JP2000336301A - Foaming type fireproof coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foaming type fireproof coating composition giving off a small amount of smoke on combustion and capable of providing a heat- insulation layer excellent in preservation of the shape because a saturated hydrocarbon-based polymer-based composition causes a large amount of the smoke on combustion when the amount of oxygen is in short supply, and when the composition is burned according to the standard heating curve, the burning down of the heat-insulation layer is caused and shape preservation after the burning is difficult. SOLUTION: This foaming type fireproof coating composition to be attached to the outer periphery of a quake-free laminated rubber device composed of a laminated structure of a metal and a rubber, and preventing the quake-free device from being burnt in case of fire consists essentially of the following components (A), (B) and (C): (A) a saturated hydrocarbon-based polymer having a hydroxy group bound to a silicon atom or a hydrolyzable group, and at least one silicon-containing group capable of being cross-linked by forming a siloxane bond; (B) a polyphosphoric acid salt compound; and (C) an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foam type fire protection composition for a fireproof covering material of a laminated rubber bearing used in a seismic isolation device or the like, and to follow the shear deformation of the seismic isolation device during an earthquake, The present invention relates to a foam type fire protection composition having an effect of protecting a seismic isolation device and maintaining seismic isolation performance by forming a foam incombustible layer at the time of flame of a structure.

[0002]

2. Description of the Related Art Conventionally, a base plate is attached to upper and lower ends of a laminated rubber bearing body in which a rubber plate and a metal plate are sequentially stacked and integrally formed, and this laminated rubber bearing member is attached to an upper structure of a building. BACKGROUND ART A laminated rubber seismic isolation device interposed between a lower structure and a lower structure is known. When such a seismic isolation device is installed on a middle floor of a building, the laminated rubber bearing is to be treated as a pillar, so that a fireproof structure is required.

[0003] The fire-resistant structure of the laminated rubber support is a foam-type fire-resistant material that expands and expands when heated to a predetermined temperature or more around a laminated rubber support in which a rubber plate and a metal plate are sequentially stacked and integrated. Coating with a rubber material of the composition has been studied. Examples of the rubber material of the foam type fire-retardant composition include a modified silicone-based material (polyether) containing a polyphosphate compound.

[0004] Incidentally, the rubber material of such a foam-type fire-retardant composition usually has elasticity equivalent to that of a laminated rubber bearing body. Not only can it follow enough, but when it is heated to a certain temperature or more by fire, it expands and expands several times,
It is necessary to form a non-combustible layer having excellent heat insulation properties, and this non-combustible layer serves as a fire-resistant heat-insulating layer to protect the internal laminated rubber bearing body.

[0005] In view of such a background, attention has been paid to the development of the above-mentioned rubber materials to make them flame-retardant. Among the above-mentioned sealing materials, a fire-resistant sealant composition using a modified silicone material is disclosed in Japanese Patent Application No. Hei. No. 163711, a fire-resistant foam composition using a saturated hydrocarbon polymer system is disclosed in Japanese Patent Application Laid-Open No. 9-530.
75. These are compounds in which ammonium polyphosphate, a polyhydric alcohol, an amino group-containing compound, a silanol compound catalyst, and the like are mixed with a polymer having a hydrolyzable silicon functional group at a terminal in a sealing material. These materials prevent inflammables such as wood by forming a non-flammable foamed carbonized layer when the sealing material is exposed to a flame, or generate smoke, flame, gas generated by combustion, etc. It is a foam type fire-resistant sealant composition for preventing outflow to the outside.

[0006] In the former modified silicone composition, there is a problem that deterioration of foaming ratio with time is recognized due to high water permeability. On the other hand, it has been revealed that the latter saturated hydrocarbon polymer composition has a low moisture permeability, thereby making it possible to prevent the deterioration of the expansion ratio over time. However, since the saturated hydrocarbon polymer composition does not have oxygen atoms in the molecule, a large amount of smoke is generated when the amount of oxygen supplied during combustion is insufficient, and when burned according to the standard heating curve. However, there is a problem that the carbonized layer is burned out (burnout of the heat insulating layer) or that it is difficult to maintain the shape after burning.

[0007]

In view of the above-mentioned problems of the prior art, the present invention provides a foam type fire-resistant coating composition which has a small amount of smoke and is excellent in shape retention of a heat insulating layer. It is intended to provide.

