JP2012214646A - Thermally expandable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermally expandable resin composition, capable of closing a gap of building materials, a through-hole or the like even if it cannot be perfectly closed by the thermally expanded residue of the thermally expandable resin composition.SOLUTION: [1] The thermally expandable resin composition includes: a thermally expanding component, a binder resin and an inorganic filler, the thermally expanding component includes a first thermally expanding component having a thermally expansion start temperature of 140-250°C and a second thermally expanding component having a thermal expansion start temperature of 251-350°C. [2] In the thermally expandable resin composition of [1], the first thermally expanding component is thermally expandable graphite having a thermal expansion start temperature of 140-250°C, the second thermally expanding component is thermally expandable graphite having a thermal expansion start temperature of 251-350°C, and the binder resin includes at least one selected from the group consisting of thermosetting resin, thermoplastic resin and rubber resin.

Description

  The present invention relates to a thermally expandable resin composition.

As a resin composition having a function of imparting a fire resistance function to building materials such as ceiling materials, flooring materials, and partition walls, a thermally expandable resin composition containing thermally expandable graphite, filler, thermoplastic resin, etc. has been developed. ing.
A thermally expandable refractory sheet or the like obtained by molding the thermally expandable resin composition expands when exposed to heat from a fire or the like to form a non-flammable thermally expandable residue.
As a specific example of applying this incombustible thermal expansion residue, there is known a structure in which the thermal expansion refractory sheet or the like is disposed in a gap in a building material such as a ceiling material, a floor material, or a partition wall, a through hole, or the like.
When this structure is exposed to heat such as fire, the thermally expandable refractory sheet or the like expands to form the thermally expanded residue, and the thermally expanded residue closes gaps, through holes, or the like of the building material.
In this way, the thermal expansion residue blocks the building material gaps, through-holes, and the like, thereby preventing a flame, smoke, heat, etc. from spreading through the building material gaps, through-holes, etc. it can.

In order for the heat-expandable fireproof sheet or the like to expand due to heat from a fire to form a heat-expandable residue, the heat-expandable graphite contained in the heat-expandable resin composition must expand rapidly due to heat from the fire or the like. In addition, it is required that the binder material contained in the thermally expandable resin composition does not hinder the expansion of the thermally expandable graphite.
As the thermally expandable graphite used in the above thermally expandable resin composition, it is known to use thermally expandable graphite having a thermal expansion start temperature exceeding 180 ° C. and not more than 250 ° C. (Patent Document 1). ).
However, since the thermal expansion residue of the thermally expandable graphite is difficult to be formed at a temperature lower than 180 ° C., the thermal expansion property is small in a small-scale fire, under conditions where the temperature rise is low at the initial stage of fire, or in a structure having a slow thermal conductivity such as a wall. There was a problem that heat necessary for expansion was not sufficiently transmitted to graphite and fire resistance was not sufficiently exhibited.
In order to cope with this problem, in order to exhibit the fire resistance performance of the thermally expandable resin composition even at a temperature lower than 180 ° C., a thermally expandable graphite having a thermal expansion start temperature exceeding 180 ° C. and not more than 250 ° C., and expansion It has been proposed to use a heat-expandable resin composition in combination with a heat-expandable graphite having a starting temperature of 140 ° C. or higher and 180 ° C. or lower (Patent Document 1).
With this thermally expandable resin composition, thermal expansion starts even at a low temperature of 180 ° C. or lower compared to the case of using a thermally expandable graphite having a thermal expansion start temperature of more than 180 ° C. and 250 ° C. or lower. Therefore, it is said that fire resistance can be demonstrated.
When the building material is exposed to heat such as a fire, the temperature of the building material rises from a low temperature to a high temperature. For this reason, when the thermally expansible resin composition described in the said patent document 1 is heated at 250 degreeC or more, the thermal expansion start temperature of the thermally expansible graphite contained in a thermally expansible resin composition is 250 degrees C or less. Therefore, a thermal expansion residue is formed before the temperature of the thermally expandable resin composition exceeds 250 ° C. This thermal expansion residue can block heat exceeding 250 ° C.
For this reason, even if the thermal expansion start temperature of the thermal expansion graphite contained in the thermal expansion resin composition is 250 ° C. or less, the thermal expansion resin composition should be used for applications that reach a temperature of 250 ° C. or more. Can do.

JP-A-11-323148

The thermal expansion residue formed by the heat of fire or the like completely closes the gaps and through-holes of the building material to block the flame and smoke of the fire and prevent the diffusion of heat.
However, after the expansion of the heat-expandable resin composition, when building materials such as metals are deformed, melted, collapsed, etc., and new gaps are formed, flames such as fire, smoke, May spread.
The object of the present invention is to prevent the spread of flames such as fire, smoke, and heat, and even when gaps occur between the thermal expansion residue and the building material after expansion of the thermal expansion resin composition, these gaps Another object of the present invention is to provide a thermally expandable resin composition capable of closing a through-hole or the like.

