JPH02185561A - Foaming resin composition, foam and structural article - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. which is lowly viscous and excellent in processability and which gives a foam with high strengths, high flame retardance and low water absorption by compounding an aq. soln. or slurry of a sugar, a polyether polyol, a phosphonate, a catalyst and an isocyanate. CONSTITUTION:An aq. soln. and/or slurry of a sugar (e.g. glucose), a polyether polyol (e.g. a reaction product of bisphenol A with ethylene oxide), a phosphonate of the formula (wherein R1, R2 and R3 are each 10C or lowr alkyl optionally contg. a heteroatom such as halogen or S) (e.g. dimethyl methylphosphonate), a catalyst (e.g. triethylamine) and an isoxyanate (e.g. tolylene diisocyanate), and if necessary a polyhydric alcohol, a foam stabilizer, a flame retardant, a fibrous material and/or a blowing agent are compounded to give a foaming resin compsn. The resulting compsn., being lowly viscous, is excellent in processability and foam density and gives a foam or structural article with high strengths, high flame retardance and low water absorption.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a foam and a structure made of a foaming resin composition 1 that produces a foam with excellent flame retardant properties.

(Prior art) Recently, flame retardant requirements for building materials, especially residential exterior wall materials, have become more severe, and a model box test No. 1372 has been added to the Ministry of Construction notification No. 1231 semi-flammability test. reached. This model box test is carried out in Ministry of Construction Notification No. 1372.After satisfying the regulation values for afterflame, temperature, time, area, and smoke generation coefficient in the same No. 1231 quasi-nonflammability test, the test specimen is made larger, and the calorific value during combustion is This is a very difficult process that involves determining the shape after combustion.

Conventionally, incyanurate foams having incyanurate rings (a type of polyurethane foam) that are foamed using industrial polyol as a raw material, phenol foams, foams that are foamed using carbohydrates as raw materials, etc. are known.

(Problems to be Solved by the Invention) Structures using conventional incyanurate foams having isocyanurate rings made from industrial polyol as a raw material undergo significant shape changes after combustion and generate a large amount of heat. It is difficult to pass the model box test No. 1372 mentioned above.

On the other hand, a structure using phenol foam has a drawback that the afterflame time after combustion is long, although the shape change is small after combustion. When switching the manufacturing equipment used to mold incyanurate foam having incyanurate rings to molding phenol foam, use a heating device that can heat at high temperature and for a long time during and after foaming. Furthermore, the method for producing phenol foam using this equipment is also extremely inefficient. Additionally, phenol foam has poor adhesion to iron plates.

There are also problems in terms of physical properties, such as brittleness and high water absorption. On the other hand, the flame retardance of structures using foams made from carbohydrates has improved somewhat compared to structures using incyanurate foams made from industrial polyols, but it is still insufficient. Furthermore, 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. As an attempt to improve strength and water absorption, there is a method of reducing the water content in carbohydrates.

In this case, if the moisture content is less than 20% by weight, the viscosity will become extremely high, or it will crystallize or become paste-like, resulting in significant problems in handling and workability. In other words, such problems were occurring.

The present invention has been made in view of such problems, and
A foaming resin composition that provides a foam with a working viscosity (resin viscosity) comparable to that of polyurethane, excellent flame retardancy, high strength (high bending strength), and low water absorption, and a foam using the same. and structures.

(Means for Solving the Problems) The present invention provides an aqueous solution and/or slurry of carbohydrates (13 polyether polyol, formula R, +OP=0 (R1l
R2 R2 and R3 are alkyl groups having 10 or less carbon atoms, and may contain heteroatoms such as halogen and sulfur.
R1, R2 and R3 may be the same or different. ) A phosphonate compound represented by

A foaming resin composition containing a reaction catalyst, an incyanate compound, and, if necessary, a polyhydric alcohol, a foam stabilizer, a flame retardant, a fiber material, and/or a foaming agent.

The present invention relates to a foam obtained from this foaming resin composition and a structure in which a plate or sheet is provided on at least one side of the foam obtained from this foaming resin composition.

The aqueous solution and/or slurry of carbohydrates used in the present invention includes monosaccharides such as fructose, cricose, and xylose.

