CN108778424A - Fireproof construction body, solidification compound, refractory material and the fireproof construction body forming method of structure - Google Patents
Fireproof construction body, solidification compound, refractory material and the fireproof construction body forming method of structure Download PDFInfo
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- CN108778424A CN108778424A CN201780015555.5A CN201780015555A CN108778424A CN 108778424 A CN108778424 A CN 108778424A CN 201780015555 A CN201780015555 A CN 201780015555A CN 108778424 A CN108778424 A CN 108778424A
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C2/00—Fire prevention or containment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/92—Protection against other undesired influences or dangers
- E04B1/94—Protection against other undesired influences or dangers against fire
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Abstract
A kind of fireproof construction body, solidification compound, refractory material and fireproof construction body forming method using the structure with the solidfied material for playing excellent fire resistance after mobility appropriate, solidification before solidification is provided.The fireproof construction body of structure has：Structure；And the solidfied material of solidification compound, it is set at least part on the surface of the structure, the solidification compound has mobility at normal temperatures, for the solidfied material, it is 40 or more according to the JIS K6253-3 A type hardness tester meter hardness acquired, in the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, the solidfied material after the volume of the solidfied material after burning is 20 times or more of the volume of the solidfied material before burning and burns has shape retention.
Description
Technical field
The present invention relates to a kind of fireproof construction body of structure, solidification compound, refractory material and the fireproof construction bodily forms
At method.
Background technology
Defence in the inside of the structures such as building, it is external that theres is a situation where fire, it is desirable that structure is with preventing fire
The function of sprawling.Therefore, the fireproof construction using various refractory materials is proposed in the past.Such as, it is proposed that one kind for
Long dimension direction has the thermal expansivity refractory material of the purposes of the hollow portion injection of the resinous framework component of hollow portion, wherein
The thermal expansivity refractory material at least contains (i) reaction curable resin ingredient, (ii) thermally expands ingredient, (iii) liquid point
Powder and (iv) inorganic filler, by the drip molding formed by resin identical with resinous framework component in liquid dispersant
(iii) at a temperature of 50 DEG C impregnated of 5 days when, in the liquid dispersant (iii) before dipping with the drip molding after dipping
Weight change is less than 1% (for example, referring to patent document 1).Thermal expansivity refractory material recorded in patent document 1, energy
The thermal expansivity refractory material for showing stable fire line for a long time is provided.
Existing technical literature
Patent document
Patent document 1：International Publication No. 2014/162718
Invention content
Problems to be solved by the invention
However, require for structure etc. refractory material have corresponding to variously-shaped structure mobility with
And when suitably completely cutting off the various performances such as flame in the case where being exposed to flame, for including the heat recorded in patent document 1
For the existing refractory material of dilatancy refractory material, it is difficult to make the isolation performance of the flame after mobility before curing, solidification
Etc. multiple performances it is good.
Therefore, the object of the present invention is to provide a kind of using excellent with being played after mobility appropriate, solidification before solidification
Fireproof construction body, solidification compound, refractory material and the fireproof construction bodily form of the structure of the solidfied material of different fire resistance
At method.
Technical solution
The present invention in order to achieve the above objectives, provides a kind of fireproof construction body of structure, has：Structure；And
The solidfied material of solidification compound, is set at least part on the surface of structure, and solidification compound has at normal temperatures
Mobility, for solidfied material, the A type hardness tester meter hardness acquired according to JIS K6253-3 is 40 or more, make its in air
In, burnt 20 minutes under 400 DEG C of atmosphere in the case of, the volume of the solidfied material after burning is the body of the solidfied material before burning
Long-pending 20 times or more and the solidfied material after burning have shape retention.
In addition, in the fireproof construction body of above-mentioned structure, preferably make solidfied material in air being picked up with speed 2.0mm/s
In, in the case of the combustion residue that has burnt after twenty minutes under 400 DEG C of atmosphere, the volume of the combustion residue after picking up relative to
The volume of combustion residue before picking up is 80% or more.
In addition, in the fireproof construction body of above-mentioned structure, solidification compound can contain：(A) in a molecule
(methyl) acrylic ester polymer containing at least one bridging property silicon substrate and (B) thermally expandable graphite.