  As a result of intensive studies by the inventor in order to solve the above problems, a first thermal expansion component having a thermal expansion start temperature in the range of 140 to 250 ° C. and a second thermal expansion starting temperature in the range of 251 to 350 ° C. The present invention has been completed by finding that a thermally expandable resin composition containing a thermal expansion component is suitable for the purpose of the present invention.

That is, the present invention
[1] a thermal expansion component;
A binder resin,
An inorganic filler;
A resin composition comprising:
The thermal expansion component includes a first thermal expansion component having a thermal expansion start temperature in the range of 140 to 250 ° C and a second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C. The heat-expandable resin composition is provided.

One of the present invention is
[2] The first thermal expansion component is thermal expansion graphite having a thermal expansion start temperature in the range of 140 to 250 ° C.
The second thermal expansion component is thermal expansion graphite having a thermal expansion start temperature in the range of 251 to 350 ° C.
The thermally expandable resin composition according to the above [1], wherein the binder resin contains at least one selected from the group consisting of a thermosetting resin, a thermoplastic resin, and a rubber resin.

One of the present invention is
[3] The thermally expandable resin composition according to the above [1] or [2], wherein the binder resin contains a thermosetting resin.

One of the present invention is
[4] The binder resin is at least one selected from the group consisting of urethane resin, isocyanurate resin, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, alkyd resin, melamine resin, diallyl phthalate resin and silicone resin. The thermally expansible resin composition in any one of said [1]-[3] containing is provided.

The heat-expandable resin composition of the present invention includes a first heat-expandable component having a heat expansion start temperature in the range of 140 to 250 ° C. For this reason, when the heat-expandable resin composition receives heat from a fire or the like, it rapidly expands to form a first heat-expandable residue.
At this time, even if the binder resin is melted or burnt out by heat such as a fire in a temperature range of 140 to 250 ° C., the first thermal expansion residue does not cause melting, burning, etc. it can.
The thermal expansion residue contains a second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C.
For this reason, after the first thermal expansion residue is formed, if the first thermal expansion residue is heated to a temperature of 251 ° C. or higher by the heat of a fire or the like, the thermal expansion start temperature is 251 to 350 this time. The second thermal expansion component in the range of 0 C can expand to form a second thermal expansion residue.

  In the case of the conventional thermally expandable resin composition, the resin composition is determined from the viewpoint of efficiently expanding the thermally expanded resin composition exposed to heat such as fire in the early stage of fire, When the resin composition is heated in the range of 140 to 250 ° C., there is no prior document that discloses a technique that positively leaves a thermal expansion component in the thermal expansion residue formed by heating.

  On the other hand, the thermally expandable resin composition of the present invention is heated in the range of 140 to 250 ° C., so that, for example, even when the binder resin is melted, burned, etc., the first thermal expansion is performed. The residue retains the second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C.

For example, although a molded body such as a heat-expandable fireproof sheet applying the heat-expandable resin composition of the present invention has formed a first thermal expansion residue by heat from a fire or the like, a gap in a building material, a through hole, etc. are completely Suppose that there was a case where the gap could not be closed. Even in this case, when a flame such as a fire passes through the gap, the second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C. contained in the first thermal expansion residue is heated and expanded. To do.
As a result, the gap between the building materials and the through-holes cannot be completely blocked by the first thermal expansion residue, and even when there is a gap, the second thermal expansion residue is formed and the gap is closed later. be able to.

  In addition, even when a crack or the like occurs in the first thermal expansion residue after the first thermal expansion residue completely closes the gaps or through holes of the building material, a flame such as a fire has passed through the crack or the like. In some cases, the second thermal expansion component expands with heat to form a second thermal expansion residue. Thereby, the said crack etc. can be obstruct | occluded.

  Further, after the expansion of the first thermal expansion component of the thermally expandable resin composition is completed, a molded body such as a thermally expandable refractory sheet to which the thermally expandable resin composition of the present invention is applied is installed in the building material. After that, even if some building materials such as metals in the vicinity of the molded body melt and collapse and a new gap is generated between the first thermal expansion residue and the building material, a fire or the like When the flame passes, the second thermal expansion component is expanded by heat to form a second thermal expansion residue. Thereby, the gap can be closed.

As described above, the thermal expansion resin composition of the present invention forms the first thermal expansion residue after being heated in the range of 140 to 250 ° C., and the thermal expansion start temperature is in the first thermal expansion residue. It has a function of holding the second thermal expansion component in the range of 251 to 350 ° C.
For this reason, the second thermal expansion residue is formed when the first thermal expansion residue is further strongly heated by heat of fire or the like and the temperature of the first thermal expansion residue becomes 251 ° C. or higher.

That is, the heat-expandable resin composition of the present invention has a characteristic that a stronger heat-expansion residue is formed as the heat-expandable resin composition is heated more strongly by a flame such as a fire.
This feature makes it possible to close gaps, cracks, and the like of thermal expansion residues that have been difficult to prevent so far, so that the thermally expandable resin composition of the present invention is more excellent in fire resistance.