Mannose, trisaccharides such as sucrose, maltose, lactose, sugar derivatives 7'c and t are sugar alcohols such as sorbitol, mannitol, arabitol, xylit 7Z, methyl glycoside, etc. These are an aqueous solution in which glucosides and the like are dissolved alone or in combination in water, a slurry in which these are dispersed in water, or a mixture of the aqueous solution and the slurry. Commercially available products include isomerized sugar F-42, F-55, and HC manufactured by Oji Cornstarch Co., Ltd.

Examples include 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 Ichikenmatsu Kogyo Co., Ltd., is an aqueous solution of fructose, glucose, and oligosaccharides.

In addition, Revros 5F-A (fructose aqueous solution) manufactured by Dai-Kogyo Seiyaku Co., Ltd., Revlos 20K (solid) manufactured by Dai-Kogyo Seiyaku Co., Ltd., and Sorvit 1 manufactured by Towa Kasei Kogyo Co., Ltd. ) -70, sorbitol) W-70 (aqueous solution of sorbitol), xyliso) (solid), Mannitol P (solid), Mannitol S (solid)
Sugar alcohols such as xylose XL (solid), Multi Towa (sugar aqueous solution).

PO-Towa (aqueous solution of starch saccharide).

Crysta (glucose, solid) manufactured by Sanmatsu Kogyo Co., Ltd.

LG-85 (glucose aqueous solution) 9 Nissin Pharmaceutical Industries Co., Ltd. There are sucrose, etc., and some are commercially available in solid form, but these may also be used in the form of an aqueous solution and/or slurry. Particularly preferred are aqueous solutions and/or slurries of isomerized sugar, sorbitol, xylitol, or mixtures thereof.

The water content in the aqueous solution and/or slurry of carbohydrates is not particularly limited, but is preferably 5 to 25% by weight. If it exceeds 25% by weight, the strength of the foam will decrease,
Moreover, if it is less than 5 weight i%, the viscosity tends to increase and workability tends to decrease.

The formula of the invention RHO-P = 0 (Rs, & and R
3 is R2 an alkyl group having 10 or less carbon atoms, and is a halogen.

May contain heteroatoms such as sulfur<, R+,
R2 and R3 may be the same or different. )
An example of a phosphonate compound (hereinafter abbreviated as a phosphonate compound) that can be expressed as dimethylmethylphosphoone) (Rt = R2 = R3CH3)
, diethyl ethyl fluorophone) (R+&=
Rs = CH3CH2), diisoprobyl isoglobil phosphonate [rtl2R2= R3=
(CH3)2CI-ICH2].

Diethyl methyl phosphonate [Rt= R2= C
H3CH2゜几5=cHs〕, diethylglobylphosphonate C&=R2CH3CH2, R5=CH
5CH2CH2).

CH2C02CH3 C) 13CH20P = OCR+= Rz= CHs
CM□, 几.

CH3CH20 CH2CO2Ckls] etc. A commercially available example is Dolgat D manufactured by Boxui Brown Co., Ltd.
M M P (R1 = R2 = Rs = CHs)
There is.

The 7-osphoneto compound used in the present invention is compatible with carbohydrates and does not reduce flame retardancy, and is used for the purpose of lowering the viscosity of carbohydrates and improving the strength of foams.

The amount of the phosphonate compound used is preferably 2 to 20 parts by weight based on 100 parts by weight of the aqueous carbohydrate solution and/or Slur IJ-1. If it exceeds 20 parts by weight, the strength tends to decrease, and if it is less than 2 parts by weight, the viscosity increases and workability decreases.

The polyether polyols in the present invention include (1) polyalkylene glycols such as polyethylene glycol and polypropylene glycol, (2) bisphenol A, phenol resin, L polyhydric alcohol, etc. as an initiator and R2,
A polyether polyol obtained by reacting alkylene oxide is used.

Polyether polyol obtained by reacting bisphenol A with alkylene oxide is bisphenol A
It is obtained by reacting alkylene oxide such as ethylene oxide or propylene oxide with 2.
Usually, the addition reaction cap of alkylene oxide is 2 to 30 moles per mole of bisphenol A. When the alkylene oxide is ethylene oxide or propylene oxide, the general formula of the polyether polyol is as follows (R- is -H or =CH3, n and m may be the same or different).

A commercially available example is Bisol 2BN (added with 2 moles of ethylene oxide) manufactured by Toho Chemical Industry.