[0008]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that by adding an appropriate amount of an inorganic filler to a saturated hydrocarbon polymer,
A foam type refractory coating composition having a small amount of smoke and excellent in shape retention of the heat insulating layer has been obtained.

That is, the present invention provides the following component (A):
It is a foam type refractory coating composition containing (B) and (C) as essential components. (A) a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond; (B) a polyphosphate compound (C) Inorganic filler

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (this is also referred to as a reactive silicon group in the present specification) is used. , A saturated hydrocarbon polymer having at least one (hereinafter, referred to as a saturated hydrocarbon polymer (A)) is used. The reactive silicon group is a well-known functional group, and typical examples thereof include the general formula ^{(1): - (SiR 1} 2-b X b O) m -SiR 2 3-a X a (1) [Wherein, R ¹ and R ² each independently have 1 to 1 carbon atoms.
20 alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group, or R ³ ₃ SiO- (R ³ having 7 to 20 carbon atoms is a monovalent hydrocarbon group having 1 to 20 carbon atoms and the three R ³
May be the same or different), and when two or more R ¹ or R ² are present, they may be the same or different. Is also good. X is a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a is an integer of 0 to 3,
b is an integer selected from 0 to 2, provided that a + mb ≧ 1. Further, in the m _{^{(SiR 1 2-b X b}} O), b need not be respectively identical. m is 0
Integer of ~ 19. ] Can be exemplified.

The hydrolyzable group in the general formula (1) is not particularly limited, and may be a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate Groups, amino groups, amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like. Among these, an alkoxyl group is particularly preferable in terms of mild hydrolysis and easy handling.

The hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and (a + m
b) preferably ranges from 1 to 5. When two or more hydrolyzable groups are bonded in the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon group may be one or two or more. In the case of silicon atoms connected by a siloxane bond or the like, the number is preferably up to 20. In particular, a reactive silicon group represented by the general formula (2): —SiR ² _3-a X _a (2) (wherein R ² , X and a are the same as above) is easily available. It is preferred.

The number of the reactive silicon groups is at least one, preferably 1.1 to 5 on average in one molecule of the saturated hydrocarbon polymer. If the number of reactive silicon groups contained in the molecule is less than one, the curability becomes insufficient and it becomes difficult to exhibit good rubber elasticity behavior. The reactive silicon group may be present at the terminal of the molecular chain of the saturated hydrocarbon-based polymer, may be present inside, or may be present both at the terminal and inside. Especially when the reactive silicon group is present at the molecular chain terminal, the effective network chain amount of the saturated hydrocarbon-based polymer component contained in the finally formed cured product increases, so that high strength and high elongation are obtained. It is preferable from the viewpoint that a rubber-like cured product is easily obtained. These saturated hydrocarbon polymers having a reactive silicon group may be used alone or in combination of two or more.

The saturated hydrocarbon polymer used in the present invention includes (i) ethylene, propylene, 1-butene,
A method of polymerizing an olefinic compound having 1 to 6 carbon atoms such as isobutylene as a main monomer; (ii) homopolymerizing a diene-based compound such as butadiene and isoprene; Or by hydrogenation after copolymerization of In the present invention,
It is easy to introduce a functional group at the end, control the molecular weight easily,
From the point that the number of terminal functional groups can be increased,
An isobutylene-based polymer, a hydrogenated polybutadiene-based polymer or a hydrogenated polyisoprene-based polymer is preferred.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, and the monomer units capable of copolymerizing with isobutylene are preferably contained in the isobutylene-based polymer in an amount of 50%. (% By weight, hereinafter the same), more preferably 30% or less, particularly preferably 10% or less. Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. Specific examples of such a copolymer component include, for example, 1-butene, 2
-Butene, 2-methyl-1-butene, 3-methyl-1-
Butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, pt
-Butoxystyrene, p-hexenyloxystyrene,
p-allyloxystyrene, p-hydroxystyrene, β
-Pinene, indene, vinyldimethylmethoxysilane,
Vinyltrimethylsilane, divinyldimethoxysilane,
Divinyldimethylsilane, 1,3-divinyl-1,1,1,
3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallylmethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxy Examples include silane.

