JPH0482006B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a foaming resin composition that provides excellent flame retardant properties of the resulting foam and excellent liquid fluidity during foaming. (Prior art) Recently, flame retardant requirements for building materials, especially residential exterior wall materials, have become more stringent, and a model box test No. 1372 has been added to the Ministry of Construction notification No. 1231 semi-flammability test. It came to this. The Ministry of Construction Notification No. 1372 model box test refers to the afterflame in the same No. 1231 quasi-noncombustible test.
It is a very demanding process that requires meeting the regulatory values for temperature, time, area, and smoke production coefficient, then increasing the size of the test specimen and determining the amount of heat generated during combustion and the shape after combustion.
Structures using conventional isocyanurate foam (a type of polyurethane foam) having isocyanurate rings made from industrial polyol as a raw material undergo significant shape change after combustion and have a large calorific value, so the above-mentioned No. 1372 Passing the model box test is difficult. On the other hand, structures using known phenol foams do not change their shape after combustion, but have the disadvantage of a long afterflame time after combustion. When switching manufacturing equipment that has been conventionally used for molding isocyanurate foam (a type of polyurethane foam) having isocyanurate rings to molding phenol foam, the heating device during and after foaming must be heated to high temperature. In addition, it is necessary to change to a device that can heat for a long time, and the method for producing phenol foam using this device is also extremely inefficient. On the other hand, structures using foams made from carbohydrates have improved flame retardancy compared to structures using isocyanurate foams made from industrial polyols. Due to its poor properties, it is difficult to fill the edges during panel manufacture, and only a high-density foam can be obtained, resulting in high costs and poor productivity. (Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned problems, and takes advantage of the excellent workability of polyurethane foam to provide a foam that has excellent flame retardant properties and An object of the present invention is to provide a foaming resin composition having excellent liquid fluidity. (Means for Solving the Problems) The present invention provides an aqueous solution and/or slurry of carbohydrates, a reaction catalyst, an isocyanate compound, a methyl group bonded to silicon,

[Formula] The number of moles of methyl group having units and (-CH ₂ CH ₂ O)- units and bonded to silicon is X,

[Formula] The number of moles of unit is Y and the number of moles of (-CH ₂ CH ₂ O)-unit is Z
contains a silicone foam stabilizer, a surfactant (excluding the silicone foam stabilizer) and, if necessary, a flame retardant, where Y+Z/X=0.5 to 11 and Y/Z=0 to 1.8. The present invention relates to a foaming resin composition. The carbohydrate aqueous solution and/or slurry used in the foaming resin composition of the present invention includes fructose, glucose, sugar, maltose, cellulose, etc. alone,
Alternatively, it is an aqueous solution prepared by dissolving two or more types in water, a slurry dispersed in water, or a mixed solution of the aqueous solution and slurry. Commercially available products include Oji Cornstarch Co., Ltd.
There are isomerized sugars F-42, F-55 and HC. For example, HC is fructose 55.9% by weight, glucose 39.2% by weight,
The mixture contains 4.9% by weight of other sugars and 24.5% by weight of water overall. Also manufactured by Sanmatsu Kogyo Co., Ltd., Suncraft 550
is a mixture containing 55.6% by weight of fructose, 39.3% by weight of glucose, and 5.1% by weight of oligosaccharides as sugar components, and further contains 24.5% by weight of water as a whole. Examples of the reaction catalyst in the present invention include tin compounds such as dibutyltin dilaurate and dibutyltin dioctoate, triethylamine, triethylenediamine, triethanolamine, 2-dimethylamino-2-methyl-1-propanol, and 2-amino-2-methyl- Examples include amine compounds such as 1-propanol. As the surfactant used in the present invention, any of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants can be used, and these can be used alone or in combination. Nonionic surfactants include Nonion LP-20R, Nonion OP-85R, Nonion LT-221, Nonion PT-221, and Nonion A manufactured by NOF Corporation.