The thermally expandable resin composition of the present invention will be described.
The thermally expandable resin composition includes at least a thermally expandable component, a binder resin, and an inorganic filler.
Of the components of the thermally expandable resin composition, first, the thermally expanded components will be described.

  The thermal expansion component expands upon heating. Specific examples of the thermal expansion component include vermiculite, kaolin, mica, and thermally expandable graphite.

  Examples of the thermally expandable graphite include powders such as natural scaly graphite, pyrolytic graphite, and quiche graphite, and inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, perchloric acid, perchlorate, perchlorate, and the like. Crystalline compound that has been treated with a strong oxidant such as manganate, dichromate, dichromate, hydrogen peroxide, etc. to produce a graphite intercalation compound, while maintaining the layered structure of carbon Can be mentioned.

  The heat-expandable graphite obtained by acid treatment as described above is preferably further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.

  Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine.

  Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium, and magnesium, oxides, carbonates, sulfates, and organic acid salts.

  The thermal expandable graphite preferably has a particle size in the range of 20 to 200 mesh.

  When the particle size is 20 mesh or more, the degree of expansion of graphite is large, and a sufficient thermal expansion residue is easily obtained. Further, when the particle size is 200 mesh or less, the dispersibility becomes good when kneaded with the binder resin.

  Examples of the commercially available neutralized thermally expandable graphite include “GRAFGUARD # 160”, “GRAFGUARD # 220” manufactured by UCAR CARBON, “GREP-EG” manufactured by Tosoh Corporation, and the like.

  Moreover, the said thermal expansion component used for this invention is the 1st thermal expansion component of the range whose thermal expansion start temperature is 140-250 degreeC, and the 2nd thermal expansion component whose range of thermal expansion start temperature is 251-350 degreeC. Including.

  The first thermal expansion component and the second thermal expansion component may be of the same type or different types as long as the thermal expansion start temperature is in the range of 140 to 250 ° C and 251 to 350 ° C, respectively. Although it is easy to control the moldability and the coefficient of thermal expansion of the resulting thermally expandable resin composition, it is preferable to use the neutralized thermally expandable graphite.

  When the thermal expansion start temperature of the first thermal expansion component is 140 ° C. or higher, the thermal expansion resin composition is excellent in productivity because it does not expand when kneaded with the binder resin. In addition, when exposed to heat from a fire or the like at 250 ° C. or lower, the thermally expandable resin composition quickly expands to form a first thermal expansion residue. Excellent fire resistance because it can be used.

The thermal expansion start temperature of the second thermal expansion component is 251 ° C. or higher, but the second thermal expansion component present in the first thermal expansion residue formed by the first thermal expansion component is 251 ° C. Since it does not expand below the lower temperature, the second thermally expandable component that has not expanded can be retained in the first thermally expanded residue.
Also, at 350 ° C. or lower, the first thermal expansion residue expands efficiently when heated by a flame such as a fire, and thus has excellent fire resistance.

  The thermal expansion start temperature of the second thermal expansion component is preferably in the range of 265 to 350 ° C, more preferably in the range of 280 to 350 ° C.

  The thermally expandable resin composition of the present invention includes a first thermal expansion component having a thermal expansion start temperature in the range of 140 to 250 ° C, and a second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C. including. For this reason, when the heat-expandable resin composition of the present invention is exposed to heat such as a fire and heated to a range of 140 to 250 ° C., the first resin expands even when the binder resin melts and burns out. A thermal expansion residue is formed.

A second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C. is dispersed in the first thermal expansion residue.
For this reason, when the first thermal expansion residue is heated to a temperature of 251 ° C. or higher, the second thermal expansion component expands to form a second thermal expansion residue.

  The heat-expandable resin composition of the present invention forms a second thermal expansion residue when heated to a temperature of 251 ° C. or higher even after being heated in the range of 140 to 250 ° C. to form the first thermal expansion residue. For this reason, when the molded product of the thermally expandable resin composition of the present invention is disposed in, for example, a building material, even if a gap or a crack that could not be sufficiently closed by the first thermally expanded residue occurs, the second Thermal expansion residues can block these gaps and cracks. Thus, since the heat-expandable resin composition of the present invention has a self-healing function, it has excellent fire resistance.

Next, the binder resin used for the thermally expandable resin composition of the present invention will be described.
Examples of the binder resin include synthetic resins such as thermoplastic resins and thermosetting resins, rubber resins, and the like.

  Examples of the thermoplastic resins include polypropylene resins, polyethylene resins, poly (1-) butene resins, polyolefin resins such as polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, polycarbonate resins, Examples thereof include polyphenylene ether resins, acrylic resins, polyamide resins, polyvinyl chloride resins, polyisobutylene resins and the like.

  Examples of the polyethylene resin include an ethylene homopolymer, a copolymer of ethylene and other α-olefin mainly containing ethylene, a copolymer of ethylene and a monomer other than α-olefin, and a copolymer of these. Examples thereof include a mixture and a mixture of polymers.