In addition, in the fireproof construction body of above-mentioned structure, solidification compound can contain (C) different from (A), institute
State (A) be in a molecule contain at least one bridging property silicon substrate (methyl) acrylic ester polymer, (C) be
Contain the organic polymer of at least one bridging property silicon substrate in one molecule.
In addition, in the fireproof construction body of above-mentioned structure, preferably it is different to contain mutual grain size for (B) thermally expandable graphite
The grain size of the thermally expandable graphite of the grain size and another party of at least two thermally expandable graphites and the thermally expandable graphite of a side
Absolute value of the difference be 100 μm or more.
In addition, in the fireproof construction body of above-mentioned structure, solidification compound can at least contain epoxy resin or phenol
Either one in urea formaldehyde.
In addition, the present invention in order to achieve the above objectives, provides a kind of solidification compound of fire resistance, in room temperature before solidification
There is down mobility, for the solidfied material after solidification, the A type hardness tester meter hardness that acquires according to JIS K6253-3 be 40 with
On, in the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, the volume of the solidfied material after burning is combustion
20 times or more of the volume of solidfied material before burning and the solidfied material after burning have shape retention.
Furthermore it is preferred that the solidification compound of above-mentioned fire resistance contains：(A) contain at least one crosslinking in a molecule
(methyl) acrylic ester polymer and (B) thermally expandable graphite of property silicon substrate.
In addition, the solidification compound of above-mentioned fire resistance further can contain (C) different from (A), (A) be
Contain (methyl) acrylic ester polymer of at least one bridging property silicon substrate in one molecule, (C) is in a molecule
In contain at least one bridging property silicon substrate organic polymer.
In addition, the present invention in order to achieve the above objectives, provides a kind of refractory material, has the solidification of solidification compound
Object has mobility before the solidification compound solidification, for solidfied material, is asked according to JIS K6253-3 at normal temperatures
The A type hardness tester meter hardness obtained is 40 or more, in the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, combustion
Solidfied material after the volume of solidfied material after burning is 20 times or more of the volume of the solidfied material before burning and burns has shape
Retentivity.
In addition, the present invention in order to achieve the above objectives, provides a kind of fireproof construction body forming method, have：It is coated with work
Solidification compound at normal temperatures with mobility is coated on at least part on the surface of structure by sequence；And solidification
Process makes solidification compound be solidified to form solidfied material, and for solidfied material, the A types acquired according to JIS K6253-3 are hard
Degree meter hardness is 40 or more, in the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, consolidating after burning
Solidfied material after the volume of compound is 20 times or more of the volume of the solidfied material before burning and burns has shape retention.
Advantageous effect
Fireproof construction body, solidification compound, refractory material and the fireproof construction body of structure according to the present invention are formed
Method can provide a kind of using the solidfied material for playing excellent fire resistance before solidification with mobility appropriate, after solidification
Fireproof construction body, solidification compound, refractory material and the fireproof construction body forming method of structure.
Specific implementation mode
[summary of the fireproof construction body of structure]
The fireproof construction body of the structure of the present invention has：Structure；And the solidfied material of solidification compound, it is set to
At least part on the surface of structure.In the present invention, structure includes：The building that is constituted using multiple components is constituted
Multiple components of building itself are (for example, window frame (sash), glossal canal, tongue and groove splicing (this ざ ね), sliding fit (The り あ わ
せ), (phase じ ゃ く り), key connection (employing い ざ ね), air vent etc. are docked), for air-conditioning equipment component (discharge duct etc.),
Component that controller switching equipment etc. has component of electric wire, constitutes water supply pipe or gas piping etc., other requirement to prevent fire/
Object or the component etc. of burning or sprawling from external flame/prolong burning.Moreover, the solidfied material of the present invention is being exposed to height
Carburization zone is formed in the case of temperature and the carburization zone expands, and to keep the shape after expansion to a certain degree.As a result,
The fireproof construction body of the structure of the present invention is prevented something from spreading/prolongs burning.