In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, similarly to the case of the isobutylene-based polymer, in addition to the monomer unit serving as the main component,
Other monomer units may be contained. In the present invention,
The saturated hydrocarbon polymer used as the component (A) includes butadiene, isoprene, 1,13-tetradecadiene, 1,9-decadiene and 1,5-hexadiene as long as the object of the present invention is achieved. Such a polyene compound may contain a small amount, preferably 10% or less, of a monomer unit such that a double bond remains after polymerization.

The number average molecular weight of the saturated hydrocarbon polymer, preferably isobutylene polymer, hydrogenated polyisoprene or hydrogenated polybutadiene polymer is from 500 to 100.
000, and a number average molecular weight of 1,000.
A liquid material of about ４０40000 and a material having fluidity are preferred from the viewpoint of easy handling. Further, as for the molecular weight distribution (Mw / Mn), the narrower the molecular weight distribution is, the more preferable it is from the viewpoint that the viscosity at the same molecular weight becomes lower.

The process for producing a saturated hydrocarbon polymer having a reactive silicon group will be described with reference to an isobutylene polymer and a hydrogenated polybutadiene polymer. Among the above-mentioned isobutylene-based polymers having a reactive silicon group, an isobutylene-based polymer having a reactive silicon group at a molecular terminal is a polymerization method called an inifer method (a specific method in which an initiator called a inifer and a chain transfer agent are used. Can be produced using an isobutylene-based polymer having a functional group at a terminal, preferably an all-terminal functional group, obtained by a cationic polymerization method using a compound of the formula (1). Such a production method is disclosed in JP-A-63-6003 and JP-A-63-6041.
Nos. 63-254149, 64-22904,
It is described in each specification of JP-A-64-38407.

The isobutylene-based polymer having a reactive silicon group in the molecule is obtained by adding a vinyl silane or an allyl silane having a reactive silicon group to a monomer mainly composed of isobutylene and copolymerizing the monomer. Manufactured by

Further, the isobutylene-based polymer having a reactive silicon group at both the inside and the molecular end of the molecule is mainly used in the above-mentioned polymerization for producing the isobutylene-based polymer having a reactive silicon group at the molecular end. It can be produced by copolymerizing vinylsilanes or allylsilanes having a reactive silicon group other than the component isobutylene monomer, and then introducing a reactive silicon group to the terminal.

Specific examples of the vinylsilanes and allylsilanes having a reactive silicon group include, for example, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, Allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethyldimethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like can be mentioned.

As a method for producing a hydrogenated polybutadiene-based polymer, for example, after converting a hydroxyl group of a terminal hydroxy-hydrogenated polybutadiene-based polymer into an oxymetal group such as -ONa or -OK, the general formula (3): CH ^{_{2 = CH-R 4 -Y (}} 3) wherein, Y represents a chlorine atom, a halogen atom such as iodine atom. R ^{4 is, -R 5 -, - R 5} -OC (= O) - or ^{-R 5 -C (= O) -} (R 5 represents an alkylene group, cycloalkylene group, arylene group, carbon atoms such as an aralkylene group It represents a divalent organic group represented by represents) a C 1-20 divalent hydrocarbon group, among which -CH ₂ - and _{^{-p-R 6 -C 6 H 4}} -CH 2 - (R 6 is 2 selected from hydrocarbon groups having 1 to 10 carbon atoms)
It is preferably a valent group. To produce a hydrogenated polybutadiene polymer having a terminal olefin group (hereinafter also referred to as a hydrogenated polybutadiene polymer having a terminal olefin).

Methods for converting the terminal hydroxyl groups of the above-mentioned hydroxy-terminated hydrogenated polybutadiene-based polymer into oxymetal groups include alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; , KOH and the like. In the above method, a terminal olefin hydrogenated polybutadiene-based polymer having substantially the same molecular weight as the terminal hydroxy-hydrogenated polybutadiene-based polymer used as a starting material can be obtained. Before reacting the organic halogen compound represented by the formula (3), a polyvalent organic halogen such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether or the like containing two or more halogen atoms in one molecule. By reacting with a compound, the molecular weight can be increased. After that, by reacting with an organic halogen compound represented by the general formula (3), a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at an end can be obtained. Obtainable.

