JPS62243613A - Foaming resin composition - Google Patents

Abstract

PURPOSE:To provide a foaming resin composition composed of an aqueous solution or slurry of a carbohydrate, a specific polyether polyol, a reaction catalyst and an isocyanate compound and capable of giving a foamed product having excellent flame-retardance, high strength and low water-absorption. CONSTITUTION:The objective foaming resin composition is produced by mixing (A) preferably 50-150pts.(wt.) of an aqueous solution and/or slurry of a carbohydrate (e.g. fructose) (preferably having a water-content of 5-20wt%), (B) preferably 10-100pts. of a polyether polyol produced by reacting an alkylene oxide to a sugar having cyclic structure (preferably sucrose), (C) preferably 0.5-4.0pts. of a reaction catalyst (e.g. dibutyltin laurate), (D) preferably 50-150pts. of an isocyanate (e.g. phenyl isocyanate) and, if necessary, (E) preferably 0.5-4.0pts. of a foam stabilizer (e.g. silicone polymer) and/or preferably 5-50pts. of a flame-retardant [e.g. tris(2-chloroethyl)phosphate].

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) 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 severe, and the model box test No. 1372 has been added to the semi-flammability test No. 1231 of the Ministry of Construction. It has come to pass. This model box test is carried out in Ministry of Construction Notification No. 1372, which satisfies the regulation values for afterflame and temperature-time curve 1 smoke generation coefficient in the same No. 1231 quasi-nonflammability test, and then increases the size of the test specimen to generate heat during combustion. It is extremely difficult to judge the amount and shape after combustion.

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

(Problems to be Solved by the Invention) Structures using conventional incyanurate foams having incyanurate rings formed from industrial polyol as a raw material undergo significant shape changes after combustion.

〈Because the calorific value is large, please refer to the above! It is difficult to pass the model box test No. 1372.

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 production equipment used to mold incyanurate foam having incyanurate rings to molding 7-Nol foam, heat the heating device at high temperature and for a long time during and after foaming. However, the method for producing phenol foam using this equipment also has extremely poor workability. - Although the flame retardance of the secondary structure is improved somewhat compared to the structure using incyanurate foam made from industrial polyol, it is not sufficient. I can't say it.

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 such problems, and
Taking advantage of the excellent workability of polyurethane foam, #l&
Excellent flammability. With high strength (bending strength).

It is an object of the present invention to provide a foaming resin composition that provides a foam with low water absorption.

(Means for solving problems) The present invention provides an aqueous solution and/or slurry of carbohydrates.

The present invention relates to a foaming resin composition containing a polyether polyol obtained by reacting a sugar having a cyclic structure with an alkylene oxide, a reaction catalyst, an isocyanate compound, and, if necessary, a foam stabilizer and/or a flame release agent.

The carbohydrate aqueous solution and/or slurry used in the foaming resin composition of the present invention includes fructose, grapevine, sugar,
These are an aqueous solution prepared by dissolving maltose, cellulose, etc. alone or in combination of two or more thereof in water, a slurry obtained by dispersing them in water, or a mixture of such an aqueous solution and a slurry. Examples of commercially available products include isomerized sugar F-42, F-55, (C) manufactured by Oji Cornstarch Co., Ltd., and Suncraft 550 manufactured by Sanmatsu Kogyo Co., Ltd. HC manufactured by Oji Cornstarch Co., Ltd. Aqueous solutions of fructose, glucose and other sugars, Sanmatsu Kogyo Co., Ltd., Suncraft 5
50 is an aqueous solution of fructose, glucose and oligosaccharides.

There is no limit to the water content in the carbohydrate aqueous solution and/or slurry, but it is preferably 5 to 20% by weight. When the amount exceeds 20% by weight, the strength of the foam decreases, and when it is less than 5% by weight, the viscosity tends to be high 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 oxide is 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 sucrose is used.

It is particularly effective in improving the strength of foam. As a commercially available product of this polyether polyol, Excenol 4508 manufactured by Asahi Glass Co., Ltd. Efsenol 3F5S, Exenol 4558. SANIX manufactured by Sanyo Chemical Co., Ltd.) (R-4
50F, San-X H8-209, etc.

By using this polyether polyol, it is possible to increase the strength and strength of the resulting foam and reduce its water absorption rate without increasing the smoking coefficient or combustion temperature.

As the reaction catalyst in the present invention, tin compounds such as dibutyltin dilaurate and dibutyltin dioctoate,
Amine compounds such as triethylamine, triethylenediamine, triethanolamine, 2-dimethylamino-2-methyl-1-propatol, and 2-amino-2-methyl-1-propatol are used.

The isocyanate compound in the present invention includes:

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

Diisocyanate compounds such as naphthalene diinocyanate, inphorone diisocyanate, diphenylmethane-4,4'-diisocyanate, paraphenylene diisocyanate, triisocyanate compounds such as triphenylmethane-4,4:4''-triisocyanate, etc., or isocyanates thereof. A low-molecular or high-molecular NCO-terminated prepolymer derived from is used.