-13P, Nonion MN-811, Nonion E-206,
Nonion P-208, Nonion P-215, Nonion K
-204, Nonion T-208.5, Persoft NK-60,
Persoft NK-100, Nonion NS-202, Nonion NS-240, Nonion-206, Nonion HS-
208, Nonion L-2, Nonion S-2, Nonion S-10, Nonion O-2, Nonion O-6, Nonion T-4, Pronone 102, Pronone 201, Dispanol LS-100, Dispanol K-3, Starhome F, Starhome FK, Starhome DL, Starhome DO, Starhome DO-S, Starhome T, Penezol H-100, Carbo Datsushi series, FC-170C manufactured by Sumitomo 3M Co., Ltd., FC
-430, FC-431, Nonipole 20, Nonipole 60, Nonipole 140, Nonipole 800, Nonipole D-160, Octapol manufactured by Sanyo Chemical Industries, Ltd.
45, Octapol 80, Octapol 100, Octapol 400, Nonipole Soft SM-55, Nonipole Soft SMH-30, Emulmin 40, Emulmin 70, Emulmin 240, Emulmin L-380, Ionets MS-400, Ionets MO- 400, Ionets DO-200, Ionets S-20, Ionets S-85, Ionets T-20C, Ionets T-
80C, New Paul PE-61, New Paul PE-
71, New Paul PE-108, New Paul NPE
-2700, Profan EX-24, Profan 2012E,
Profan 1281 etc. are used. Examples of anionic surfactants include Diapon S, Trax H-45, and Trax H- manufactured by NOF Corporation.
45W, Trax K-40, Trax K-300,
Trax N-300, Nurex RS, Nurex R, Nonisar OK-1, Nonisar
OK-2, Nairiyube, Persoft SFT, Persoft SLT, Persoft EF, Persoft ELT,
Persoft EDO, Rapizol B-30, Rapizol B-90, Polyster A-1060, Polyster
SMX-1, oleoylsarcosine 221P, Sanamide C-3, Fillet L, Solnon SS, Royal M, Solnon P, FC-93, FC-95, FC-98, FC-129 manufactured by Sumitomo 3M Ltd. used. Examples of cationic surfactants include Cation SA, Cation MA, Cation DTA, Cation AB, and Cation AB-600 manufactured by NOF Corporation.
Cation ABT ₂ −500, Cation BB, Cation
FB, cation PB-40, cation VB, cation
F ₂ −20R, cation F ₂ −50E, cation E ₂ −
40PO, cation L-207, Naimeen L-201,
Naimeen L-202, Naimeen F-215, Naimeen S-202, Naimeen S-220, Naimeen
T ₂ −202, Naimeen T ₂ −260, Naimeen DT−
208, Fillet Q, Asfazole 10, FC-135 manufactured by Sumitomo 3M Ltd., etc. are used. Examples of amphoteric surfactants include Anon BF, Anon BL, and Anon LG manufactured by NOF Corporation. The silicone foam stabilizer used in the present invention includes silicon-bonded methyl groups,

[Formula] The number of moles of methyl group having units and (-CH ₂ CH ₂ O)- units and bonded to silicon is X,

[Formula] Where Y is the number of moles of units and Z is the number of moles of (-CH ₂ CH ₂ O)- units, those in which Y+Z/X=0.5 to 11 and Y/Z=0 to 1.8 are used. If X, Y and Z are outside the above ranges, the fluidity during foaming will be poor. More preferably, Y+Z/X is in the range of 0.5 to 11 and Y/Z is in the range of 0 to 1.0. Examples of such silicone foam stabilizers include those represented by the following formula. In the above formula, R is an alkylene group, R' is an alkyl group, etc., and m, n, Z, and Y are 0 or a positive number. The silicone foam stabilizer used in the present invention includes TFA-4200 manufactured by Toshiba Silicone Corporation;
TSF-4452, TFA-4310, TSF-4445, SZ-1605, SZ-1623, SZ- manufactured by Nippon Unicar Co., Ltd.