For example, the case where structure has the first construction component and constructs component with the second of the first construction component cooperation
Under, the solidfied material of the present invention is set to the gap in the region by the first construction component and the second construction component cooperation.It is solid at this
In the case that compound is exposed to high temperature because of fire etc., carburization zone or carbide are formed by solidfied material and the carburization zone or
Carbide expands and blocks gap.Prevent flame and/or heat in gap moreover, plugging the carburization zone in gap or carbide
It transmits.It can prevent something from spreading as a result, in the defined time, prolong burning.In addition, such as this can be coated in the inner wall in the hole building
The solidification compound of invention makes the solidification compound of coating cure and solidfied material is arranged in the inner wall.In this case, lead to
Cross fire etc. flame and/or heat and carburization zone or carbide are formed by the solidfied material, the carburization zone or carbide occur swollen
Swollen and plugging hole.Solidfied material according to the present invention as a result, can prevent the gas generated by flame, heat, cigarette and/or fire
Deng transmission.
[detailed content of the fireproof construction body of structure]
The fireproof construction body of the structure of the present invention has：Structure；And the solidfied material of solidification compound, it is set to
At least part on the surface of structure, the solidfied material are to make consolidating for the fire resistance under room temperature (that is, 23 DEG C) with mobility
Solidfied material obtained from the property changed composition solidification.Moreover, the solidfied material of the solidification compound of the present invention has：By curability
Composition be coated on structure and make its cure after, after burning to solidfied material, compared to burning before solidfied material volume,
The volume of solidfied material after burning becomes much larger, thus isolation heat, the characteristic of flame；Do not become excessively in the case where applying external force
It is easy to restore the hardness of original-shape after shape and elimination external force；Based on the not excessive deformation in the case where applying external force, in exposure
The characteristic of the size fully expanded can be kept in the case of flame, high temperature；And after burning to solidfied material
It can keep the shape retention of shape.
Specifically, the A type hardness tester meter hardness that the hardness of the solidfied material of the present invention is acquired according to JIS K6253-3 be 40 with
On, more preferably 50 or more.In addition, in the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, burning
The volume of solidfied material afterwards is 20 times or more of the volume of the solidfied material before burning (that is, relative to the volume before burning after burning
Expansion rate be 20 times or more), more preferably 25 times or more.Moreover, even if the solidfied material of the present invention is after combustion, it may have
The shape retention of the shape before burning is kept in predetermined range.
That is, in the present invention, making solidfied material burn in air, under 400 DEG C of atmosphere being picked up with speed 2.0mm/s
In the case of combustion residue after twenty minutes, shape is not out of shape, before the volume of the combustion residue after picking up is relative to picking up
The ratio of the volume of combustion residue be 80% or more, the shape of solidfied material before combustion after it is not out of shape in the case of, be set as having
There is the shape retention for keeping the shape before burning within a predetermined range.It should be noted that for the combustion after picking up
The volume of residue is burnt for the ratio of the volume of the combustion residue before picking up, from the transmission for preventing or inhibiting flame, heat
From the viewpoint of, preferably 80% or more, more preferably 95% or more.
[detailed content of solidification compound]
The solidification compound of the present invention mainly contains (A) and contains at least one bridging property silicon substrate in a molecule
(methyl) acrylic ester polymer (hereinafter, sometimes referred to as " (A) ingredient ") and (B) thermally expandable graphite are (hereinafter, sometimes
Referred to as " (B) ingredient ").Furthermore it is preferred that containing：Contain in a molecule with (A) (methyl) of at least one bridging property silicon substrate
Acrylic ester polymer different (C) in a molecule containing at least one bridging property silicon substrate organic polymer (hereinafter,
Sometimes referred to as " (C) ingredient ").Moreover, solidification compound can be containing either one in epoxy resin or phenolic resin or double
Side.Also, it is preferred that (B) thermally expandable graphite contains at least two different thermally expandable graphites of mutual grain size and the heat of a side
The absolute value of the difference of the grain size of the grain size of expansile graphite and the thermally expandable graphite of another party is 100 μm or more.In addition, this hair
Bright solidification compound preferably at 23 DEG C have mobility, preferably have can liquid coating mobility.For example, curability
Composition has 0.1Pas or more 1000Pas viscosity below before curing.