Bisol 4EN (addition of 4 moles of ethylene oxide),
Bisol 2PO (addition of 2 moles of propylene oxide)
, Sanyo Chemical New Ball BPE2ONK, BPE
-40, BPE-60, BPE-100, BPE-85
0 (ethylene oxide derivative), New Ball BP-
2P, BP-4, P.

Examples include BP-8P and PB-10P (propylene oxide derivative).

As the phenol resin with which the alkylene oxide is reacted, either novolac type or resol type phenol resin can be used, and a polyether polyol is obtained by reacting this phenol resin with an alkylene oxide such as ethylene oxide or propylene oxide. Commercially available polyether polyols include Excenol 700R manufactured by Asahi Glass Co., Ltd.
.

701R etc.

As a sugar with which alkylene oxide is reacted.

These include fructose, glucose, and sucrose, and these are reacted with alkylene oxides such as ethylene oxide and propylene oxide in a predetermined manner.

The polyether polyol obtained when sucrose is used at 1% is effective in improving the strength of the foam.

As a commercially available product of this polyether polyol, Excenol 4508 manufactured by Asahi Glass Co., Ltd. Efsenol 3f58
．． Exenol 4558. Examples include SANIX HR-450P and SANX H8-209 manufactured by Sanyo Chemical Co., Ltd.

Examples of the polyhydric alcohol with which the alkylene oxide is reacted include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, mannitol, D-kyzyros, and erythritol.

Further, as the alkylene oxide, ethylene oxide, propylene oxide, etc. are used.

This polyether polyol is commercially available.

SANIX TP series manufactured by Sanyo Chemical Co., Ltd.

There are SANNIX GP series, SANNIX GEP series, SANNIX GL series, Newport TL series, etc.

As a commercially available polyether polyol containing sorbitol as a polyhydric alcohol, Excenol 45180 manufactured by Asahi Glass Co., Ltd. Examples include EXCENOL 500SO9 SP'-750 (average molecular weight 700) manufactured by Sanyo Chemical Co., Ltd.

The reaction catalyst used in the present invention includes tin compounds such as dibutyltin dilaurate and dibutyltin dioctoate.
h* Amine compounds such as triethylamine, triethylenediamine, triethanolamine, 2-dimethylamine, 2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, cobalt naphthenate, calcium naphthenate, nandene Organic metals such as copper acid, manganese naphdate, and dibutyltin dilaurate are used.

As the incyanate compound in the present invention.

There are no particular limitations. 9 For example, monoisocyanate compounds such as phenyl isocyanate, tolylene diisocyanate,
Hexamethylene diisocyanate.

Diisocyanate compounds such as naphthalene diisocyanate, inphorone diisocyanate, diphenylmethane-4,4'-diisocyanate, paraphenylene diisocyanate, triisocyanate compounds such as triphenylmethane-4,4'4'-) diisocyanate, and incyanates derived from these A low-molecular or high-molecular NCO-terminated prepolymer is used.

In the present invention, a silicone polymer is used as a foam stabilizer if necessary.
-520, L-540, L-5340, L-5350,
L-5410, L-5430, manufactured by Dow Corning Co., Ltd. 190°191.193. S H193, 8F2931, 5H2933, 5H manufactured by Rate Silicon Co., Ltd.
-190, 5RX298, etc.

Examples of polyhydric alcohols that can be used as needed in the present invention include propylene glycol.

Ethylene glycol, diethylene glycol, dipropylene glycol, hydrogenated bisphenol A.

1,3-butylene glycol, 1,6-hexanediol, neobenzyl glycol, triethylene glycol, glycerin, diglycerin, trimethylolpropane, pentaelite, etc. are used.

Two or more of these may be combined.

It may be in either a solution or solid state, but a solution is preferred. 3. Polyhydric alcohols are used to arbitrarily adjust the viscosity of carbohydrates and polyether polyols.

The amount of polyhydric alcohol added is not particularly limited, but it is 2 to 2 parts by weight per 100 parts by weight of the aqueous carbohydrate solution and/or Slur IJ-1.
Preferably, it is 0 parts by weight. If it exceeds 20 parts by weight, the flame retardancy will decrease, and if it is less than 2 parts by weight, the viscosity will increase and workability will tend to decrease.

Flame retardants used as necessary in the present invention! =L
"l:)IJsu(2-chloroethyl)phos7a),
Tris (2-chloropropyl) phosphate, chlorinated paraffin, hexabromobenzene.