The foam stabilizer used as needed in the present invention includes silicone polymer Ashi 2 L manufactured by Nippon Unicar Co., Ltd.
-520, L-540, L-5340゜L-5350,
There are L-5410, L-5430, 190, 191, 193 manufactured by Dow Corning Co., Ltd., and the like.

Flame retardants that may be used as needed include organic flame retardants such as tris(2-lya-loethyl) 7-o-7ate, tris(2-ly-a-loprovil) 7-o-7ate, chlorinated paraffin, and hexabromobenzene. There are inorganic flame retardants such as antisodium trioxide, aluminum hydroxide, etc., and these can be used alone or in combination.

Furthermore, it is used as a second blowing agent to improve workability such as the viscosity of the composition and to obtain a foam with a high expansion ratio.

It is also possible to use low boiling point solvents such as monofluorotrichloromethane, trifluorotrichloroethane. Commercially available products include Mitsui DuPont 70 Rochemical Co., Ltd. 7 Leon 11 (boiling point 23.8°C), Freon 113
(boiling point 47.6°C), 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 plate or sheet is provided on at least one side of the foam. Examples of this plate or sheet include aluminum kraft paper, aluminum foil, and metal foil such as copper foil.

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

Preferred are metal plates such as steel plates, stainless steel plates, aluminum plates, and copper plates, 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 take into account the material and thickness of the paint film used for the paint so as not to reduce its flame retardance, but if the paint film is thin, there are no particular restrictions on the material.2Usually commercially available colors 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 17-50
~200 parts by weight (b) Polyether polyol obtained by reacting MK alkylene oxide having a cyclic structure
5 to 200 parts by weight (C) Reaction catalyst 0.1 to 5 parts by weight (d) Isocyanate compound 50 to 200 parts by weight + 6) Blowing agent (selective) 0.1 to 5 parts by weight (f) *Fuel agent (selective) ) It is preferably used in a proportion of 0.1-100 parts by weight.

(a) Aqueous solutions and/or slurries of carbohydrates 17-50
~150 parts by weight (b) Polyether polyol obtained by reacting alkylene oxide with sugar having a cyclic structure
10 to 100 parts by weight (C1 reaction catalyst
0.5 to 4.0 parts by weight (d) Isocyanate compound 50 to 150 parts by weight (e) Foam stabilizer (selective) 0.5 to 4.0 parts by weight (f) Flame retardant (
(Optional) It is preferable to use KIE in a proportion of 5 to 50 parts by weight. In addition, due to workability, for example (2)
A mixture of a), (b) and (C) and (d).

It is also possible to prepare a mixture of (e) and (f), mix the two, 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 also not particularly limited, but is 1.000 to 7.
．． 000 revolutions/min is preferred. When molding a foam or structure, it is preferable to use a mold, although there are no particular restrictions.2 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. Place the mold at a temperature of 30°C to 60°C, which is preferable to obtain a uniform foam.
Warm it up. Next, each of the materials for the foam is stirred and mixed and poured into the mold, followed by a flame-retardant or non-combustible plate or sheet, which is preferably heated at 30°C to 60'CK to obtain a uniform foam. Place the warmed upper mold with the plate or sheet side facing the solution mixture, clamp the mold, and let it foam.

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 in a sand-inch structure in order to improve the flame-retardant properties. In this case, the flame-retardant or noncombustible plates or sheets provided on both sides of one 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 111 parts of tap water, a polyether polyol obtained by reacting an alkylene oxide with a sugar having a P!J structure (Asahi Glass Co., Ltd.) Company name: EXCENOL 4508
) were mixed to obtain solution A. 80 parts by weight of diphenylmethane diisocyanate (trade name Millionate M It-100, manufactured by Nippon Polyurethane Co., Ltd.), 1.0 parts by weight of a foam stabilizer (trade name Foam Stabilizer 190, manufactured by Dow Corning Co., Ltd., and 20 parts by weight of tris (2-chloroethyl) phosphate). and mixed to obtain Solution B. Next, 100 parts by weight of Solution A and 100 parts by weight of Solution B were mixed and stirred for 5 seconds at 2,000 rpm with a stirrer equipped with turbine blades.

The mixture was poured into a wooden mold (220 x 220 x height 15 mm) with an open top and bottom kept at 40°C, and an upper mold kept at 40°C was placed on top and the mold was clamped. After 10 minutes, the mold was demolded to obtain a foam (thickness: 15 m+■). This foam had a density of 0.039/cm", a bending strength of 1.6 kg/cm", and a water absorption rate of 3.

Two reference examples of flame-retardant structures obtained using the foamable resin composition of the present invention are shown below.

Reference example: Wooden mold with open top and bottom (inner volume 220mu+X
220arm
0.27 arm) and warm the mold to 40°C.

