was significantly lowered, and no product that passed the standard values could be obtained. Example 6 16.8 parts of ferrocene and 1 part of R-1116 were dissolved in 101 parts of PAPI 5801, and 21.8 parts of Epicote 819 was added thereto to prepare solution A.
78 parts of 23.4 parts of ethylenediamine chelate of copper acetate dissolved in 4.6 parts of -2505, BPX-11 (ring-opening addition polymerization of propylene oxide to bisphenol A, 0H value 310, Asahi Denka Co., Ltd. )59.5
Part, HHT3l part, SH-19336 part and R-11
A mixture of 50 parts was used as liquid B, and liquid A and liquid B were mixed to form a foam (NCO/OH=7.3).

After keeping this foam at 70°C for more than 24 hours, 2.
5×22×22? Cut to size, JISA-1321
A flame retardant class 2 test was conducted.

As a result, a test piece was obtained with a smoke generation coefficient CA4O, an exhaust temperature Tdθ55, an afterflame time of less than 5 seconds, no deformation or cracks in the test piece itself, and which passed the standard values. Foamed products other than ethylene diamine chelate, ferrocene, and copper acetate were severely deformed after combustion, and no product that passed the standard values could be obtained. Example 7 16.8 parts of ferrocene and 1 part of R-1116 were dissolved in 1011 parts of PAPI 580, and 1.8 parts of Epicote 81,921.8 parts and 10 parts of tris-2,3-dibromopropyl phosphate were added thereto to prepare solution A.
78 parts of 23.4 parts of copper acetate ethylenediamine chelate dissolved in 4.6 parts of P-250, BPX-11 (
Ring-opening addition polymerization of propylene oxide to bisphenol A, OH value 310, manufactured by Asahi Denka Kogyo Co., Ltd.) 59.
5 parts, HHT3l parts, SH-19336 parts and R11
A mixture of 150 parts was used as liquid B, and liquid A and liquid B were mixed to form a foam (NCO/OH=7.3).

After keeping this foam at 70°C for more than 24 hours, 2.
5x22x22 (cut to V7l size, JISA-1
321 flame retardant class 2 test was conducted. As a result, the smoke generation coefficient C
A test piece was obtained with A45, exhaust temperature Tdθ42, and afterflame time of 5 seconds or less, with no deformation or cracks in the test piece itself, and which passed the standard values. On the other hand, foams to which ferrocene and copper acetate ethylenediamine chelate compounds are not added are severely deformed after combustion, making it impossible to obtain foams that pass the standard values. Example 8 Add 30 parts of adipic acid to 135,970 parts of PAPI and add 80 parts of adipic acid.
C. for 3 hours to synthesize a polymer with an NCO equivalent of 145 (NCO equivalent of PAPI135=135).

To 780 parts of this prepolymer, 25.6 parts of ferrocene, R
-11,100 parts and 81,939 parts of Epicoat were dissolved,
This was used as Solution A, and on the other hand, 35 parts of GP-25, 25 parts of ethylenediamine chelate of copper acetate, 6 parts of HHTl, SH-
19325.6 parts and 1128 parts of R-1 were dissolved, this was used as liquid B, and liquid A and B were mixed with an electric drill to form a foam (NCO/OH=16). The density of this foam was 0.0327/CTlt. This foam was subjected to the JISA-1321 flame retardant grade 2 test in the same manner as in Example 3, and the results showed that the smoke generation coefficient CA33 and the exhaust temperature Tdθ10
The afterflame time was 1 second or less, passing the standard value. For comparison, we made a foam without adding ferrocene and copper acetate ethylenediamine chelate and conducted a similar experiment. As a result, the deformation was extremely large at a smoke generation coefficient CA of 85, an exhaust temperature Tdθ of 80, and an afterflame time of 0 seconds, and it failed to meet the standard values. Example 9 After heating and dissolving 17.5 parts of acetylacetone iron chelate in 856 parts of PAP-580, 1100 parts of R-11 and 17.6 parts of Epicoat 819 (epoxy resin manufactured by Mitsubishi Yuka Co., Ltd.) were added to prepare solution A. On the other hand, 14 parts of ethylenediamine chelate of copper acetate was dissolved in 58 parts of GP-25, and 8.5 parts of HHTl, 330 parts of SH-193 and R-1190 were dissolved in 58 parts of GP-250.
The mixture was made into liquid B, and liquids A and B were combined and mixed vigorously with an electric drill to form a foam (NCO/
0H=8.7).

