JPH0137263B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a laminate in which at least one surface material is a noncombustible material and the core material is a urethane-modified isocyanurate foam. Conventionally, building materials such as ceiling materials and wall materials have typically been made of wood, gypsum, etc. as a core material and a surface material such as decorative paper or iron plate layered on one side.
Such construction materials have a high specific gravity, are heavy, have poor workability, have low heat insulation properties, are highly hygroscopic, and have the drawbacks of large deterioration over time due to dimensional changes. Also,
Recently, from the point of view of heat insulation and light weight, hard polyurethane foam or polyisocyanurate foam is used as the core material, and the surface material is board paper or 0.1 mm thick.
The following architectural panels using aluminum foil or plate-like bodies are also known, but although these panels can be used as interior materials for houses and buildings, they have problems with mechanical strength and durability when used as exterior wall materials. Yes, it is unusable. In addition, using a hard polyurethane foam as a base material, a large amount of flame retardant, smoke retardant, inorganic granules, etc. are mixed and filled into the foam layer, and relatively thick steel plates such as colored iron plates are laminated in one layer using these foams as a core material. It is also known that the building materials made of
There are problems with both flame retardancy and smoke-emitting properties, and the product passes grade 2 flame retardancy (quasi-noncombustible materials) in the Japanese Industrial Standard JIS A-1321 ``Test methods for flame retardancy of building interior materials and construction methods.'' There was no building material that passed the surface test, perforation test, and gas toxicity test. In addition, when the above-mentioned hard polyurethane foam is used as a core material and inorganic granules are mixed and filled, the density of the inorganic granules itself is high, and the expansion ratio of the foam itself is reduced, so the density of the core material becomes large and the laminate is The drawbacks were that it was relatively heavy and its insulation performance was reduced. Furthermore, the addition of inorganic particulates tends to increase the brittleness of the rigid polyurethane foam itself, posing problems in handling. Unmodified polyisocyanurate foam is heat resistant,
Although it has good flame retardancy and low smoke generation, it is extremely brittle, so it is usually modified with urethane. However, as the degree of urethane modification increases, brittleness is improved, but heat resistance and flame retardance are reduced, so it is usual to compromise on adequate performance. Therefore, in a laminate in which the surface material is a noncombustible material and the core material is urethane-modified isocyanurate foam, there is less brittleness and good adhesion between the surface material and the core material.
In addition, there have been no known materials that have good heat resistance, flame retardancy, and low smoke generation, and of course, no laminated materials that pass grade 2 flame retardancy (semi-noncombustible materials) have been known either. According to the present invention, by providing a laminated material in which at least one of the surface materials is a noncombustible material and the core material is a urethane-modified isocyanurate foam, it has good heat insulation properties and heat retardance, and has low smoke generation. A laminate material that is lightweight and has good adhesiveness between the surface material and the core material can be obtained. That is, the present invention provides a laminated material in which at least one surface material is a noncombustible material and the core material is a urethane-modified isocyanurate foam, in which the polyisocyanate used for producing the urethane-modified isocyanurate foam is polymethylene polyphenyl isocyanate. and using 2.0 to 8.0 equivalents of the polyisocyanate per equivalent of polyol,
and the catalyst used for producing the urethane-modified isocyanurate foam is at least one catalyst selected from the group consisting of alkali metal hydroxides, alkali metal fatty acid salts, and alkali metal alkoxides, and an organic amine compound catalyst. It is a laminated material. The surface material used to produce the laminate of the present invention has at least one side made of a noncombustible material, and the other side may be made of a noncombustible material or may be made of other materials such as paper (decorative paper, board paper, etc.), aluminum. Foil-laminated paper, asbestos paper, metal with a thickness of 0.1 mm or less (aluminum foil, etc.), synthetic resin sheets, wooden products (plywood, etc.), etc. may also be used. In the present invention, the noncombustible material has a thickness of 0.1 mm.
