JPS61266238A - Flame-retardant structure - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a structure with excellent flame retardant properties useful as a building material.

(Prior art) Recently, flame retardant requirements for building materials, especially residential exterior wall materials, have become more severe, and the Ministry of Construction Notification No. 1231 quasi-flammability test includes the Ministry of Construction notification No. 137.2 model box test. It ended up being added. The above-mentioned Ministry of Construction Notification No. 1372 model box test is the afterflame, temperature time area 2 in the same No. 1231 quasi-noncombustible test.
It is a very strict test that requires meeting the smoke emission coefficient regulation value, then increasing the size of the test specimen and determining the calorific value during combustion and the shape after combustion. Structures using conventional isocyanurate foams (a type of polyurethane foam) having isocyanurate rings made from industrial polyol as a raw material undergo significant shape change after combustion and generate a large amount of heat, so they are not suitable for use in No. 1372. It is difficult to pass the model box test. On the other hand, structures using known phenol foams are
Although there is little change in shape after combustion, it has the disadvantage of a long afterflame time after combustion. Conventional incyanurate foam with isocyanurate rings (a type of polyurethane foam)
When switching the production equipment used for molding phenolic foam to molding phenol foam, the heating equipment during and after foaming must be changed to equipment that can heat at high temperatures and for long periods of time. The method for producing phenol foam using the method also has extremely poor workability.

(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 reduce shape change during combustion. The purpose of the present invention is to provide a flame-retardant structure using a polyurethane foam with low calorific value.

(Failure to solve the problem) The present invention provides an aqueous solution and/or slurry of carbohydrates.

A flame-retardant structure comprising a polyurethane foam obtained from a composition containing a reaction catalyst, a polyisocyanate, and optionally a foam stabilizer and a flame retardant, and a flame-retardant or non-flammable plate or sheet provided on at least one side of the polyurethane foam. .

Examples of flame-retardant or noncombustible plates or sheets in the present invention include aluminum kraft paper, aluminum foil, metal foil such as copper foil, and aluminum asbestos sheet.

Metal plates such as wood wool cement boards, iron plates, steel plates, stainless steel plates, aluminum plates, copper plates, slate boards, calcium silicate boards, gypsum boards, cement boards, and inorganic noncombustible boards such as glass fiber reinforced cement boards.

These flame-retardant or noncombustible boards or sheets may be painted in outside areas for reasons such as 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.

The carbohydrate aqueous solution and/or slurry used in the polyurethane foam of the present invention is 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. A commercially available product is manufactured by Oji Cornstarch Co., Ltd.

There are isomerized sugars F-42, F-55 and HC. For example, H
C contains 55.9% by weight of fructose, 39.2% by weight of glucose, and 4.9% by weight of other sugars.

Furthermore, the mixture contained 24.5% by weight of water as a whole. In addition, Suncraft 550 manufactured by Sanmatsu Kogyo Co., Ltd. contains 55.6% by weight of fructose, 39.3% by weight of glucose, and 5.1% by weight of oligosaccharide as sugar components, and has a total water content of 24.5% by weight. It is a mixture containing % by weight.

As the reaction catalyst in the present invention, soot compounds such as dibutyltin dilaurate and dibutyltin dioctoate,
Examples include amine compounds such as triethylamine, triethylenediamine, triethanolamine, 2-dimethylamino-2-methyl-1-propatol, and 2-amino-2-methyl-1-propatol. In the present invention, silicone polymers are used as foam stabilizers if necessary.1 L-520, L-54 manufactured by Nippon Unicar Co., Ltd.
0, L-5340, L-5350, L-5410, L-
5430, manufactured by Dow Corning Co., Ltd., 190, 191
, 193 etc. Further, flame retardants that may be used as necessary include tris(2-fluorochloroethyl) sulfate, tris(2-7-oloroprobyl) phosphate, and chlorinated halafine.

Examples include organic flame retardants such as hexabromobenzene, and inorganic flame retardants such as antimony dioxide and aluminum hydroxide, and these can be used alone or in combination.

Examples of the polyisocyanate in the present invention include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4
Polyisocyanates, such as polymethylene polyphenylisocyanate, mixtures thereof, or derivatives of these incyanates, may be used.Refined or crude polyisocyanates can be used.

In the present invention, there are no particular restrictions on the blending ratio of each material used in molding the polyurethane foam. Weight part (C)
Foam stabilizer (selective) 01 to 5 parts by weight (d) Polyisocyanate 50 to 200 parts by weight (e) Flame release agent (selective) Used preferably in a proportion of 0.1 to 100 parts by weight, more preferably (b) Reaction catalyst 0.5 to 4.0 parts by weight (C
) Foam stabilizer (selective) 0.5 to 4.0 parts by weight ((11 polyisocyanate 50 to 150 parts by weight) (e) Flame retardant (selective) 5 to 50 parts by weight. Also, workability In the relationship, for example, a mixture of (a) and (b) and (e),
It is also possible to prepare a mixture of (d) and (e), mix the two, cause two reactions, and foam. The reaction temperature is not particularly limited, but is preferably 10 to 50°C.
There is no limit to the number of rotations of the stirrer during mixing, but 1. OO
0 to 7,000 revolutions/min is preferred. When molding the foam, there are no particular restrictions, but it is preferable to use a mold.2 For example, a mold with an open top and a bottom is used.

Place a flame-retardant or non-combustible board or sheet on this bottom surface,
The mold is preferably heated to 30°C to 60'C to obtain a uniformly luminous foam.
K Keep warm. Next, the materials for the polyurethane foam are stirred and mixed and poured into the mold. Next, 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 for obtaining a uniform foam, is placed on the mold with the side of the plate or sheet facing the mixture. Mold clamping 9
When a foamed structure is obtained, it can be made.

In the present invention, a flame retardant or noncombustible plate or sheet may be provided on one side of the foam -C, but it is preferable to have a sandwich structure in which it is provided on two surfaces in order to improve flame retardant properties. In this case, the flame-retardant or noncombustible plates or sheets provided on both sides of the two foams may be the same or a combination of different types.

(Example) The present invention will be explained below with reference to Examples.

Example 1 Solution A was obtained by adding and mixing 25 parts by weight of tap water and 1.5 parts by weight of triethanolamine to 75 parts by weight of fructose. Diphenylmethane diisocyanate B'EJ (manufactured by Honpolyurethane Co., Ltd., trade name: Millionate MR-ioo); 1.0 parts by weight of foam stabilizer (manufactured by Dow Co., Ltd., trade name: Foam Stabilizer 190)
Parts by weight and tris(2-chloroethyl)phosphate zo weight m were added and mixed to obtain a solution B. Next, a wooden mold with an open top and a bottom (inner volume 220mm x 2'20
A color iron plate (thickness: 0.27 mm) was placed on the bottom surface of the mold, and the mold was heated to 40°C.

Next, 100 parts by weight of solution B was added to 100 parts by weight of solution A, and the mixture was stirred and mixed for 5 seconds at 2,000 rpm in a stirrer equipped with a Tanibin-type blade. The upper mold, which had been pasted and heated to 40°C, was placed with the aluminum clarad paper side facing the solution mixture, and the mold was clamped. After 10 minutes, the mold was removed to obtain a flame retardant structure in which a color iron plate was adhered to the surface of the polyurethane foam (thickness: 15 mm) and aluminum kraft paper was adhered to the back surface. The foam that is the core of this structure has a density of 0.035 g/am" and a compressive strength (at 20% compression) of 0.25 g 70 m", and has a uniform and fine cell structure. Ta. Table 1 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 example has an external appearance after combustion and an afterflame.

It was extremely excellent in terms of smoke generation coefficient and temperature/time area.

Example 2 To 100 parts by weight of solution B obtained in Example 1, 30 parts by weight of aluminum hydroxide (manufactured by Showa Denko K.K., trade name Hisilite H32) was added and mixed, and to the mixture was added 100 parts by weight of solution A obtained in Example 1. Thereafter, in the same manner as in Example 1, a flame-retardant structure using a polyurethane foam as a core material was obtained. The density of this foam is 0.0409/Cm", and the compressive strength is 20 inches when compressed>
h6. a o kg/am" and was a foam with a uniform and fine cell structure.The results of a quasi-noncombustibility test based on Ministry of Construction Notification No. 1231 using the same combustible structure were as follows: 1 is shown in Table 1. As is clear from Table 1, the flame retardant structure of this example is more flame retardant than the structure of Example 1.

Furthermore, the appearance, shape, smoke generation coefficient, and exhaust temperature after 5 minutes were improved.

Comparative Example 1 Hetero 7 ohm 2'8264 (manufactured by Hooker, trade name)
'21.1! Part f, Heteo:y;t-A 2969
6 (manufactured by Hooker Co., trade name) 23.5 parts by weight, DC-1
93 (manufactured by Dow Corning, trade name) 1 part by weight.

Polycat 41 (manufactured by Sun Abbott, product name) 1.4
2 parts by weight of Freon 11 (manufactured by Mitsui Fluorochemical Co., Ltd., trade name) 25 parts by weight of isone) 580
(manufactured by Upjohn Co., Ltd., trade name) was added in the same manner as in Example 1 to obtain a structure having an isocyanurate foam as a core material.

The density of this foam was 0, and the compressive strength (at 20% compression) was 0.90 kg/cm2. 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, in the structure of this comparative example, the external appearance changed significantly after combustion, and most of the foam was burned out. Smoke generation coefficient 9
It was also significantly inferior in terms of time and area.

Comparative Example 2 Danfenone 110A (manufactured by Hodogaya Chemical Co., Ltd., trade name) 1
00 parts by weight and Freon 11 (manufactured by Mitsui Fluorochemical Co., Ltd.,
Product name) Danphenone 11 in a solution mixed with 15 parts by weight
0B curing agent (manufactured by Hodogaya Chemical Co., Ltd.)

A solution containing 40 parts by weight of Danphenon 11oc (product name) and 15 parts by weight of Danphenon 11oc foam stabilizer (manufactured by Hodogaya Chemical Co., Ltd., product name) was added, and the same procedure as in Example 1 was carried out to prepare a structure having phenol foam as the core material. Obtained. but.

Phenol foam is rated 1o because its curing properties are extremely poor.

After-cure was performed for 30 minutes. The density of this foam is 0.040 g/cm3. The compressive strength (at 20% compression) was 0.95 kg/Cm2. In addition, this structure had poor adhesion to aluminum kraft paper and colored iron plates because 7 pores were formed on the surface of the 7 elastomer foam. Table 1 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 had a good appearance after combustion, but the afterflame (effect of the invention) Compared to structures using phenol foam or incyanurate foam made from industrial polyol, it has extremely superior characteristics in terms of external appearance after combustion, afterflame 2 smoke emission coefficient, and temperature-time area. This is a flame-retardant structure.

Procedural amendment (spontaneous) April 24, 1985 1, Indication of the case 1985 Patent Application No. 107789 2, Name of the invention Flame retardant structure 3, Person making the amendment Relationship to the case Patent applicant name Name (445) Hitachi Chemical Co., Ltd. 5, Column lines for claims and detailed description of the invention in the specification subject to amendment, page 4, line 7, page 6, line 10, page 7, bottom 5 lines From line 4, page 8, line 2, page 9, line 11, and page 10, line 7, "polyurethane foam" is replaced with "foam".
I will correct it.

3) Page 13 (Table 1) of this Specification H is corrected as follows.

Attached Claim 1, Aqueous solution and/or slurry of carbohydrate, reaction catalyst,
A flame retardant structure comprising a foam obtained from a composition containing a polyisocyanate and optionally a foam stabilizer and a flame retardant, and a flame retardant or nonflammable plate or sheet provided on at least one side of the foam.

Claims (1)

[Claims] 1. Aqueous carbohydrate solution and/or slurry, reaction catalyst,
A flame-retardant structure comprising a polyurethane foam obtained from a composition containing a polyisocyanate and, if necessary, a foam stabilizer and a flame retardant, and a flame-retardant or non-combustible plate or sheet provided on at least one side of the polyurethane foam.