  Examples of the α-olefin in the ethylene-based copolymer of ethylene and other α-olefin include 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1- Examples include pentene.

  Examples of the copolymer of ethylene and a monomer other than α-olefin include an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-methacrylate copolymer.

  Examples of the ethylene homopolymer or a copolymer of ethylene and another α-olefin include those polymerized using, for example, a Ziegler-Natta catalyst, a vanadium catalyst, a metallocene compound containing a tetravalent transition metal, or the like as a polymerization catalyst. Among them, a polyethylene resin obtained using a metallocene compound containing a tetravalent transition metal as a catalyst is preferable.

  Examples of the thermosetting resin include urethane resin, isocyanurate resin, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, alkyd resin, melamine resin, diallyl phthalate resin, and silicone resin.

As said urethane resin, what contains the polyisocyanate compound as a main ingredient, the polyol compound as a hardening | curing agent, a catalyst, etc. is mentioned, for example.
Examples of the polyisocyanate compound that is the main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like. .
Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldisicyclohexylmethane diisocyanate, and the like.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.
The said polyisocyanate compound can use 1 type, or 2 or more types.
The main component of the urethane resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.

  Examples of the polyol compound that is a curing agent for the urethane resin include aromatic polyols, alicyclic polyols, aliphatic polyols, polyester-based polyols, and polymer polyols.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldisicyclohexylmethanediol, and the like.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
Examples of the polyester-based polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, and a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone. Examples thereof include condensates, and condensates of hydroxycarboxylic acids with the above polyhydric alcohols.

Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid.
Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. It is done.
Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate on the aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, and the like. Coalesced, polybutadiene polyol, or hydrogenated products thereof.

The ratio of the active hydrogen group (OH) in the polyol compound and the active isocyanate group (NCO) in the polyisocyanate compound (NCO / OH) is determined by combining the polyisocyanate compound as the main component of the urethane resin and the polyol compound as the curing agent. It is preferable to mix so that it may become 1.2-15 in equivalent ratio. More preferably, it is the range of 1.2-12.
If the equivalent ratio is 1.2 or more, the viscosity of the urethane resin can be prevented from becoming too high, and if it is 15 or less, good adhesive strength can be maintained.

  Examples of the urethane resin catalyst include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′— Amino such as trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N′-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group And system catalysts.

  Next, as the isocyanurate resin, for example, using the polyurethane resin described above, the isocyanate group contained in the polyisocyanate compound which is the main component of the polyurethane resin was reacted to trimerize, thereby promoting the generation of the isocyanurate ring. The thing etc. can be mentioned.

In order to promote the formation of an isocyanurate ring, for example, as a catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro Aromatic compounds such as -S-triazine, carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate, quaternary ammonium salts of carboxylic acids, and the like may be used.
The main component and curing agent of the isocyanurate resin are the same as those of the previous polyurethane resin.

  Next, examples of the epoxy resin include a resin obtained by reacting a monomer having an epoxy group with a curing agent.

  Examples of the monomer having an epoxy group include, as a bifunctional glycidyl ether type, a polyethylene glycol type, a polypropylene glycol type, a neopentyl glycol type, a 1,6-hexanediol type, a trimethylolpropane type, and a propylene oxide-bisphenol A. And monomers such as hydrogenated bisphenol A type, bisphenol A type, and bisphenol F type.

  Examples of the glycidyl ester type include monomers such as hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, and p-oxybenzoic acid type.

  Further, examples of the polyfunctional glycidyl ether type include monomers such as phenol novolac type, orthocresol type, DPP novolac type, dicyclopentadiene, and phenol type.

  These can use 1 type, or 2 or more types.

Examples of the curing agent include a polyaddition type curing agent and a catalyst type curing agent.
Examples of the polyaddition type curing agent include polyamines, acid anhydrides, polyphenols, polymercaptans, and the like.
Examples of the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes.
The method for curing these epoxy resins is not particularly limited, and can be performed by a known method.

  In addition, what adjusted the melt viscosity of the said resin component, a softness | flexibility, adhesiveness, etc. can use what mixed 2 or more types of resin components.

Next, as said phenol resin, a resol type phenol resin composition etc. are mentioned, for example.
The resol type phenol resin composition includes, for example, a resol type phenol resin as a main agent, a curing agent, and the like.

As the main component of the phenol resin, for example, phenols, cresol, xylenol, paraalkylphenol, paraphenylphenol, resorcin and other phenols and modified products thereof, and aldehydes such as formaldehyde, paraformaldehyde, furfural, and acetaldehyde are used as catalysts. Although what is obtained by making it react in presence of alkalis, such as quantity of sodium hydroxide, potassium hydroxide, calcium hydroxide, is mention | raise | lifted, it is not limited to this.
The mixing ratio of phenols and aldehydes is not particularly limited, but is usually in the range of 1.0: 1.5 to 1.0: 3.0 in terms of molar ratio. The mixing ratio is preferably in the range of 1.0: 1.8 to 1.0: 2.5.