Asahi Denka Co., Ltd. FC-450, FC-330°FL-
500, Daihachi Chemical Co., Ltd. CR-104゜ Dainippon Ink RF-420, RF-1020゜RN-660,)
I, N-720, Mobil Chemical Co., Ltd. Virco
l 82, Phylol 6 manufactured by Stouffer Chemical Co.
, UCC NN1ax RO-350° Kasei Upjohn Isonol 36. Organic flame retardants such as RF-230 manufactured by Orlin, antimony trioxide, aluminum hydroxide, and water conserving magnesia.

There are inorganic flame retardants such as silicon oxide and water glass, and these can be used alone or in combination.

In the present invention, in order to improve the strength and flame retardance of the foam, if necessary, inorganic fibers such as glass milled fibers and glass fibers, and organic fibers such as nylon and vinylon may be added as fiber materials for foaming. It is possible.

Furthermore, in order to improve workability such as viscosity of the composition and obtain a foam with a high expansion ratio, a low boiling point solvent such as monofluorotrichloromethane or trifluorotrichloroethane is used as a blowing agent as necessary. It is also possible.

Commercially available products include 7 Leon 11 (boiling point 23.8°C) and Freon 113 (manufactured by Mikata-DuPont Fluorochemical Co., Ltd.).
boiling point: 47.6°C).

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 plate or sheet is provided on at least one side of one foam, and this plate or sheet may be aluminum kraft paper, aluminum foil, metal foil such as copper foil, etc.

Aluminum asbestos sheet, wood wool cement board, iron plate.

Metal plates such as steel plates, stainless steel plates, aluminum plates, copper plates, slate plates, calcium silicate plates9 Inorganic noncombustible plates such as gypsum boards, cement plates, glass fiber reinforced cement plates,
Flame-retardant or noncombustible plates or sheets, such as glass fiber reinforced plastics (FRP) plates, are preferred.

These flame-retardant or noncombustible boards or sheets may be painted for reasons such as appearance or corrosion prevention. It is necessary to take into account the material of the paint used for painting and the thickness of the paint film 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. Even iron plates can be used as sufficiently nonflammable plates.

There are no particular restrictions on the blending ratio.

(a) Aqueous solution and/or slurry of carbohydrates - 50-2
00i parts (b) Polyether polyol 5 to 200 parts by weight (C) 0.5 to 100 parts by weight of the above-mentioned 7 osphonate compound (d) Reaction catalyst 0.1 to 6 parts by weight (e) Incyanate compound 50 ~200
Part by weight (f) Polyhydric alcohol (selective) 0.5-1
00 parts by weight (g) Foam stabilizer (selective) 0.1-5 parts by weight (h) Flame retardant (selective) 0.1-100 parts by weight (
i) Fiber material (selective) 5 to 100 parts by weight U) Local blowing agent (selective) Preferably used in a proportion of 2 to 150 parts by weight (a) Aqueous solution and/or slurry of carbohydrates 10 to 100 parts by weight 1
50 parts by weight (b) Polyether polyol 10 to 100 parts by weight (C) 1 to 20 parts by weight of the above phosphonate compound (d) Reaction catalyst 05 to 4 parts by weight (e) Isocyanate compound 50 to 150 parts by weight (f ) Polyhydric alcohol (selective) 1-20
Heavy lid part (g) Foam stabilizer (selective) 0.5 to 4 parts by weight (
h) Flame retardant (selective) 5-50 parts by weight [i) Fiber material (selective) 10-80 parts by weight ('') Blowing agent (selective) 5-100 parts by weight 1
It is more preferable to use the proportion of 1 part. Also, due to workability, 9 e.g. fa), (b), (c), (d
i, (fl, (g).

It is also possible to prepare a mixture of (h) and (j) and (e), mix the two, react, and foam.

There is no particular restriction on the reaction temperature, but 10 to 50°C is preferable.
There is no particular limit to the rotation speed of the stirrer during mixing, but it is 1.000.
~7,000 revolutions per minute is preferred. When molding a foam or structure, it is preferable to use a mold, although there are no particular limitations. The temperature is preferably 30°C to 60°C to obtain a uniform foam.