1610, F-318, F-341 manufactured by Shin-Etsu Chemical Co., Ltd.
There are F-347, F-350S, etc. Number of moles of each segment of silicone foam stabilizer X,
Y and Z are usually measured by NMR spectroscopy. If the peak of the methyl group of tetramethylsilane is 0 ppm, (a) the peak of the methyl group bonded to silicon is 0.05~
Since it appears at 0.30 ppm, X is the value obtained by dividing the integral value of this peak by the number of protons in the methyl group, which is 3. (b)

In the [formula] unit, the peak of CH ₃ − (methyl group) appears at 0.90 to 1.30 ppm, so Y is the value obtained by dividing the integral value of this peak by the number of protons of the methyl group, which is 3. (c) (-CH ₂ CH ₂ O) - 3.10~ in units
Since a CH ₂ peak appears at 3.90 ppm, Z is the value obtained by dividing the integral value of this peak by the number of protons, 4. The values of Y+Z/X and Y/Z are determined from X, Y, and Z obtained as described above. Flame retardants used as necessary in the present invention include organic flame retardants such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, chlorinated paraffin, hexabromobenzene, antimony trioxide, and water. There are inorganic flame retardants such as aluminum oxide, and these can be used alone or in combination. Isocyanate compounds in the present invention include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, polymethylene polyphenyl isocyanate, mixtures thereof, derivatives of these isocyanates, etc., and purified or crude Any isocyanate compound can be used, and monoisocyanate compounds such as phenyl isocyanate can also be used in combination. In addition, when building a structure using the foaming resin composition of the present invention, a flame-retardant or non-combustible plate or sheet is provided on at least one side of the foam obtained from the resin composition. Or sheets include aluminum kraft paper, metal foil such as aluminum foil, copper foil, aluminum asbestos sheet, wood wool cement board, iron plate, steel plate, stainless steel plate, aluminum plate, metal plate such as copper plate, slate plate, calcium silicate plate. , inorganic noncombustible boards such as gypsum board, cement board, and glass fiber reinforced cement board. These flame-retardant or noncombustible boards or sheets may be painted for reasons such as appearance or corrosion prevention. It is necessary to carefully consider the material or thickness of the paint film used for the paint so as not to reduce its flame retardance, but as long as the paint film is thin, there is no particular restriction on the material, and usually commercially available colors can be used. Even iron plates can be used as sufficiently nonflammable plates. Although there is no particular restriction on the blending ratio of each component in the foamable resin composition of the present invention, (a) an aqueous carbohydrate solution and/or slurry;
50 to 200 parts by weight (b) Reaction catalyst 0.1 to 5 parts by weight (c) Surfactant (excluding silicone foam stabilizers) 0.1 to 5 parts by weight (d) 0.1 to 5 parts by weight of the above silicone foam stabilizers ( e) Isocyanate compound 50-200 parts by weight (f) Flame retardant (selective) Preferably used in a proportion of 0.1-100 parts by weight, (a) Aqueous carbohydrate solution and/or slurry
50 to 150 parts by weight (b) Reaction catalyst 0.5 to 4.0 parts by weight (c) Surfactant (excluding silicone foam stabilizers) 0.5 to 4.0 parts by weight (d) 0.5 to 4.0 parts by weight of the above silicone foam stabilizers ( e) Isocyanate compound 50 to 150 parts by weight (f) Flame retardant (selective) It is more preferably used in a proportion of 5 to 50 parts by weight. In addition, due to workability, for example, a mixture of (a) and (b) and (c),
It is also possible to prepare a mixture of (d), (e) and (f), mix them, react and foam. The reaction temperature is not particularly limited, but is preferably 10 to 50°C, and the rotation speed of the stirrer during mixing is not particularly limited, but is preferably 1000 to 7000 rpm. When molding the foam, there are no particular restrictions, but it is preferable to use a mold. For example, a mold with an open top and bottom is used, and a flame retardant or noncombustible plate or sheet is placed on the bottom surface of the mold. The mold is heated to a temperature of 30°C to 90°C, which is preferable to obtain a uniform foam. Next, the above-mentioned materials are stirred and mixed and poured into the mold, which is then equipped with a flame-retardant or non-combustible plate or sheet, preferably at 30°C to obtain a uniform foam.