  Examples of the phenol resin curing agent include inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as benzenesulfonic acid, ethylbenzenesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphtholsulfonic acid, and phenolsulfonic acid. It is done.

Next, examples of the urea resin include urea as a main agent, formaldehyde as a curing agent, a basic compound as a catalyst, and a composition containing an acidic compound.
The urea and formaldehyde form a urea resin by a polymerization reaction.

Next, as unsaturated polyester resin, the composition etc. which contain the unsaturated polybasic acid as a main ingredient, the polyol compound as a hardening | curing agent, a catalyst, etc. are mentioned.
Specific examples of the main component of the unsaturated polyester resin include maleic anhydride and fumaric acid.

Specific examples of the curing agent for the unsaturated polyester resin include a polyol compound used for the urethane resin described above.
The unsaturated polyester resin may be used in combination with a saturated polybasic acid such as phthalic anhydride or isophthalic acid, if necessary.

Further, a crosslinking vinyl monomer such as styrene, vinyl toluene, methyl methacrylate or the like which is polymerized with the main component of the unsaturated polyester resin can be added.
Specific examples of the unsaturated polyester resin catalyst include t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy octoate, and t-butyl peroxy. Examples thereof include organic peroxides such as isopropyl carbonate and 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone.

Next, as an alkyd resin, the composition containing the polybasic acid as a main ingredient, the polyol compound as a hardening | curing agent, fats and oils, etc. are mentioned, for example.
Specific examples of the main component of the alkyd resin include maleic anhydride, phthalic anhydride, and adipic acid.

Specific examples of the curing agent for the alkyd resin include a polyol compound used for the urethane resin described above.
Examples of the fats and oils include soybean oil, coconut oil, and linseed oil.

Next, as a melamine resin, the composition containing the melamine as a main ingredient, formaldehyde as a hardening | curing agent, etc. are mentioned, for example.
A benzoguanamine etc. can also be added to the said composition as needed.

Next, examples of the diallyl phthalate resin include a composition containing a polybasic acid such as phthalic anhydride as a main agent, allyl alcohol as a curing agent, and a crosslinking agent.
Examples of the crosslinking agent include styrene and vinyl acetate.

  Next, as the silicone resin, for example, a composition containing a platinum compound such as chloroplatinic acid or the like as a curing agent, or the like as a main component, such as dialkylsilyl dichloride or dialkylsilyl diol, a reaction inhibitor as a trialkylsilyl chloride or trialkylsilyl diol or the like. Can be mentioned.

Specific examples of the dialkylsilyl dichloride include dimethylsilyl dichloride, diethylsilyl dichloride, dipropylsilyl dichloride, and the like.
Specific examples of the dialkylsilyldiol include dimethylsilyldiol, diethylsilyldiol, and dipropylsilyldiol.
Specific examples of the trialkylsilyl chloride include trimethylsilyl chloride, triethylsilyl chloride, tripropylsilyl chloride, and the like.
Specific examples of the trialkylsilyldiol include trimethylsilylol, triethylsilylol, tripropylsilylol, and the like.
The reaction inhibitor is bonded to the terminal of the polysiloxane main chain and plays a role in controlling the reaction and controlling the degree of polymerization of the polysiloxane main chain.

  Examples of the rubber resin include natural rubber, butyl rubber, silicone rubber, polychloroprene rubber, polybutadiene rubber, polyisoprene rubber, polyisobutylene rubber, styrene / butadiene rubber, butadiene / acrylonitrile rubber, nitrile rubber, ethylene / propylene / diene. And rubber resins such as ethylene / α-olefin copolymer rubbers such as polymers.

  These synthetic resins and / or rubber substances can be used singly or in combination.

  Among the synthetic resins and / or rubber substances, those which are halogenated are preferable in that they are highly flame retardant per se and are crosslinked by a heat dehalogenation reaction to improve the strength of the residue after heating.

  The synthetic resin and / or rubber substance may be further subjected to crosslinking or modification within a range not impairing the fire resistance of the thermally expandable resin composition in the present invention.

  There is no particular limitation on the timing of the crosslinking and modification of the synthetic resin and / or rubber substance, and the synthetic resin and / or rubber substance crosslinked and modified in advance may be used. Crosslinking or modification may be performed at the same time when other components such as are blended.

  Moreover, after mix | blending another component with the said synthetic resin and / or rubber substance, you may bridge | crosslink and modify | denature, and the said bridge | crosslinking and modification | denaturation may be performed in any step.

  The crosslinking method is not particularly limited, and can be carried out by a crosslinking method that is usually performed for the synthetic resin and / or rubber substance. For example, a crosslinking method using various crosslinking agents, peroxides, and the like, and a crosslinking method by electron beam irradiation are included.

  In addition, what adjusted the melt viscosity of the said resin component, a softness | flexibility, adhesiveness, etc. can use what mixed 2 or more types of resin components.