When using fiber material (i), 9 For example, glass milled fiber is (a), (b), (c), (d),
(f), (gl, (h) and (j) can be added directly to the mixture and then (e) can be mixed and foamed.On the other hand, when using glass fiber or organic fiber, the fibers can be added to the mold in advance. After that, a foaming resin mixture is poured into the fibers and the foam is molded into one piece.

Next, the above-mentioned materials are stirred and mixed and poured into the mold. Place an upper mold equipped with a plate or sheet in step b and heated to a temperature of 30°C to 60°C, which is preferable to obtain a uniform foam, with the side of the plate or sheet facing the solution mixture; By clamping the mold and foaming, a structure in which the foam and the plate or sheet are in close contact can be obtained. Here, the plate or sheet may be provided on either one side or both sides of the foam, but it is preferable to provide it on one side in a sandwich structure in order to improve flame retardancy. In this case, the plates or sheets provided on both sides of the two foams may be the same or a combination of different types.

(Example) The invention will be explained by examples.

Example 1 1 part by weight of 25 polyether polyol (product name: Excenol 45180, manufactured by Asahi Glass Co., Ltd., a reaction product of nlubitol and alkylene oxide).

Additive flame retardant tris(2-chloroethyl) phosphate 20 parts by weight, silicone foam stabilizer (manufactured by Dow Conning,
Trade name: Foam stabilizer 19011.0 parts by weight.

Triethanolamine 1.0 parts by weight, glycerin 7 parts 1 part
Freon 1 was mixed while keeping the solution at 20°C.
1 (manufactured by Mikata DuPont Fluorochemical Company).

(trade name) was added and mixed to obtain solution A.

Separately, 82 parts by weight of fructose, 1 part by weight of tap water, phosphonate compound dimethylmethylphosphonate (R+=&
=&=CH5) (manufactured by Box I Brown, trade name: Dolgard DMMP) and 1.0 parts by weight of triethanolamine were mixed to obtain solution B.

70 parts by weight of solution A and 880 parts by weight of solution were mixed, and 150 parts by weight of diphenylmethane diisocyanate (Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.) was mixed with this mixture. Stir and mix the mixture and keep it warm at 40℃ in a wooden mold with an open top and bottom (220 x 220 x height 15
mm), and an upper mold kept at 40°C was placed on top of the mold and the mold was clamped. After 10 minutes, the mold was removed to obtain a foam (thickness: 15 mm). The density of this foam is 1d0.03297cm3
+ Bending strength 2.8 kg/cm2. The water absorption rate was 3.

A wooden mold with an open top and a bottom (inner volume 220 x 22
0Tr11n×15TII! Place a colored iron plate (0.27 inch thick) on the underside of the mold (IL) and heat the mold to 40°C.

Next, 880 parts by weight of the above solution A70 and 150 parts by weight of diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Millionate MfL-100) were added, and the mixture was heated at 6,000 revolutions/minute using a stirrer equipped with a turbine blade. The mixture was stirred for seconds to mix, and the mixture was poured into the above-mentioned mold. Aluminum kraft paper was pasted on the upper surface of this, and an upper mold heated to 40° C. was placed with the aluminum kraft paper facing the solution mixture, and the mold was clamped. After 10 minutes, the mold was removed and the foam (thickness 15
A flame-retardant structure was obtained in which a color iron plate (thickness: 0.27 mm) was adhered to the front surface of the frame and aluminum kraft paper was adhered to the back surface.

The density of the foam that is the core material of this structure is 0.032g
/crr? , bending strength 2.8 kg/cm2. The water absorption rate was 3%, and the foam had a uniform and 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 using this structure in accordance with Ministry of Construction Notification No. 1231. As is clear from Table 1, this structure is extremely superior in terms of external appearance after combustion, afterflame 1 smoke generation coefficient, temperature coefficient, and temperature time area.

Further, the viscosity of the mixture of solutions A and B was significantly lowered to 800 cps, to the extent that it could be easily foamed in a normal low-pressure foaming machine, indicating that it has handling properties comparable to polyurethane.

Example 2 35 parts by weight of the polyether polyol used in Example 1,
Additive flame retardant tris(2-chloroethyl) phosphate 20 parts by weight, silicone foam stabilizer (manufactured by Dow Corning, trade name Foam Stabilizer 190) 1.0 parts by weight, triethanolamine 1.0 parts by weight.