Although the above-mentioned metals (such as steel plates), slate plates, asbestos plates, and gypsum boards are available, steel plates with a thickness of 0.1 to 1.0 mm are preferable. The steel plate is usually coated with anti-rust coating, and the outer surface is usually finished coated. Furthermore, embossing, ricin coating, etc. are also applied when manufacturing the laminated material, if necessary. The polyisocyanate used in the present invention is polymethylene polyphenyl polyisocyanate. This polyisocyanate is a polynuclear polyisocyanate represented by the following general formula (1) obtained by the reaction of a low polycondensate of aniline and formaldehyde with phosgene, and is also called crude MD1 or polymeric isocyanate. It is something. (n is an integer of 0 or 1 or more) The average number of functional groups of this polyisocyanate is 2.1 to
3.5 is preferable. When the average number of functional groups is less than 2.1, brittleness is large and heat resistance and flame retardance are also poor. If the average number of functional groups exceeds 3.5, the brittleness and viscosity are similarly high, resulting in poor workability during foam molding. The preferred amount of the binuclear composition of the polyisocyanate is 30 to 70% by weight. The appropriate NCO/OH Index during production of the urethane-modified isocyanurate foam of the present invention is 2.0 to 8.0. If this Index is less than 2.0, the flame retardancy and heat resistance of the foam will be poor, and smoke generation will be large. If the index exceeds 8.0, the foam will be brittle and the adhesion between the foam and the surface material during foaming will be poor. It becomes defective. The catalyst used in the production of the urethane-modified isocyanurate foam of the present invention includes at least one catalyst selected from the group consisting of alkali metal hydroxides, alkali metal fatty acid salts, and alkali metal alkoxides, and the above-mentioned amine. By using a compound catalyst in combination, adhesion to the surface material during foaming is good, flame retardancy and heat resistance are good, and smoke generation is reduced. Among the above-mentioned catalysts used in the present invention, an organic amine compound catalyst causes the initial reaction of the reaction system mainly consisting of polyol, polyisocyanate, etc., that is, the urethanization reaction, and at the same time prevents the vaporization of the blowing agent due to the reaction heat. It has the function of gradually causing an isocyanurate reaction at the same time as foaming begins. Smooth initiation of this initial urethanization reaction improves the adhesion between the foam core material and the surface material. Among the above-mentioned catalysts used in the present invention, alkali metal hydroxides, alkali metal fatty acid salts, and alkali metal alkoxides mainly act effectively on the late reaction of the reaction system, that is, the reaction of converting isocyanate groups into isocyanurate, and almost completely suppress the main reaction. It has the effect of bringing it to a conclusion. Examples of the amine compound catalysts used in the present invention include amine-based urethanation catalysts (triethylamine, N-methylmorpholine, N-ethylmorpholine, triethanolamine, dimethylethanolamine, monomethylethanolamine, diethylenetriamine, Monoethanolamine, diethanolamine, tripropylamine,
Tributylamine, triethylenediamine, tetramethylbutanediamine, dimethylcyclohexylamine, N,N-dimethylbenzylamine,
N,N-dimethylbenzizylamine, N,N,
N′,N′-tetramethylhexamethylenediamine,
N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethyl-1,
Azacyclic compounds such as 3-butanediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N-dialkylpiperazines, various N,N',N''-trialkylaminoalkyls hexahydrotriazines, etc.), tertiary amine isocyanurate catalyst (N,N',N''-tris(dialkylaminoalkyl)hexahydro-s
-triazine, 2,4,6-tris(dimethylaminomethyl)phenol, diazabicyclooctane, dimethylstearylamine, hexahydromethylaniline, dimethylpiperazine, N,N,
N',N''-tetramethyl-1,3-butanediamine, triethylene diamine, tetramethylethylene diamine, etc.), but 2,4,6-tris (dimethylaminomethyl)phenol, N,N',N''-tris(dialkylaminoalkyl)hexahydro-s-triazine are preferred. Among the catalysts used in the present invention, examples of alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Among the catalysts used in the present invention, examples of the alkali metal fatty acid salts include sodium acetate, sodium n-octoate, sodium 2-ethylhexanoate, sodium benzoate, sodium adipate, potassium acetate, potassium n-octoate,
Potassium 2-ethylhexanoate, potassium benzoate, potassium adipate, etc. Among the catalysts used in the present invention, examples of the alkali metal alkoxide include sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium butoxide, potassium butoxide, sodium phenolate, potassium phenolate, etc. . In addition to the above-mentioned catalysts, the catalysts of the present invention include organometallic urethanation catalysts (dibutyltin dilaurate,