The binder resin used in the present invention is preferably a thermosetting resin in order to prevent melting easily even when exposed to heat such as a fire.
The binder resin used in the present invention is more preferably an epoxy resin or a urethane resin from the viewpoint of handleability, and more preferably an epoxy resin.

  Next, the said inorganic filler is demonstrated among each component of the thermally expansible resin composition of this invention.

  The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, hydroxide Magnesium, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium silicate and other potassium salts, talc, clay, Mica, montmorillonite, bentonite, activated clay, ceviolite, imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon bal , Charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, inorganic phosphorus Compound, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber and the like can be mentioned.

  These can use 1 type, or 2 or more types.

  The said inorganic filler plays the role of an aggregate and contributes to the improvement of the expansion | swelling heat insulation layer produced | generated after a heating, and the increase in a heat capacity.

  When the inorganic filler used in the present invention is granular, the particle size is preferably in the range of 0.5 to 200 μm, more preferably in the range of 1 to 50 μm.

  When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance, so that a small particle size is preferable. However, if the particle size is less than 0.5 μm, secondary aggregation occurs and the dispersibility may deteriorate. is there.

  In addition, when the amount of inorganic filler added is large, the viscosity of the resin composition increases and moldability decreases as high filling proceeds, but the viscosity of the resin composition is decreased by increasing the particle size. From the point of being able to do, the thing with a large particle size is preferable among the said range.

  In addition, when a particle size exceeds 200 micrometers, the surface property of a molded object and the mechanical physical property of a resin composition may fall.

Among the inorganic fillers, calcium carbonate, zinc carbonate and other metal carbonates that play an aggregate role in particular,
In addition to the aggregate role, water-containing inorganic substances such as aluminum hydroxide and magnesium hydroxide that give an endothermic effect during heating are preferred.

  It is considered that the combined use of the hydrated inorganic substance and the metal carbonate greatly contributes to improving the strength of the combustion residue and increasing the heat capacity.

  Among the inorganic fillers, in particular, water-containing inorganic substances such as aluminum hydroxide and magnesium hydroxide are endothermic due to the water generated by the dehydration reaction during heating, and the temperature rise is reduced and high heat resistance is obtained. This is preferable in that the oxide remains as a combustion residue and this acts as an aggregate to improve the strength of the combustion residue.

  Magnesium hydroxide and aluminum hydroxide have different temperature ranges that exhibit dehydration effects, so when used together, the temperature range that exhibits dehydration effects becomes wider, and more effective temperature rise suppression effects can be obtained. It is preferable to do.

  When the particle size of the water-containing inorganic substance is small, the bulk increases and it becomes difficult to achieve high filling. Therefore, in order to increase the dehydration effect, a large particle size is preferable.

  Specifically, it is known that when the particle size is 18 μm, the filling limit amount is improved by about 1.5 times compared to the particle size of 1.5 μm.

  Further, by combining a large particle size and a small particle size, higher packing can be achieved.

  As a commercial item of the said water-containing inorganic substance, for example, as aluminum hydroxide, “trade name: Hygielite H-42M” (manufactured by Showa Denko) with a particle diameter of 1 μm, “trade name: Hygilite H-31 with a particle diameter of 18 μm”. (Made by Showa Denko KK) and the like.

  Examples of commercially available calcium carbonate include “trade name: Whiten SB red” (manufactured by Shiraishi Calcium Co., Ltd.) having a particle size of 1.8 μm, and “trade name: BF300” (manufactured by Bihoku Flour & Chemical Co., Ltd.) having a particle size of 8 μm. Etc.

Moreover, a phosphorus compound can be added to the heat-expandable resin composition of the present invention.
The phosphorus compound is used for improving the flame retardancy or for exhibiting a thermal expansion function in combination with a nitrogen compound, alcohol or the like.

The phosphorus compound is not particularly limited, and examples thereof include red phosphorus,
Various phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate,
Metal phosphates such as sodium phosphate, potassium phosphate, magnesium phosphate,
Ammonium polyphosphates,
Examples thereof include compounds represented by the following chemical formulas.

  These phosphorus compounds can be used alone or in combination of two or more.

  Among these, from the viewpoint of fire resistance, red phosphorus, a compound represented by the following chemical formula, and ammonium polyphosphates are preferable, and ammonium polyphosphates are more preferable in terms of performance, safety, cost, and the like.

In the above chemical formula, R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.

R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, or a C 1 to 1 carbon atom.
6 linear or branched alkoxyl groups, aryl groups having 6 to 16 carbon atoms, or aryloxy groups having 6 to 16 carbon atoms.

  Examples of the compound represented by the chemical formula include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2, 3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid , Diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid and the like.

  Among them, t-butylphosphonic acid is preferable in terms of high flame retardancy although it is expensive.

  The ammonium polyphosphates are not particularly limited, and examples include ammonium polyphosphate and melamine-modified ammonium polyphosphate. Ammonium polyphosphate is preferred from the viewpoint of flame retardancy, safety, cost, and handleability. Used.