While keeping the mixed solution at 20°C, Freon 11 (manufactured by DuPont DuPont Fluorochemical Co., Ltd., trade name) 16 was added to the mixed solution.
Parts by weight were added and mixed to obtain solution C.

Separately, 82 parts by weight of fructose, 1 part by weight of tap water, phosphonate compound diethyl ethyl phosphonate (R+-R
2=Rls=CH3CH2) 6 parts by weight and 2 parts by weight of triethanolamine were mixed to obtain a solution.

70 parts by weight of Solution C and 80 parts by weight of Solution D were mixed, 150 parts by weight of diphenylmethane diisocyanate (Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.) was mixed with this mixture, and the mixture was stirred at 6000 rpm for 5 seconds using a stirrer equipped with turbine blades. The mixture was stirred and mixed in the same manner as in Example 1 to obtain a structure in which a colored iron plate was adhered to the surface of a foam (thickness: 15 mm) and aluminum kraft paper was adhered to the back surface. In this case, the density of the foam is 0.036 g 7cm3. Bending strength 3.0k
g/cm2, and is a foam with a uniform and fine cell structure.

Compared to conventional foams, it was comparable in terms of compressive strength and water absorption. Using this structure, the Ministry of Construction Notification 1
Table 1 shows the results of the nonflammability test based on No. 231.

As is clear from Table 1, this structure was extremely excellent in terms of external appearance after combustion, afterflame 9 smoke generation coefficient, temperature coefficient, and temperature time area.

In addition, the viscosity of the mixture of solution C and solution is 1050CpS
(20° C.) and has a viscosity that allows easy foaming in a normal low-pressure foaming machine.

Comparative Example 1 A solution E was obtained by mixing 87 parts by weight of fructose, 13 parts by weight of tap water, and 1.0 parts by weight of triethanolamine.

7. Mix 80 parts by weight of solution E with 70 parts by weight of solution C obtained in Example 2 and 150 parts by weight of diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name: Millionate MR-100). 6000 with a stirrer with turbine blades
The mixture was stirred and mixed at a rotation speed of 5 seconds per minute, and then the same procedure as in Example 1 was carried out to obtain a structure in which a colored iron plate was adhered to the surface of a foam (thickness 15 mm) and aluminum kraft paper was adhered to the back surface.

In this case, the density of the 9 foam is 0.036 g 7 cm3.
The foam has a bending strength of 2.0 kg/cm3 and has a uniform and fine cell structure, and has a higher compressive strength than conventional foam.
It was comparable in terms of water absorption.

Table 1 shows the results of a nonflammability test conducted using this structure in accordance with Ministry of Construction Notification No. 1231. As is clear from Table 1, this structure has an external appearance after combustion.

It was extremely excellent in terms of afterflame 1 smoke generation coefficient, temperature coefficient, and temperature time area.

Note that the viscosity of the mixture of solutions C and E is s, o o o.

It had a high CpS (20°C) and was inferior to the polyurethane resin and Example 1.

Comparative Example 2 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.

Diphenylmethane diincyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name: Millionate MR-100180) 1.0 parts by weight of silicone foam stabilizer (manufactured by Dow Corning, trade name: Foam Stabilizer 190), tris (2-chloroethyl) phosphate in the heavy lid. A 20 m lid was added and mixed to obtain solution E.

8,100 parts by weight of the solution was added to 50 parts by weight of the solution DI, and stirred and mixed for 5 seconds at 6,000 rpm using a stirrer equipped with a turbine blade.
Colored iron plate on 5m1 surface.

A structure with aluminum kraft paper adhered to the back was obtained.

In this case, the density of foam 9 was 0.03367 cm 3 + bending strength 0.7 kg/cm 2 , and the foam had a uniform and fine cell structure. Table IK also shows the results of a quasi-inflammability test based on Ministry of Construction Notification No. 1231 using this structure. As is clear from Table 1, the structure of this comparative example has a better appearance after combustion than structures using incyanurate foam or phenol foam.
Although there was an improvement in the exhaust temperature after 1 minute, the basic properties required for a structure, such as a decrease in bending strength and an increase in water absorption, decreased.

The viscosity of the mixture of solutions C and D is 900 CpS (20
℃).