The foam and the flame-retardant or noncombustible plate or sheet are bonded by placing an upper mold heated to 90°C with the side of this plate or sheet facing the solution mixture, clamping the mold, and causing foaming. A close-fitting structure can be obtained. Here, the flame-retardant or noncombustible plate or sheet may be provided on either one or both sides of the foam, but it is preferable to provide it on both sides to form a sandwich structure in order to improve flame retardant properties. In this case, the flame-retardant or noncombustible plates or sheets provided on both sides of the foam may be the same or a combination of different types. (Examples) Example 1 An example of the present invention will be described. In the examples, X, Y, and Z represent the number of moles of the above groups. 75 parts by weight of fructose, 25 parts by weight of tap water, amphoteric surfactant (manufactured by NOF Corporation, product name Nitsusan Anon BF)
1.5 parts by weight of triethanolamine was added to 1.0 parts by weight and mixed well to obtain solution A. Diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Millionate MR-100)
80 parts by weight, 1.0 parts by weight of silicone foam stabilizer (manufactured by Nippon Unicar Co., Ltd., trade name Foam stabilizer SZ-1623, measured value by NMR spectroscopy: Y+Z/X=1.32, Y/Z=0), tris(2-chloroethyl) ) 20 parts by weight of phosphate was added and mixed to obtain solution B. In order to evaluate fluidity, panel filling properties, etc. were investigated. The ability to fill the corners of the panel (flowability) was evaluated on a five-point scale (higher scores indicate better filling ability), and the evaluation was conducted using the following method. Add 100 parts by weight of solution A and 150 parts by weight of solution B, stir for 5 seconds at 2000 rpm using a stirrer equipped with turbine blades, and keep the mixture at 70°C to make a flat panel making mold (made of iron, internal dimension 350 mm). ×250mm×height
15mm). After 90 seconds, the mold was demolded to obtain a panel (thickness: 15 mm). The panel filling property was given a score of 5. 100 parts by weight of solution A and 150 parts by weight of solution B were stirred for 5 seconds at 2000 rpm using a stirrer equipped with a turbine blade, and the mixture was kept at 25°C and placed in a wooden box with an open top and bottom ( The height of the foam was 350 mm after 120 seconds. 100 parts by weight of Solution A and 150 parts by weight of Solution B were stirred for 5 seconds at 2000 rpm using a stirrer equipped with turbine blades, and the mixture was poured into the wedge shape shown in Figure 1 (mold temperature 70°C) and 90% After seconds, the mold was removed and the flow distance was measured, and the flow distance of this foam was 230 mm. Next, 100 parts by weight of solution A and 100 parts by weight of solution B were added and stirred for 5 seconds at 2000 rpm with a stirrer equipped with turbine blades. 220 mm x 220 mm x height 15 mm), placed an upper mold kept at 40°C on top, and clamped the mold. After 10 minutes, the mold was demolded to obtain a foam (thickness: 15 mm). The density of this foam is 0.024
g/cm ³ , and the water absorption amount at the end was 90 g/m. Reference examples of flame-retardant structures using the foamable resin composition of the present invention are shown below. Reference example 1 Wooden mold with open top and bottom (inner volume 220mm
×220mm×15mm) Colored iron plate (thickness 0.27mm) on the bottom surface
mm) and warm the mold to 40℃. Next, 150 parts by weight of solution B was added to 100 parts by weight of solution A used in Example 1, and the mixture was rotated at 2000 rpm using a stirrer equipped with turbine blades.
Stir for 5 seconds to mix, pour this into the above mold, paste aluminum kraft paper on the top surface, heat the upper mold to 40℃, place the aluminum kraft paper towards the solution mixture, and tighten the mold. did. After 10 minutes, the mold was removed to obtain a flame-retardant structure in which a colored iron plate (0.27 mm thick) was adhered to the surface of the foam (15 mm thick), and aluminum kraft paper was adhered to the back side. The density of the foam, which is the core material of this structure, is 0.024g/cm ³ , and the water absorption amount at each end is 90g/cm 3 .
The foam had a uniform and fine cell structure, and was comparable to conventional foams in terms of water absorption and fluidity. Table 1 shows the results of a nonflammability test conducted on this structure based on Ministry of Construction Notification No. 1231. As is clear from Table 1, this structure has an external appearance after combustion, an afterflame, a smoke generation coefficient,
It was extremely excellent in terms of temperature coefficient and temperature time area. This structure also had excellent adhesion to colored iron plates and aluminum kraft paper. Example 2 75 parts by weight of fructose, 25 parts by weight of tap water, 1.0 parts by weight of the silicone foam stabilizer used in Example 1, nonionic surfactant (manufactured by NOF Corporation, trade name: Nonion NS-
200) 1.5 parts by weight of triethanolamine was added to 1.0 parts by weight and mixed well to obtain solution C. Add 150 parts by weight of solution C to 100 parts by weight of solution A obtained in the example.
Add the weight parts and mix by stirring at 2000 rpm for 5 seconds using a stirrer equipped with a turbine blade.Then, do the same as in Reference Example 1 and place a color iron plate on the surface of the foam (thickness 15 mm) and an aluminum plate on the back side. A structure with kraft paper glued was obtained. In this case, the panel filling property of the foam is 5 points, the foam height is 350 mm, the flow distance is 225 mm, the density of the foam is 0.026 g/cm ³ , the water absorption at the end is 130 g/m, and it has a uniform and fine cell structure. It was foam. In addition, Table 1 shows the results of a semi-flammable test conducted on this structure based on Ministry of Construction Notification No. 1231.
As is clear from Table 1, the amount of water absorbed at the end was larger than that of Reference Example 1, but the same results were obtained in fluidity and flame retardance. Comparative Example 1 1.5 parts by weight of triethanolamine was added to 75 parts by weight of fructose and 25 parts by weight of tap water and mixed well to obtain a solution D. Diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Millionate MR-100)
80 parts by weight, 1.0 part by weight of silicone foam stabilizer (manufactured by Toshiba Silicone Co., Ltd., trade name TSF-4450, measured value by NMR spectroscopy: Y+Z/X=9.86, Y/Z=2), and tris(2-chloroethyl) phosphate. 20 parts by weight were added and mixed to obtain solution E. Add 150 parts by weight of solution E to 100 parts by weight of solution D, stir and mix for 5 seconds at 2000 rpm using a stirrer equipped with a turbine blade. A structure was obtained with a colored iron plate attached to the top and aluminum kraft paper glued to the back. In this case, the panel fillability of the foam is 2 points, the foam height is 290 mm, the flow distance is 180 mm, and the foam density is
The foam had a uniform and fine cell structure with a water absorption of 0.035 g/cm ³ and an end water absorption of 100 g/m. In addition, Table 1 shows the results of a semi-flammable test conducted on this structure based on Ministry of Construction Notification No. 1231. As is clear from Table 1, the structure of this comparative example is better than the structure using isocyanurate foam or phenol foam in terms of external shape after combustion, smoke emission coefficient, and exhaust temperature after 5 minutes. Although it has improved, its liquidity has been poor. Comparative example 2 Heteroform 28264 (manufactured by Futsker, trade name)
21.1 parts by weight, 23.5 parts by weight of Heteroform 29696 (manufactured by Futzker, trade name), 1 part by weight of DC-193 (manufactured by Dow Corning, trade name), Polycat 41
To a solution containing 1.42 parts by weight of Freon 11 (manufactured by Sun Abot Co., Ltd., trade name) and 25 parts by weight of Freon 11 (manufactured by Mitsui Fluorochemical Co., Ltd., trade name), 101 parts by weight of Isonate 580 (manufactured by Abbot Co., Ltd., trade name) was added. Stir and mix for 5 seconds at 2000 rpm with the attached stirrer, and use the same procedure as in Reference Example 1 to obtain a structure in which the isocyanurate foam (thickness 15 mm) has a colored iron plate on the surface and aluminum kraft paper on the back. Ta. In this case, the panel filling property of the foam was 4 to 5 points, the foaming height was 290 mm, the wedge-shaped flow distance was 210 mm, the density of the foam was 0.035 g/cm ³ , and the water absorption at the edges was 40 g/m. Also, using this structure, Ministry of Construction Notification No. 1231
Table 1 shows the results of the quasi-nonflammability test based on No. As is clear from Table 1, the water absorption amount of the structure of this comparative example was superior to that of the foam of the reference example, but the change in appearance after combustion was significant and most of the foam was burned out. It was also significantly inferior in terms of smoke generation coefficient and time-temperature area. Comparative example 3 Danphenon 110A (manufactured by Hodogaya Chemical Co., Ltd., trade name)
Add 40 parts of Danphenone 110B curing agent (manufactured by Hodogaya Chemical Co., Ltd., trade name) to a solution of 100 parts by weight and 15 parts by weight of Freon 11 (manufactured by Mitsui Fluorochemical Co., Ltd., trade name).
A solution containing 15 parts by weight of Danphenon 110C foam stabilizer (manufactured by Hodogaya Chemical Co., Ltd., trade name) was added, and the mixture was stirred for 5 seconds at 2000 rpm with a stirrer equipped with turbine blades. Reference Example 1 is shown below. In the same manner as above, a structure was obtained in which a colored iron plate was adhered to the surface of a phenol foam (thickness 15 mm) and aluminum kraft paper was adhered to the back surface.
However, since the phenol foam has significantly poor curing properties, after-curing was performed at 100°C for 30 minutes. In this case, the panel filling property of the foam was 2 points, the foaming height was 230 mm, the wedge-shaped flow distance was 100 mm, the density of the foam was 0.040 g/cm ³ , and the water absorption at the edges was 210 g/m. Since flyability occurred on the surface of the phenol foam, the adhesion between the foam and the aluminum kraft paper and the colored iron plate was poor. Table 1 shows the results of semi-flammability tests conducted on this structure based on Ministry of Construction Notification No. 1231. As is clear from Table 1, the structure of this comparative example had a good appearance after combustion, but the afterflame was long and inferior.

[Table] (Effects of the Invention) The foaming resin composition of the present invention is a foaming resin composition that provides excellent flame retardant properties of the resulting foam and excellent fluidity of the liquid during foaming.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of the mold used for measuring the wedge-shaped flow distance in Examples and Comparative Examples.

Claims (1)

[Scope of Claims] 1. An aqueous solution and/or slurry of carbohydrates, a reaction catalyst, an isocyanate compound, a methyl group bonded to silicon, having [formula] units and (- CH ₂ CH ₂ O)- units, When the number of moles of the bonded methyl group is X, the number of moles of the [Formula] unit is Y, and the number of moles of the (-CH ₂ CH ₂ O)- unit is Z, Y + Z / X = 0.5 to 11 and Y / Z = 0 to 1.8, a surfactant (excluding the silicone foam stabilizer), and optionally a flame retardant. 2. The foaming resin composition according to claim 1, wherein the surfactant is a nonionic surfactant. 3. The foaming resin composition according to claim 1, wherein the surfactant is an anionic surfactant. 4. The foaming resin composition according to claim 1, wherein the surfactant is a cationic surfactant. 5. The foaming resin composition according to claim 1, wherein the surfactant is an amphoteric surfactant. 6. The foaming resin composition according to claim 1, wherein the silicone foam stabilizer is a silicone foam stabilizer in which Y+Z/X=0.5-11 and Y/Z=0-1.0.