  Examples of commercially available products include “trade name: EXOLIT AP422” and “trade name: EXOLIT AP462” manufactured by Clariant.

  It is considered that the phosphorus compound reacts with metal carbonates such as calcium carbonate and zinc carbonate to promote the expansion of the metal carbonate. In particular, when ammonium polyphosphate is used as the phosphorus compound, a high expansion effect is obtained. can get.

  It also acts as an effective aggregate and forms a highly shape-retaining residue after combustion.

The nitrogen compound is not particularly limited, but is preferably a melamine compound or the like.
The alcohols are not particularly limited, but polyhydric alcohols such as pentaerythritol are preferable.

  As described above, the thermally expandable resin composition of the present invention includes the above-described thermoplastic resin, thermosetting resin, binder resin such as rubber resin, the thermally expandable component, the inorganic filler, and the like. Examples of these are described below.

  The thermally expandable resin composition preferably contains 20 to 350 parts by weight of the thermal expansion component and 50 to 400 parts by weight of the inorganic filler with respect to 100 parts by weight of the binder resin.

  The total of the thermal expansion component and the inorganic filler is preferably in the range of 200 to 600 parts by weight.

  Such a thermally expandable resin composition expands by heating to form a thermally expanded residue. According to this formulation, the thermally expandable resin composition expands by heat such as fire, and can obtain a necessary volume expansion coefficient. After expansion, a residue having a predetermined heat insulation performance and a predetermined strength is obtained. It can be formed, and stable fireproof performance can be achieved.

When the total amount of the thermal expansion component is 20 parts by weight or more, the expansion ratio is improved, and sufficient fire resistance and fire prevention performance can be obtained.
On the other hand, when the total amount of the thermal expansion component is 350 parts by weight or less, the pseudo-collection force is improved, and the strength as a molded product is improved.

The weight ratio of the first thermal expansion component having a thermal expansion start temperature in the range of 140 to 250 ° C. and the second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C. (of the first thermal expansion component) The weight / weight of the second thermal expansion component is preferably in the range of 0.1-10.
When the weight ratio is 0.1 or more, the second thermal expansion component expands rapidly when the first thermal expansion residue by the first thermal expansion component is heated. Moreover, when this weight ratio is 10 or more, when a thermally expansible resin composition is heated, it expand | swells rapidly.

Moreover, since the remaining volume after combustion increases that the quantity of the said inorganic filler is 50 weight part or more, sufficient fireproof heat insulation layer is obtained.
Furthermore, since the ratio of a combustible material falls, a flame retardance improves.

  On the other hand, when the amount of the inorganic filler is 400 parts by weight or less, the blending ratio of the binder resin is increased, so that the cohesive force is improved and the strength as a molded product is improved.

  When the total amount of the thermal expansion component and the inorganic filler in the thermally expandable resin composition is 200 parts by weight or more, the amount of residue after combustion is increased and sufficient fire resistance is obtained. There is little deterioration of physical properties and it can withstand actual use.

The thermally expandable resin composition according to the present invention has a volume of the first thermal expansion residue per unit weight formed when heated at a temperature of 140 to 250 ° C. for 1 hour as V ₁ , and the first thermal expansion. When the volume of the second thermal expansion residue per unit weight formed when the residue is heated at a temperature of 251 to 350 ° C. for 1 hour is V ₂ , the volume ratio (V ₂ / V ₁ ) is 1. A range of 2 to 100 is preferable, a range of 2 to 70 is more preferable, and a range of 5 to 50 is more preferable.

  Further, the thermally expandable resin composition of the present invention is a range that does not impair the object of the present invention, and if necessary, in addition to antioxidants such as phenol-based, amine-based, sulfur-based, foaming agents, foam regulating agents An additive such as an agent, a metal harm-preventing agent, an antistatic agent, a stabilizer, a cross-linking agent, a lubricant, a softening agent, a pigment and a tackifying resin, and a tackifying agent such as polybutene and a petroleum resin can be added.

By using a foaming agent and a foam stabilizer in combination with the binder resin contained in the thermally expandable resin composition used in the present invention, a foam is obtained when the thermally expandable resin composition is molded. Is also possible.
Since the foam has heat insulation properties, the thermally expandable resin composition can be widely applied to the heat insulation field.

  Examples of the blowing agent include low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, and isobutyl. Organic physical foaming such as chlorinated aliphatic hydrocarbon compounds such as chloride, pentyl chloride, isopentyl chloride, fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane, ethers such as diisopropyl ether, or mixtures of these compounds Agents, inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas and carbon dioxide gas, water and the like.

  The amount of the foaming agent used for the binder resin is appropriately set depending on the binder resin to be used. For example, the amount used is usually in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. It is preferable if it is in the range of 5 to 10 parts by weight.

Examples of the foam stabilizer include organosilicon surfactants.
The amount of foam stabilizer used with respect to the binder resin is appropriately set depending on the binder resin to be used. For example, 0.01 to 5 parts by weight with respect to 100 parts by weight of the binder resin If it is the range, it is preferable.