Comparative Example 3 Heteroform 28264 (polyol manufactured by Hooker Co., trade name) 21.1 parts by weight, Heteroform 29696
(Polyol manufactured by Hooker Co., product name a) 23.5 parts by weight,
DC-193 (foam stabilizer manufactured by Dow Corning, trade name) 1
Parts by weight, Polycat 41 (catalyst manufactured by Sun Abbott, trade name > 1.42 parts by weight.

Freon 11 (manufactured by Mikata DuPont Fluorochemical Company).

Product name) 58
Add 101 parts by weight of 0 (incyanate compound manufactured by Upjohn Co., Ltd., trade name) and mix with a stirrer equipped with turbine blades.
Stir for 5 seconds at ,000 rpm.

After mixing, the same procedure as in Example 1 was carried out to obtain a structure in which a colored iron plate was adhered to the surface of an incyanurate foam (thickness: 1511 tn) and aluminum kraft paper was adhered to the back surface.

In this case, the density of one foam was 0.03567 cm3+ and the bending strength was 2.4 kg/cm2. Table 1 shows the results of a quasi-flammability test based on Ministry of Construction Notification No. 1231 using the Amadako structure. As is clear from Table 1, the structure of this comparative example was equivalent to the foam of the example in terms of bending strength and water absorption, 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 temperature/time area.

Further, the viscosity of solution F was 300 cps (20°C).

Comparative Example 4 Danphenon 110B curing agent was added to a solution containing 100 parts by weight of Danfenone 110A (phenol resin manufactured by Hodogaya Chemical Co., Ltd., trade name) and 15 parts by weight of 7Leon 113 (blowing agent, trade name manufactured by DuPont Mikata Fluorochemical Co., Ltd.). (manufactured by Hodogaya Chemical Co., Ltd., trade name) 40 parts by weight, Danphenone 110C (manufactured by Hodogaya Chemical Co., Ltd.).

Add a solution containing 15 parts by weight of Incyanate (trade name) and stir for 5 seconds at 2,000 rpm with a stirrer equipped with a turbine blade to mix.Then, the process is repeated in the same manner as in Example 1 to form a phenol foam (thickness: 15 TEIn). A structure was obtained in which a colored iron plate was glued to the front surface and aluminum kraft paper was glued to the back surface. Since the phenol foam has extremely poor curing properties, after-curing was performed at 100° for 30 minutes. In this case 2 foam density 1
do, 0409/Cm3. Bending strength 1.2 kg/cm
It was 2. Although the structure was similar to the example in terms of bending strength and water absorption, flyability (chipping) occurred on the surface of the phenol foam, so the foam and aluminum kraft paper and color Adhesion to the iron plate was poor.

Ministry of Construction Notification No. 1231 using foam properties and structures
Table 1 shows the results of the quasi-nonflammability test based on No.

As is clear from Table 1, the structure of the comparative example had a good appearance after combustion, but the afterflame was long and inferior.

In addition, the viscosity of Danfenone 110A is 12. oo.

cps (20° C.), 9 In a normal low-pressure foaming machine, adhesion was determined by visually observing the state of adhesion between the foam and the colored iron plate and peeling them off by hand.

The water absorption rate was determined by the change in weight of the foam after immersing it in water for 24 hours.

The bending strength was measured according to JIS A 9514.

(Effects of the Invention) The foaming resin composition of the present invention has low viscosity and has excellent workability and foaming density, resulting in foaming with high flame retardancy, high strength (flexural strength) and low water absorption. A body and a structure equipped with the same can be obtained.

Claims (1)

[Claims] 1. Aqueous solution and/or slurry of carbohydrates, polyether polyol, formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R
_1, R_2 and R_3 are alkyl groups having 10 or less carbon atoms, and may contain a heteroatom such as halogen or sulfur, and R_1, R_2 and R_3 may be the same or different. ), a reaction catalyst, an incyanate compound, and optionally a polyhydric alcohol, a foam stabilizer, a flame retardant, a fiber material, and/or a foaming agent. 2. The foaming resin composition according to claim 1, wherein the water content of the aqueous solution and/or slurry of carbohydrates is 5 to 25% by weight. 3. The foaming resin composition according to claim 1, wherein the phosphonate compound is dimethylmethylphosphonate. 4. A foam obtained from the foaming resin composition according to claim 1. 5. A structure formed by providing a plate or sheet on at least one side of a foam obtained from the foaming resin composition according to claim 1.