(Sibutyltin diacetate, dibutyltin dichloride, tin octoate, lead octoate, lead naphthenate, etc.) can also be used if necessary. The amount of catalyst used in the catalyst system of the present invention, that is, the system in which at least one catalyst selected from the group consisting of alkali metal hydroxide, alkali metal fatty acid salt, and alkali metal alkoxide is combined with an organic amine compound catalyst is as follows:
Polyisocyanate, foaming agent, foam stabilizer,
Cream time when producing the urethane-modified isocyanurate foam core material of the present invention by stirring other additives (flame retardants, fillers, etc.) as necessary (the reaction stock solution foams and becomes creamy from the start of stirring) The amount is such that the tack-free time (the time from the start of stirring until the surface tackiness of the foam disappears) is 3 to 30 seconds, and the tack-free time is 10 to 120 seconds. The amount of the catalyst system of the present invention used is usually 0.1 to 30.0 parts by weight per 100 parts by weight of the polyisocyanate (hereinafter, parts represent parts by weight). Examples of polyols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, hexylene glycol, hexane glycol, glycerin,
Low molecular weight polyols such as trimethylolpropane, compounds such as water ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose; ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Aliphatic polyamines; methylene orthochloroaniline,
Aromatic polyamines such as 4,4'-diphenylmethanediamine, 2,4-tolylene diamine, and 2,6-tolylene diamine; ethylene oxide, propylene oxide, butylene to alkanolamines such as triethanolamine and diethanolamine, etc. These include polyether polyols to which alkylene oxide such as oxide is added, polytetramethylene ether polyols, polyester polyols, and the like. The amount of polyisocyanate and polyol used is
Polyisocyanate per equivalent of polyol
Use at a ratio of 2.0 to 8.0 equivalents. The blowing agent used in the production of the urethane-modified isocyanurate foam of the present invention is an inert low-boiling solvent, examples of which include trichloromonofluoromethane, methylene chloride, dichlorodifluoromethane, trichlorotrifluoroethane, and dibromochloride. Examples include tetrafluoroethane, trichloroethane, pentane, and n-hexane, with trichloromonofluoromethane being particularly preferred. The amount of blowing agent added is usually 5% to the foam stock solution.
~50% by weight (hereinafter % represents weight%) is used. The foam stabilizers used in the production of the urethane-modified isocyanurate foam of the present invention include various silicone foam stabilizers provided for the production of rigid urethane foam, oxyethylated alkylphenols, and oxyethylated aliphatic foams. Surfactants such as alcohols and block copolymers of ethylene and propylene oxide can be used. For example, silicone foam stabilizers include L-5340, L-5350, L-5420 manufactured by Nippon Unicar Co., Ltd.
SH- manufactured by Toray Silicone, such as L-5430
193, SH-195, etc. The amount of the foam stabilizer added is 0.01 to 5.0 parts per 100 parts of polyisocyanate. The method for industrially manufacturing the laminated material of the present invention includes a foaming machine that stirs and injects the foaming stock solution, a conveyor that conveys the upper and lower surface materials, a caterpillar that compresses the surface materials, a heating furnace that accelerates the hardening of the foam foam, There is a method of continuous production using a known double conveyor type hard urethane foam laminate production apparatus equipped with a cutter or the like for cutting the produced laminate into appropriate lengths. Of course, it is also possible to manufacture the panel by foaming the panel using a suitable mold. The laminates of the present invention generally do not require the addition of inorganic particulates to the core foam. By not using inorganic particulates, it is possible to lower the density of the urethane-modified isocyanurate foam of the core material, and it is possible to avoid the increase in density due to the addition of inorganic particulates and the increase in manufacturing costs due to the complexity of the processing process. In addition, the laminated material of the present invention has good heat resistance and flame retardancy, and can pass the flame retardant class 2 (semi-noncombustible material) test depending on the selection of raw materials, face materials, and surface treatment used in the production of urethane-modified isocyanurate foam. It is possible to pass. The laminated material of the present invention can be used for various purposes such as interior partition materials and exterior wall materials. As an exterior wall material, it can be used as an exterior wall material whose surface exposed outdoors is metal, that is, a metal sizing material. When using the laminated material according to the present invention as a metal sizing material, depending on the selection of raw materials, face materials, surface treatment, etc., it may be necessary to pass the fire protection structure test specified in Japanese Industrial Standards JISA-1301 and JISA-1302. is also possible.