Next, the manufacturing method of the said thermally expansible resin composition is demonstrated.
The method for producing the thermally expandable resin composition is not particularly limited. For example, when the binder resin contained in the thermally expandable resin composition is a thermoplastic resin or a rubber resin, each of the resin compositions A method in which the components are supplied to a known kneading apparatus such as an extruder, Banbury mixer, kneader mixer, and melt kneading, or each component of the resin composition is suspended in an organic solvent or heated and melted to form a paint. The resin composition can be obtained by a method such as forming a slurry or preparing a slurry by dispersing in a solvent.

  Further, when the binder resin contained in the thermally expandable resin composition is the thermosetting resin, for example, the thermally expandable resin composition is suspended in an organic solvent, or heated and melted. The resin composition can be obtained by a method such as coating to form a slurry, a method of preparing a slurry by dispersing in a solvent, or a method of melting the resin composition under heating.

  The thermally expandable resin composition is obtained by kneading the above components using a known apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a lycra machine, and a planetary stirrer. Obtainable.

Alternatively, a filler having a reactive functional group such as an epoxy group and a curing agent may be kneaded separately and kneaded with a static mixer, a dynamic mixer or the like immediately before molding.
The thermally expandable resin composition kneaded as described above can be appropriately formed into a necessary shape by a known molding technique such as extrusion molding, injection molding, mold molding, or press molding.

  By the method described above, the thermally expandable resin composition of the present invention can be obtained.

The thermal expansion resin composition is not particularly limited as long as it is thermally insulated by forming a thermal expansion residue when exposed to a high temperature such as in a fire, and has the strength of the thermal expansion residue. It is preferable if the volume expansion coefficient after heating for 30 minutes under a heating condition of / m ² is 3 to 50 times.
When the volume expansion coefficient exceeds three times, the expansion volume can sufficiently fill the burned-out portion of the binder resin, and the fireproof performance is good. Moreover, the intensity | strength of a thermal expansion residue is maintained as it is 50 times or less, and the effect which prevents the penetration of a flame improves. More preferably, the volume expansion coefficient is in the range of 5 to 40 times, and more preferably in the range of 8 to 35 times.

In order for the thermal expansion residue to be self-supporting, the thermal expansion residue needs to have a high strength. As the strength, a 0.25 cm ² indenter is used to compress the thermal expansion residue. It is preferable that the stress at break when the sample is measured at a compression speed of 0.1 m / s is 0.05 kgf / cm ² or more. When the stress at break exceeds 0.05 kgf / cm ² , the adiabatic expansion layer becomes self-supporting and fireproof performance is improved. More preferably, it is 0.1 kgf / cm ² or more.

Moreover, the said thermally expansible resin composition of this invention is preferable if it does not have fluidity at the temperature of 25 degreeC, and maintains a fixed shape so that it can shape | mold into a thermally expansible fireproof sheet etc.
In order to keep the heat-expandable resin composition of the present invention in a certain shape, the heat-expandable resin composition is contained in the heat-expandable resin composition to the extent that the heat-expandable resin composition does not have fluidity at a temperature of 25 ° C. What is necessary is just to increase the weight ratio of a thermal expansion component, an inorganic filler, etc. which are made.

The thermally expandable resin composition of the present invention can be appropriately formed into a molded body such as a thermally expandable fireproof sheet, and these molded bodies can be installed in building materials. The molded body such as the heat-expandable fireproof sheet is exposed to heat from a fire or the like to form the first thermal expansion residue. Form.
For this reason, even if a gap or a crack is generated in the vicinity of the building material where the molded body such as the heat-expandable fireproof sheet is installed, the second thermal expansion cannot be sufficiently blocked by the first thermal expansion residue. It can be blocked by residue.
Thereby, the heat-expandable resin composition of the present invention can be widely applied to building material applications.

Claims (4)

A thermal expansion component;
A binder resin,
An inorganic filler;
A resin composition comprising:
The thermal expansion component includes a first thermal expansion component having a thermal expansion start temperature in the range of 140 to 250 ° C and a second thermal expansion component having a thermal expansion start temperature in the range of 251 to 350 ° C. A heat-expandable resin composition. The first thermal expansion component is thermal expansion graphite having a thermal expansion start temperature in the range of 140 to 250 ° C.
The second thermal expansion component is thermal expansion graphite having a thermal expansion start temperature in the range of 251 to 350 ° C.
The thermally expandable resin composition according to claim 1, wherein the binder resin contains at least one selected from the group consisting of a thermosetting resin, a thermoplastic resin, and a rubber resin.   The heat-expandable resin composition according to claim 1 or 2, wherein the binder resin contains a thermosetting resin.   The binder resin includes at least one selected from the group consisting of urethane resin, isocyanurate resin, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, alkyd resin, melamine resin, diallyl phthalate resin, and silicone resin, The thermally expansible resin composition in any one of Claims 1-3.