Specific examples of the organic halogen compound represented by the general formula (3) include, for example, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene and allyl ( Chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy)
Examples include, but are not limited to, benzene and allyloxy (chloromethyl) benzene. Of these, allyl chloride is preferred because it is inexpensive and easily reacts.

The introduction of a reactive silicon group into a hydrogenated polybutadiene polymer having a terminal olefin is represented, for example, by the general formula (1), as in the case of an isobutylene polymer having a reactive silicon group at a molecular terminal. hydrosilane compound having a hydrogen atom bonded to the group, preferably, for example, the general formula _{^{(4): HSiR 2 3-}} a X a (4) (. wherein, R ^2, X and a are same as defined above) with This can be achieved by subjecting the indicated compound to an addition reaction using a platinum catalyst.

Specific examples of the hydrosilane compound having a hydrogen atom bonded to the group represented by the general formula (1) include, for example, halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane; Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane And ketoxime silanes such as bis (cyclohexyl ketoximate) methyl silane, and the like, but are not limited thereto. Of these, halogenated silanes and alkoxysilanes are particularly preferred.

Component (B) of the present invention is a polyphosphate compound. The polyphosphate compound functions as a catalyst for dehydrating organic substances in a heated environment and also has a function of forming a nonflammable inorganic phosphoric acid film itself. The polyphosphate compound is not particularly limited as long as it is a salt of polyphosphoric acid, but is preferably a salt of polyphosphoric acid with ammonia or an organic base, more preferably a salt of polyphosphoric acid with ammonia or an amine, and more preferably ammonium polyphosphate. More preferred.

The amine compound forming the salt includes:
Methylamine, ethylamine and the like can be mentioned. When a polyphosphoric acid salt with ammonia or an amine reaches a decomposition temperature by heating, condensed phosphoric acid is generated by deamination such as deammonification. This acid acts as an organic dehydration catalyst,
As a result of carbonizing the organic matter, a fire-resistant carbonized layer is formed. In addition, ammonia gas or the like generated at this time acts as a foaming agent and expands the entire composition.

The salt of polyphosphoric acid with ammonia or amine used in the present invention has a phosphorus content of 15% by weight,
With a nitrogen content of 14% by weight and a decomposition temperature of 200 ° C. or higher,
Further, those having low hygroscopicity are suitable from the viewpoint of easy handling.

The salt of polyphosphoric acid with ammonia or amine is not particularly limited. Examples thereof include ammonium polyphosphate (trade name “Sumisafe P”) manufactured by Sumitomo Chemical Co., Ltd., and insoluble polymer phosphoric acid. Compound (trade name “Sumisafe PM”) and the like.

The amount of the component (B) is not particularly limited, but is 10 to 200 parts by weight, or 100 parts by weight of a plasticizer, based on 100 parts by weight of the saturated hydrocarbon polymer as the component (A). When blended, the amount is preferably 10 to 200 parts by weight based on 100 parts by weight of the total of the component (A) and the plasticizer. When the amount of component (B) is below this range,
Effective carbonization and foaming of the entire composition cannot be expected. On the other hand, when the amount of the component (B) is more than this range, the viscosity of the compound becomes high and the workability is lowered, which is not preferable.

By blending the composition of the present invention with an appropriate amount of the inorganic filler (C), the following properties during use can be dramatically improved. First, since the amount of the combustible component in the composition is reduced, the supply of oxygen during combustion is less likely to be insufficient and the amount of smoke is reduced as compared with the case where the component (C) is not added. Second, even after the char layer formed in the initial stage of combustion is burned off as the combustion proceeds,
By sintering the inorganic filler (C), a non-flammable heat insulating layer is formed, and the shape can be maintained even after prolonged combustion.

Another advantage is that the workability of the composition of the present invention can be freely controlled. That is, depending on the mixing conditions at the time of preparing the compound,
From the self-leveling composition that can be processed into a sheet by pouring into a mold by controlling the viscosity and viscosity ratio, a composition with a high thixotropic property that can seal and seal vertical parts on site The point is that you can freely design things.

[0034] Such fillers include reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, and talc; heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, Fillers such as clay, titanium oxide, bentonite, ferric oxide, zinc oxide and activated zinc white; fibrous fillers such as glass fibers and filaments can be used. Among these inorganic fillers, precipitated silica, fumed silica, crystalline silica, fused silica, dolomite, calcium carbonate, titanium oxide, talc and the like are preferable. These fillers may be used alone or in combination of two or more.