The thickness of the core material foam of the present invention is preferably 7 to 25 mm. If the thickness is less than 7 mm, the insulation and mechanical strength will be insufficient, and if the thickness exceeds 25 mm, it will not pass the semi-flammability test. Next, the present invention will be described in more detail with reference to Examples. The raw materials used for producing the urethane-modified isocyanurate foams described in the Examples are as explained in (1) to (7) below. (1) MDI-CR-200 Polymethylene polyphenyl polyisocyanate (NCO 30.8%) manufactured by Mitsui Toatsu Chemical Co., Ltd. (2) L-5340 Silicone foam stabilizer manufactured by Nippon Unicar Co., Ltd. (3) F-11A Mitsui Fluoro Trifluoromonofluoromethane (4) manufactured by Chemical Co., Ltd. MN-300, MN-450, PE-450, SU-
450LA, HS-700N Polyoxypropylene polyol manufactured by Mitsui Nisso Urethane Co., Ltd. Initiator, OH
The values are shown in Table 1.

[Table] (5) Polycat#41 Isocyanurate catalyst manufactured by Sun Abbott (6) DMP-30 Isocyanurate catalyst manufactured by Rohr & Haas (7) Kaolizer No.1 Urethane catalyst manufactured by Kao Soap Co., Ltd. As described in the examples The tests carried out were based on the method described below. (a) Surface test Compliant with JISA-1321. (b) Drilling test Compliant with JISA-1321. (c) Crack deformation Compliant with JISA-1321. The JIS A-1321 flame retardant grade 2 (quasi-noncombustible material) passing standard values are as follows.

[Table] Examples 1 to 6 [Manufacture of laminated materials] Colored iron plates (thickness: 0.3 mm) cut to the same dimensions were laid on an aluminum formwork of 36 cm in length and width.
Fix both of them and warm them to about 45℃ in advance. On top of this, each component is mixed in the same manner as in the case of foam manufacturing, and after stirring at high speed, the mixed liquid is poured onto the above-mentioned collar iron plate, and then it is mixed with the other side material through a spacer to achieve a predetermined thickness of the laminated material. The mold was firmly fixed with an aluminum top lid lined with aluminum foil on the inside, and the mold was pressed to the extent that it could withstand the foaming pressure.The mold was cured in an oven at approximately 100℃ for 1 hour, and after curing, the mold was removed and laminated. I got the material. Table 2 shows the composition (parts by weight), surface test and perforation test results of this laminate. As shown in Table 2, it can be seen that the laminated material produced by the method of the present invention has good adhesion, heat insulation, and flame retardancy, and has low smoke generation. It has also passed the JISA-1321 flame retardant class 2 (quasi-noncombustible material) surface test and perforation test. Comparative Example 1 Example 1 except that the NCO/OH equivalent ratio was 1.3.
A laminate was obtained in the same manner as above. The test results are shown in the second
Also listed in the table. The laminated material of this comparative example had a smoke emission coefficient as high as 90 in the perforation test compared to the laminated material of Example 1, and did not pass the perforation test of the semi-flammability test. Comparative Example 2 A laminate was obtained in the same manner as in Example 1 except that the NCO/OH equivalent ratio was 10. The test results are also listed in Table 2. Although the laminated material of this comparative example had excellent flame retardancy, the foam was brittle and the adhesiveness between the foam and the surface material was poor, making it unsuitable for practical use.

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Claims (1)

[Claims] 1. In a laminated material in which at least one surface material is a noncombustible material and the core material is a urethane-modified isocyanurate foam, the polyisocyanate used in the production of the urethane-modified isocyanurate foam is polymethylene polyphenyl isocyanate, and The polyisocyanate is used in an amount of 2.0 to 8.0 equivalents per equivalent of the polyol, and the catalyst used for producing the urethane-modified isocyanurate foam is selected from the group consisting of alkali metal hydroxides, alkali metal fatty acid salts, and alkali metal alkoxides. A laminated material comprising at least one type of catalyst and an organic amine compound catalyst.