This foam was heated at 70°C for 3 days, left at room temperature for 2 months, and tested according to JISA-11321. There was no deformation or crack, and it was flame retardant with a smoke generation coefficient of CA45, an exhaust temperature of Tdθ70, and an afterflame time of 7 seconds. It had excellent heat resistance.

When this foam was foamed by removing the iron acetylacetone chelate and the ethylenediamine chelate of copper acetate, it was severely deformed after combustion, and the exhaust temperature was 180°C.
As a result, the flame retardant and heat resistance significantly decreased. Example 10 R-1191.5 to Is0nate580556.3 parts
part, 15 parts of Ferrocene, and 81,930 parts of Epicote were dissolved, and this was used as Solution A, while 26 parts of GP-250 and 81,930 parts of Epicote were dissolved.
1 part ethylenediamine chelate of copper benzoate to 2 parts HTl
Dissolve 0 parts of SH-193, and add 19.7 parts of SH-193 and R
-1130 parts dissolved was used as liquid B, and liquid A and B were mixed with an electric drill to make a foam (NCQ/0H
=12.7).

Is this form 2.5 x 22 x 22? Cut into pieces of size,
A JISA-1321 flame retardant grade 2 test was conducted. As a result, smoke generation coefficient CA25, exhaust temperature Tdθ70, afterflame time 3
The test piece itself was not deformed within seconds and passed the standard values. On the other hand, those without the addition of ferrocene and ethylenediamine chelate of copper benzoate had deformation and cracks, and could not meet the standard values. Example 11 A foam was prepared in the same manner as in Example 10 except that 10 parts of ethylenediamine chelate of cobalt acetate was added in place of the ethylenediamine chelate of copper benzoate added in Example 10 (NCQ/0H-12.7).

Regarding this form, in the same manner as in Example 10, JIS
A-1321 flame retardant class 2 test was conducted. As a result, a test piece was obtained that passed the standard values, with a smoke generation coefficient CA of 45, an exhaust temperature Tdθ of 70, an afterflame time of within 3 seconds, and no deformation or cracks in the test piece itself. Example 12 A foam was prepared in the same manner as in Example 10 except that 10 parts of ethylenediamine chelate of nickel acetate was added in place of the ethylenediamine chelate of copper benzoate added in Example 10 (NCQ/0H-12.7).

Claims (1)

[Scope of Claims] 1. Polyisocyanate and a blowing agent, optionally at least one of polyols, epoxy compounds, polycarboxylic acids, acid anhydrides, and other compounds that can react with the isocyanate, and optionally a catalyst. , foam stabilizers and other auxiliaries to produce flame-retardant foams, dicyclopentadienyl iron, mono- and di-lower alkyl (1 to 8 carbon atoms) di- An iron compound selected from the group consisting of cyclopentadienyl iron, acetylacetone iron and iron chloride and soluble in the production stock solution,
0.05 to 10% by weight of iron element based on the stock solution
A method for producing a flame-retardant foam, characterized in that when a polyol is added and used in combination as a raw material, the NCO/OH equivalent ratio is set to 1.5 or more. 2 Polyisocyanate and blowing agent, optionally polyol, epoxy compound, polycarboxylic acid, acid anhydride,
In producing flame-retardant foam by reacting a production stock solution consisting of at least one compound capable of reacting with isocyanates and other isocyanates, and if necessary, a catalyst, a foam stabilizer, and other auxiliary agents. Cyclopentadienyl iron, mono-
and di-lower alkyl (1 to 8 carbon atoms) dicyclopentadienyl iron, iron acetylacetonate, and iron chloride, and an iron compound soluble in the stock solution, in an amount of iron element relative to the stock solution. When adding an ethylenediamine metal chelate compound that is soluble in the stock solution in an amount of 0.05 to 10% by weight, and also using a polyol as a raw material, the NCO/OH equivalent ratio should be 1.5 or more. A method for producing flame-retardant foam characterized by: