JPH0228609B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a foaming resin composition that produces a foam with excellent flame retardant properties and the like. (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. This Ministry of Construction Notification No. 1372 model box test is the afterflame in the same No. 1231 quasi-nonflammability 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. Conventionally, isocyanurate foams having isocyanurate rings (a type of polyurethane foam), phenol foams foamed using industrial polyol as a raw material, foams foamed using carbohydrates as a raw material, etc. are known. (Problems to be Solved by the Invention) Structures using conventional isocyanurate foams having isocyanurate rings made from industrial polyol as a raw material undergo significant shape change after combustion and generate a large amount of heat. It is difficult to pass the No. 1372 model box test. On the other hand, a structure using a phenol foam has a drawback that the afterflame time after combustion is long, although the shape change is small after combustion. When switching manufacturing equipment used to mold isocyanurate foams having isocyanurate rings to molding phenol foams, change the heating equipment during and after foaming to equipment that can heat at high temperatures and for long periods of time. Furthermore, the method for producing phenol foam using this equipment is also extremely difficult to work with. On the other hand, the flame retardance of structures using foams made from carbohydrates has improved somewhat compared to structures using isocyanurate foams made from industrial polyols, but it is still insufficient. figure,
In addition, as a result of improving flame retardancy, adverse effects such as a decrease in strength (bending strength) and an increase in water absorption have appeared. The present invention was made in view of these problems, and takes advantage of the excellent workability of polyurethane foam to provide a material with excellent flame retardancy and high strength (flexural strength).
An object of the present invention is to provide a foaming resin composition that provides a foam with a low water absorption rate. (Means for Solving the Problems) The present invention provides a polyether polyol obtained by reacting an alkylene oxide with an aqueous solution and/or slurry of carbohydrates, and a sugar having a cyclic structure;
The present invention relates to a foaming resin composition containing a reaction catalyst, an isocyanate compound, and, if necessary, a foam stabilizer and/or a flame retardant. The carbohydrate aqueous solution and/or slurry used in the foamable resin composition of the present invention refers to an aqueous solution in which fructose, glucose, sugar, maltose, cellulose, etc., alone or in combination of two or more thereof, are dissolved in water; It is a slurry dispersed in water or a mixture of an aqueous solution thereof and a slurry. Commercially available products include isomerized sugar F-42, F-55, and HC manufactured by Oji Cornstarch Co., Ltd., and Suncraft 550 manufactured by Sanmatsu Kogyo Co., Ltd. HC manufactured by Oji Cornstarch Co., Ltd. is an aqueous solution of fructose, glucose and other sugars, and Suncraft 550 manufactured by Sansho Kogyo Co., Ltd. is an aqueous solution of fructose, glucose and oligosaccharides. There is no particular restriction on the water content in the carbohydrate aqueous solution and/or slurry, but it is 5 to 20% by weight.
It is preferable that When the content exceeds 20% by weight, the strength of the foam decreases, and when it becomes less than 5% by weight, the viscosity tends to increase and workability tends to decrease. In the present invention, a polyether polyol prepared by reacting alkylene oxide with a sugar having a cyclic structure is used in view of shape retention of the foam after combustion. Examples of sugars having a cyclic structure with which alkylene oxides are reacted in the present invention include fructose, glucose, and sucrose, and these are reacted with alkylene oxides such as ethylene oxide and propylene oxide by a predetermined method. The polyether polyol obtained when using sucrose is
It is particularly effective in improving the strength of foam. Commercial products of this polyether polyol include Excenol 450S, Excenol 375S, manufactured by Asahi Glass Co., Ltd.
Examples include Exenol 455S, Sannix HR-450P manufactured by Sanyo Chemical Co., Ltd., and Sannix HS-209. By using this polyether polyol, the strength of the resulting foam can be increased and the water absorption rate can be reduced without increasing the smoking coefficient or combustion temperature. 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, 2-amino-2-methyl- Amine compounds such as 1-propanol are used. The isocyanate compound in the present invention is not particularly limited, and includes, for example, monoisocyanate compounds such as phenyl isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'-diisocyanate, and paraphenylene diisocyanate. diisocyanate compounds such as, triisocyanate compounds such as triphenylmethane-4,4′,4″-triisocyanate, and low-molecular or polymeric compounds derived from these isocyanates.
NCO terminated prepolymers are used. In the present invention, silicone polymers can be used as foam stabilizers if necessary, such as L-520, L-540, L-5340, L-
5350, L-5410, L-5430, 190, 191, 193 manufactured by Dow Corning Co., Ltd., etc. Flame retardants that may be used as needed include organic flame retardants such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, chlorinated paraffin, hexabromobenzene, antimony trioxide, aluminum hydroxide, etc. There are inorganic flame retardants, etc., and these can be used alone or in combination. Furthermore, in order to improve workability such as viscosity of the composition and obtain a foam with a high expansion ratio, as a blowing agent,
It is also possible to use low boiling point solvents such as monofluorotrichloromethane and trifluorotrichloroethane. A commercially available product is Freon 11 (boiling point 23.8) manufactured by Mitsui Dupont Fluorochemical Co., Ltd.
℃), Freon 113 (boiling point 47.6℃), etc. The amount used is preferably in the range of 2 to 15% by weight based on the foaming resin composition. Further, a foam can be obtained using the foaming resin composition of the present invention, and a structure including this foam can also be obtained. When building a structure, a board or sheet is provided on at least one side of the foam, and examples of this board or sheet include aluminum kraft paper, aluminum foil, metal foil such as copper foil, aluminum asbestos sheet, wood wool cement board,
Preferred are metal plates such as iron plates, steel plates, stainless steel plates, aluminum plates, and copper plates, and flame-retardant or noncombustible plates or sheets such as slate plates, calcium silicate plates, gypsum boards, cement plates, and glass fiber-reinforced cement plates. 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. In the present invention, there is no particular restriction on the blending ratio of each component in the foaming resin composition, but (a) carbohydrate aqueous solution and/or slurry
50-200 parts by weight (b) Polyether polyol obtained by reacting alkylene oxide with sugar having a cyclic structure
5-200 parts by weight (c) Reaction catalyst 0.1-5 parts by weight (d) Isocyanate compound 50-200 parts by weight (e) Blowing agent (selective) 0.1-5 parts by weight (f) Flame retardant (selective) 0.1- Preferably used in a proportion of 100 parts by weight, (a) an aqueous solution and/or slurry of carbohydrates;
50-150 parts by weight (b) Polyether polyol obtained by reacting alkylene oxide with sugar having a cyclic structure
10-100 parts by weight (c) Reaction catalyst 0.5-4.0 parts by weight (d) Isocyanate compound 50-150 parts by weight (e) Foam stabilizer (selective) 0.5-4.0 parts by weight (f) Flame retardant (selective) 5 More preferably, it is used in a proportion of ~50 parts by weight. Also, due to workability, for example, a mixture of (a), (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 a foam or structure, it is preferable to use a mold, although there are no particular restrictions. 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. and warm the mold to a temperature of 30°C to 60°C, which is preferable for obtaining a uniform foam. Next, each material of the foam is stirred and mixed,
The surface of this plate or sheet is poured into the mold, and then an upper mold equipped with a flame-retardant or noncombustible plate or sheet and heated to a temperature of 30°C to 60°C, which is preferable to obtain a uniform foam, is placed so that the surface of this plate or sheet is heated. Place it towards the solution mixture;
By clamping and foaming, a structure in which the foam and a flame-retardant or noncombustible plate or sheet are in close contact 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. (Example) Example 1 59 parts by weight of fructose, 1.5 parts by weight of triethanolamine in 11 parts by weight of tap water, and a polyether polyol obtained by reacting alkylene oxide with a sugar having a cyclic structure (trade name: EXCENOL, manufactured by Asahi Glass Co., Ltd.) 450S) were mixed to obtain solution A.
Add 80 parts by weight of diphenylmethane diisocyanate (trade name: Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.) to a foam stabilizer (trade name: Foam stabilizer, manufactured by Dow Corning Co., Ltd.)
190) 1.0 parts by weight and 20 parts by weight of tris(2-chloroethyl) phosphate were added and mixed to obtain solution B. Next, mix 100 parts by weight of solution A and 100 parts by weight of solution B, and use a stirrer equipped with turbine blades to rotate the mixture at 2000 rpm.
Stir for 5 seconds and keep the mixture at 40℃.A wooden mold with an open top and bottom (220 x 220 x height)
15 mm), placed an upper mold kept at 40°C on top, and closed the mold. After 10 minutes, the mold was demolded to obtain a foam (thickness: 15 mm). The density of this foam is 0.03g/
cm ³ , bending strength 1.6 Kg/cm ² , and water absorption rate 3%. Reference examples of flame-retardant structures obtained 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, 100 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 that is the core material of this structure is 0.033g/cm ³ , the bending strength is 1.6Kg/cm ² ,
The water absorption rate was 3%, and the foam had a uniform fine cell structure, and was comparable to conventional foams in terms of compressive strength and water absorption rate. 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 was extremely excellent in terms of appearance after combustion, afterflame, smoke generation coefficient, temperature coefficient, and temperature-time area. Reference 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 C. Add the solution to 100 parts by weight of solution B obtained in Example 1.
Add 100 parts by weight of C and mix by stirring at 2000 rpm for 5 seconds using a stirrer equipped with turbine blades, and then proceed in the same manner as in Reference Example 1. Color iron plate is placed on the surface of the foam (thickness 15 mm), and aluminum craft is placed on the back side. A structure with paper adhered was obtained. In this case, the density of the foam is 0.035
g/cm ³ and bending strength of 0.7 Kg/cm ² , and the foam had a uniform and fine cell structure. 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 reference comparative example is superior to 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 improvements have been made, the basic properties required for structures, such as a decrease in bending strength and an increase in water absorption, have deteriorated. Reference Comparative Example 2 Heteroform 28264 (polyol manufactured by Futsker, trade name) 21.1 parts by weight, Heteroform 29696
(Polyol manufactured by Futsuker, trade name) 23.5 parts by weight,
DC-193 (foam stabilizer manufactured by Dow Corning, trade name)
Isonate 580 (an isocyanate compound manufactured by Appdition Co., Ltd., a commercial product) was added to a solution containing 1 part by weight, 1.42 parts by weight of Polycat 41 (catalyst manufactured by Sunabott Co., Ltd., trade name), and 25 parts by weight of Freon 11 (manufactured by Mitsui Dupont Fluorochemical Co., Ltd., trade name). ) Add 101 parts by weight and run at 2000 rpm with a stirrer equipped with turbine blades.
The mixture was stirred and mixed for seconds, and then the same procedure as in Reference Example 1 was carried out to obtain a structure in which a colored iron plate was adhered to the surface of the isocyanurate foam (thickness: 15 mm) and aluminum kraft paper was adhered to the back surface. In this case, the density of the foam is 0.035g/cm ³ ,
The bending strength was 2.4Kg/ ^cm2 . 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, although the structure of this reference comparative example was similar to the foam of the reference example in terms of bending strength and water absorption, the change in appearance after combustion was significant, with most of the foam being burned away. Ta. It was also significantly inferior in terms of smoke generation coefficient and time-temperature area. Reference Comparative Example 3 Danphenon 110B curing agent ( Manufactured by Hodogaya Chemical Co., Ltd., trade name) 40 parts by weight, Danphenone 110C foam stabilizer (manufactured by Hodogaya Chemical Co., Ltd., trade name) 15
Add the solution mixed with parts by weight, stir for 5 seconds at 2000 rpm with a stirrer equipped with a turbine blade, and prepare a phenol foam (thickness:
We obtained a structure with a colored iron plate (15 mm) on the front surface and aluminum kraft paper glued on the back surface. Since phenol foam has significantly poor curing properties, after-curing was performed at 100°C for 30 minutes. In this case, the density of the foam is
The weight was 0.040g/cm ³ and the bending strength was 1.2Kg/cm ² . Although the structure was similar to Example 1 in terms of bending strength and water absorption, flyability (chipping) occurred on the surface of the phenol foam. Adhesion to the color iron plate was poor. Using the characteristics and structure of foam, the Ministry of Construction Notification No.
Table 1 shows the results of the quasi-nonflammability test based on No. 1231. As is clear from Table 1, the structure of the reference comparative example had a good appearance after combustion, but the afterflame was long and inferior.

[Table] (Effects of the Invention) As is clear from the above, the foaming resin composition of the present invention produces a foam with high flame retardant properties, high strength (high bending strength), and low water absorption. It is a resin composition for

Claims (1)

[Claims] 1. An aqueous solution and/or slurry of carbohydrates, a polyether polyol obtained by reacting alkylene oxide with a sugar having a cyclic structure, a reaction catalyst, an isocyanate compound, and if necessary a foam stabilizer and/or a foam stabilizer. A foaming resin composition containing a fuel agent. 2. The foaming resin composition according to claim 1, wherein the sugar is sucrose. 3. Claim 1, wherein the carbohydrate aqueous solution and/or slurry has a water content of 5 to 20% by weight.
The foaming resin composition according to item 1 or 2.