When the inorganic filler (C) is used, the amount used is preferably from 10 to 1,000 parts by weight, more preferably from 30 to 500 parts by weight, per 100 parts by weight of the component (A). If the amount of component (C) is below this range,
Insufficient formation of the formed non-combustible layer may result in reduced long-term fire resistance, and the foaming ratio may be increased, so that the strength of the heat insulating layer may be reduced to such an extent that the shape cannot be maintained. Conversely, if the amount of the component (C) exceeds this range, the foaming ratio may decrease, resulting in a decrease in heat insulation performance, or the viscosity of the compound may increase, resulting in poor workability. Therefore, it is not preferable.

When it is desired to obtain a cured product having high strength using these fillers, a reinforcing filler such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, or talc is mainly used. Then, a cured product having a high strength and a high modulus in mechanical properties can be obtained. On the other hand, when it is desired to obtain a cured product having low modulus and high elongation, heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, clay, titanium oxide, bentonite, ferric oxide,
Fillers such as zinc oxide and activated zinc white may be used. Of course, these fillers may be used alone or in combination of two or more. The filler may be added to component (A) or may be added to other components.

In the present invention, a silanol condensation catalyst may be used. The silanol condensation catalyst is conventionally known, and specific examples thereof include, for example, titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin diurarate, dibutyltin maleate,
Tin carboxylate salts such as dibutyltin diacetate, tin octylate, tin naphthenate; reaction products of dibutyltin oxide and phthalic acid ester; dibutyltin diacetylacetonate; aluminum trisacetylacetonate; aluminum trisethylacetoacetate; Organoaluminum compounds such as isopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine , Triethanolamine, diethylenetriamine, triethylenetetramine,
Oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine,
Amine compounds such as 2-ethyl-4-methylimidazole and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), or salts of these amine compounds with carboxylic acids and the like; excess polyamine Low molecular weight polyamide resin obtained from a polybasic acid and a polybasic acid; a reaction product of an excess polyamine and an epoxy compound; an amino group such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane And other known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more.

The compounding amount of the silanol condensation catalyst is preferably about 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the saturated hydrocarbon polymer as the component (A). If the amount is less than this range, the curing speed may be slow, and the curing reaction may not proceed sufficiently. On the other hand, if the compounding amount exceeds this range, local heat generation and foaming may occur during curing, and it is difficult to obtain a good cured product, and the pot life may be too short, from the viewpoint of workability. Is also not preferred.

In the present invention, the components (A) and (B)
In addition to (C) and (C), a polyfunctional alcohol may be used. The polyfunctional alcohol expands by heating, and forms a foamed carbonized film by carbonization in the presence of a polyphosphate compound as a dehydration catalyst. As a polyfunctional alcohol, the decomposition temperature of carbonization by heating is 200 ° C or higher,
Preferably, those having a temperature of 300 ° C. or higher can be used. Examples of such polyfunctional alcohols include, but are not limited to, polyhydric alcohols such as mono, di, and tripentaerythritol, polysaccharides such as starch and cellulose, and oligosaccharides such as glucose and fructose. Not something. These may be used alone or in combination of two or more.

The blending amount of the polyfunctional alcohol is not particularly limited, but 10 to 100 parts by weight or a plasticizer is blended with respect to 100 parts by weight of the saturated hydrocarbon polymer as the component (A). In this case, the amount is preferably from 10 to 100 parts by weight based on 100 parts by weight of the total of the component (A) and the plasticizer. If the amount is less than this range, the expansion may be insufficient. If the amount is more than this range, the formation of the carbonized foam may be insufficient.

Further, in the present invention, the above component (A),
An amino group-containing compound may be used in addition to (B) and (C). The amino group-containing compound acts as a swelling agent,
The non-flammable gas such as nitrogen and ammonia is generated with the decomposition by heating, and the whole composition is expanded to an appropriate size. Specific examples include, but are not limited to, dicyandiamide, melamine, guanamine, guanidine, urea, azodicarbonamine, and amino resins such as melamine resin, guanamine resin, and urea resin.
These may be used alone or in combination of two or more.