Next, add solution B1 to 100 parts by weight of solution A used in Example 1.
Add 0.00 parts by weight and mix with a stirrer equipped with turbine blades.
Stir and mix at 00 revolutions/min for 5 seconds, pour this into the above mold, paste aluminum kraft paper on the top surface, heat the upper mold to 40 ° C, and direct the aluminum kraft paper toward the solution mixture. The mold was then placed and clamped. After 10 minutes, the mold was removed and a colored iron plate (thickness 0) was placed on the surface of the foam (thickness 15IIIu).
．． 27 mm) A flame-retardant structure with aluminum kraft paper adhered to the back surface was obtained.

The density of the foam that is the core material of this structure is 0.033g/
cm's bending strength 1.6 kg/cm" e water absorption rate is 3
%, the foam has a uniform and fine cell structure, and is comparable to conventional foams in terms of compressive strength and water absorption. Using this structure, Ministry of Construction Notification 12
Table 1 shows the results of the nonflammability test based on No. 31. As is clear from Table 1, this structure has an external shape after combustion,
It was extremely excellent in terms of afterflame 2 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.

Solution 0100 was added to 100 parts by weight of solution B obtained in Example 1.
Add parts by weight and mix with a stirrer equipped with turbine blades to 2,000
The mixture was stirred and mixed at 0 revolutions/min for 5 seconds, and the procedure was repeated in the same manner as in Reference 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 2
The density of the foam is 0.035 g/c♂1 and the bending strength is 0.7
kg/cm", and was a foam with a uniform and fine cell structure. Table 1 shows the results of a semi-flammability test based on Ministry of Construction Notification No. 1231 using this structure. Table 1. As is clear from 1, the structure of this reference comparative example has a higher appearance shape and smoke emission coefficient after combustion than structures using in-annulate foam or phenol foam.

Although the exhaust temperature after 5 minutes has improved in each point, 2
The basic properties required for structures, such as a decrease in bending strength and an increase in water absorption, have declined.

Reference Comparative Example 2 Heteroform 28264 (polyol manufactured by 7Tsuriki Co., Ltd., trade name) 21.1 parts by weight, Heteroform 2969
6 (Polyol manufactured by Hooker Co., Ltd., trade name) 23.5 parts by weight, DC-193 (foam stabilizer manufactured by Dow Corning Company, trade name) 1 part by weight, Polycat 41 (catalyst manufactured by Sun Abbott, trade name) 1 .42 parts by weight.

7 Leon 11 (manufactured by DuPont Mitsui Fluorochemical Co., Ltd.).

Product name) Add Isonate 580 to the solution mixed with 25-layer lid.
(Isocyanate compound manufactured by Upjohn Company.

Add 1 part by weight of product name 310 and stir and mix for 5 seconds at 2,000 rpm using a stirrer equipped with a turbine blade.
A structure was obtained in which a colored iron plate was adhered to the front surface of the nu) and aluminum kraft paper was adhered to the back surface. In this case, the density of the two foams is 0.
0356/am” and bending strength Z 4 kg/cm2.This structure was also used to comply with Ministry of Construction Notification No. 1231.
Table 1 shows the results of the quasi-nonflammability test based on No. Table 1
As is clear from the above, although the structure of this reference comparative example was equivalent 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. It was also significantly inferior in terms of smoke generation coefficient and 2-hour temperature area.

Reference Comparative Example 3 Danfenone 110B curing agent was added to a solution containing 100 parts by weight of Tanfenone 110A (phenol resin manufactured by Hodogaya Chemical Co., Ltd., trade name) and 15 parts by weight of 7 Leon 11 (blowing agent manufactured by DuPont Mitsui Fluorochemicals, trade name). Add a solution containing 40 parts by weight of Danfenone 110C foam stabilizer (manufactured by Hodogaya Chemical Co., Ltd., trade name) and 15 parts by weight of the foam stabilizer (manufactured by Hodogaya Chemical Co., Ltd., trade name), and rotate at 2,000 revolutions using a stirrer equipped with turbine blades. /min for 5 seconds, and 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 a phenol foam (thickness: 15 m) and aluminum kraft paper was adhered to the back surface. Since the phenol foam has extremely poor curing properties, it was subjected to after-airing at 100° C. for 30 minutes.

In this case 9 foam density Fio, 040 G101+
3. The bending strength was 1.2 kg/cm''.Although the structure was similar to Example 1 in terms of bending strength and water absorption, the surface of the phenol foam had a Because of this, the adhesion between the foam and the aluminum kraft paper and colored 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 reference comparative example had a good appearance after combustion, but the afterflame was long and inferior.

(Effects of the Invention) As is clear from the above, the foaming resin composition of the present invention has high flame retardant properties, high strength (high bending strength), and low water absorption. This is a foaming resin composition that produces a foam body.

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 optionally a foam stabilizer and/or A foaming resin composition containing a flame retardant. 2. The foaming resin composition according to claim 1, wherein the sugar is castor sugar. 3. Claim 1 or 2, wherein the carbohydrate aqueous solution and/or slurry has a water content of 5 to 20% by weight.
The foaming resin composition described in .