The amount of the amino group-containing compound is not particularly limited, but is 5 to 50 parts by weight or 100 parts by weight of a plasticizer based on 100 parts by weight of the saturated hydrocarbon polymer as the component (A). In this case, the amount is preferably 5 to 50 parts by weight based on 100 parts by weight of the total of the component (A) and the plasticizer. If the amount is less than this range, the expansion may be insufficient. If the amount is more than this range, the strength of the foamed carbonized film may be insufficient.

In addition to the above components, the composition of the present invention may further comprise, if necessary, a plasticizer, a hindered phenol-based or hindered amine-based antioxidant, or an ultraviolet ray, depending on the required characteristics for each application. An absorber, a light stabilizer, a pigment, a surfactant, and an adhesion-imparting agent such as a silane coupling agent can be appropriately added.

Among these, the plasticizer is used to adjust the flow characteristics and improve workability, and a commonly used plasticizer can be used. The component (A) used in the present invention can be used.
Those having good compatibility with the saturated hydrocarbon-based polymer are preferred. Specific examples of the plasticizer having good compatibility include, for example, polybutene, hydrogenated polybutene, α-methylstyrene oligomer, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, and atactic polypropylene. Preferably, hydrocarbon compounds such as hydrogenated polybutene containing no unsaturated bond, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, and atactic polypropylene are preferred. These plasticizers may be used alone or in combination of two or more. In addition, plasticizers that have poor compatibility by themselves,
It can be used if the compatibility is improved by the combined use with the above-mentioned hydrocarbon compounds.

The method for preparing the foam type refractory coating composition of the present invention is not particularly limited. For example, the above components are blended and kneaded at room temperature or under heat using a mixer, roll, kneader, or the like. A conventional method such as mixing after dissolving the components in the above solvent can be employed. In addition, by appropriately combining these components, a two-pack type composition can be mainly produced and used.

The refractory foamed material obtained by curing the composition of the present invention thus obtained has an expansion ratio of 10 due to combustion.
It is preferably at most twice. Further, the refractory foamed material obtained by curing retains its shape even after burning.

[0047]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 150 parts by weight of an isobutylene polymer having reactive silicon (Epion EP505S, manufactured by Kaneka Chemical Industry Co., Ltd.), which is a saturated hydrocarbon polymer (A), and a paraffin-based process oil was used as a plasticizer. (Idemitsu Kosan PS-
32), 100 parts by weight of polyphosphoramide (Sumitomo Chemical Industries, Ltd. Sumisafe PM), 40 parts by weight of pentaerythritol (Mitsubishi Chemical Corporation) as a polyhydric alcohol, inorganic filler (C) ) As heavy calcium carbonate, 300 parts by weight of Ryton A (Shiraishi calcium (manufactured)), 15 parts by weight of melamine (Nissan Chemical Industry (manufactured)) as an amino group-containing compound, carbon black (CB # 30 manufactured by Mitsubishi Chemical (manufactured by Mitsubishi Chemical)) 0.5 parts by weight, titanium oxide (Ishihara Sangyo R820) 5 parts by weight and water (tap water) 2.5
The mixture was stirred at room temperature, and further kneaded with a twin-screw stirrer (Inoue Seisakusho Co., Ltd. BDM-50) for 1 hour to form a paste. To this composition, 3 parts by weight of tin octylate (Nitto Kasei (Neostan U-28)) as a curing catalyst, and 0.75 part by weight of laurylamine (Kao (Pharmaine) 20D) as a curing aid are added, followed by stirring. A composition was obtained. The composition thus obtained was used as Example 1
The characteristics were evaluated by the following methods. (Combustion test) A test of foaming characteristics was performed by the following method. That is, after a cured product of 1 cm square was prepared (cured at 23 ° C. for 1 week and further at 50 ° C. for 1 week), it was heated with a flame of 900 ° C. by a gas burner, and the expansion ratio and shape after burning were observed. did. (Smoke emission measurement) A cone calorimeter (manufactured by Atlas Co., Ltd.) was used as a test device.
After measuring the amount of smoke during combustion by vertical installation at KW, the average amount of smoke was calculated according to the following equation. Average smoke amount (m ² / kg) = smoke flow rate (l / s) × specific extinction coefficient (1 / m) ÷ weight reduction rate (g / s · m ² ) ÷ surface area (m ² )

Comparative Example 1 A composition was prepared in the same manner as in Example 1 except that Ryton A as the inorganic filler (C) was removed from the composition in Example 1.

As a result of the evaluation of the above items, Example 1 was foamed to four times the volume (compared to before combustion) and the foam maintained its shape and did not collapse, whereas Comparative Example 1 It was found that since the foamed layer burned out with the progress of combustion, there was almost no residue left, and the shape before combustion could not be maintained. Since the sample of Comparative Example 1 was burned out, the expansion ratio could not be measured. The measurement result of the amount of smoke generated was 3 m in Comparative Example 1 compared to 250 m ² / kg in Example.
It is 80 m ² / kg, and it is understood that the amount of smoke generated in the event of fire is reduced with the composition of the present invention.

Example 2 Instead of Ryton A used as an inorganic filler (C) in Example 1, heavy calcium carbonate (Maruo Calcium (manufactured by Snow Light SS)) and colloidal calcium carbonate (Shiraishi Kogyo (manufactured by Shiraishi Kagaku)) CC), talc (Maruo calcium (product) LMR), clay (Shiraishi calcium (product) ST-)
301), silica (Tatsumori (made by) Hughes Rex E-
Each of the compositions was prepared using 40 parts by weight of 1) and subjected to a combustion test in the same manner as in Example 1. As a result, in all cases, the expansion ratio after combustion was 2 to 5 times, I confirmed that I could get my body.

[0052]

According to the present invention, an appropriate amount of an inorganic filler is added to a blend comprising a saturated hydrocarbon polymer and a polyphosphate, thereby producing a foam-type refractory coating having a small amount of smoke and excellent shape retention of a heat insulating layer. A composition was obtained. This composition is particularly useful as a fireproof covering material for seismic isolation devices for structures requiring fireproof and fireproof performance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/22 C08L 23/22 4J038 23/26 23/26 101/10 101/10 C09D 5/18 C09D 5 / 18 7/12 7/12 Z 143/04 143/04 183/04 183/04 201/10 201/10 C09K 3/10 C09K 3/10 G 21/12 21/12 21/14 21/14 E04B 1 / 94 E04B 1/94 U E04H 9/02 331 E04H 9/02 331A (72) Inventor Nagao Hori 4-640 Shimoseito, Kiyose-shi, Tokyo Inside Obayashi-Gumi Technical Research Institute, Inc. (72) Inventor Koichiro Takahashi, Kiyose-shi, Tokyo 4-640 Shimoseito Obayashi Corporation Technical Research Institute Co., Ltd. (72) Yoshiaki Hirayama 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Works (72) Inventor Koji Noda 1-112 Akasaka, Minato-ku, Tokyo Turn 32 (72) Inventor Makoto Chinami 1-8 Miyamae-cho, Takasago-cho, Takasago City, Hyogo Prefecture Kanebuchi Chemical Industry Co., Ltd. F-term in Oligomer Research Group (Ref.) DE107 DE117 DE137 DE237 DH056 DJ007 DJ017 DJ037 DJ047 DL007 FA047 FD017 FD136 GL00 4J038 CB131 EA011 GA03 HA286 HA426 HA446 HA526 HA536 KA08 NA15

Claims (6)

[Claims] 1. The following components (A), (B) and (C) which are attached to the outer periphery of a laminated rubber seismic isolation device having a laminated structure of metal and rubber, and which prevent the seismic isolation device from burning out in the event of a fire.
A foam type refractory coating composition comprising, as an essential component. (A) a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond; (B) a polyphosphate compound (C) Inorganic filler 2. The polymer (A) wherein the total amount of repeating units derived from isobutylene is 50% by weight or more.
The foam type refractory coating composition according to the above. 3. An inorganic filler (C) comprising calcium carbonate,
The foam type refractory coating composition according to claim 1 or 2, wherein the composition is at least one selected from the group consisting of silica, talc, and clay. 4. The foam-type refractory coating composition according to claim 1, wherein component (C) is contained in an amount of 10 to 1000 parts by weight based on 100 parts by weight of component (A). 5. The foam type refractory coating composition according to claim 1, wherein the expansion ratio by burning of the refractory foam material obtained by curing is 10 times or less. 6. The refractory foamed material obtained by hardening retains its shape even after burning.
Or the foam type refractory coating composition according to 4.