[(A) contains (methyl) acrylic ester polymer of at least one bridging property silicon substrate in a molecule]
As (A) ingredient, main chain is essentially (methyl) acrylic ester polymer, can use and be put down in a molecule
Organic polymer containing the bridging property silicon substrate of at least more than one.(A) ingredient is to be fired in the solidfied material of solidification compound
In the case of having burnt, (methyl) acrylic ester polymer that the shape of solidfied material is kept can help to.
(A) the bridging property silicon substrate of ingredient is to have the hydroxyl or hydrolization group with silicon atom bonding, through the air etc.
Moisture and form siloxanes key, thus, it is possible to crosslinked groups.As bridging property silicon substrate, such as it can enumerate and be shown by general formula (1)
The group gone out.
[chemical formula 1]
In formula (1), R1For the alkyl of carbon atom number 1~20, the alkyl of carbon atom number 1~20, carbon atom number 3~20
Naphthenic base, the aryl of carbon atom number 6~20, the aralkyl of carbon atom number 7~20, by R1 3SiO-(R1It indicates as hereinbefore)
Triorganosiloxy or-CH2OR1Base (R1As hereinbefore).In addition, R1It indicates on 1 to 3 carbon atom at least
One hydrogen atom is by halogen ,-OR2、-NR3R4,-N=R5、-SR6(R2、R3、R4、R6Respectively hydrogen atom or have carbon atom
The substituent group of number 1~20 or alkyl, R without substituent group5For with carbon atom number 1~20 divalent substituent or do not have
The alkyl of substituent group), the perfluoroalkyl of carbon atom number 1~20 or cyano substitution after carbon atom number 1~20 alkyl.At these
Among, preferably R1For methyl.In R1In the case of there are two or more, multiple R1It may be the same or different.X indicates hydroxyl
Or hydrolization group, in the case where X has more than two, multiple X may be the same or different.During a is 0,1,2 or 3
Any one integer.Consider curability, in order to obtain the solidification compound with enough curing rates, in formula (1), a is excellent
It is selected as 2 or more, more preferably 3.
Hydrolization group, hydroxyl can in 1~3 range with a silicon atom bonding.In hydrolization group, hydroxyl
In the case of being bonded two or more in bridging property silicon substrate, they may be the same or different.Form the silicon of bridging property silicon substrate
Atom can be one, or it is more than two, by the silicon atom of the connections such as siloxanes key, or
20 or so.
As hydrolization group represented by X, as long as other than F atom and it is not particularly limited.Such as it can enumerate：Alkane
Oxygroup, acyloxy, amino, amide groups, aminooxy group, alkenyloxy group etc..Among those, from water-disintegrable stabilization and easily operated sight
Point consideration, preferably alkoxy.Among alkoxy, the reactivity of the few group of carbon atom number is high, according to methoxyl group>Ethyoxyl>
The sequence of propoxyl group, carbon atom number more at most reactivity are lower.It can be selected according to purpose, purposes, but usually using methoxy
Base, ethyoxyl.
As bridging property silicon substrate, such as can enumerate：The tri-alkoxies silicon such as trimethoxy silane base, triethoxysilicane alkyl
Alkyl ,-Si (OR)3, methyl dimethoxysilane base, dialkoxy silicanes the base ,-SiR such as methyldiethoxysilane base1
(OR)2.Here, R is the alkyl such as methyl, ethyl.In addition, bridging property silicon substrate can be used, or two or more may be used.
Bridging property silicon substrate can be bonded to main chain or side chain or be bonded to both sides.It is only located at the main chain of strand in bridging property silicon substrate
End in the case of, effective screening length of the component of polymer contained in finally formed solidfied material is elongated, therefore is easy to
Obtain showing the rubber-like solidfied material of high intensity, high elongation rate and low elastic modulus.Moreover, from the solidification of solidification compound
From the viewpoint of the physical properties excellent of the solidfied materials such as the tensile properties of object, preferably bridging property silicon substrate is present in molecule chain end.
In addition, in (A) ingredient, from the viewpoint of the physical property such as tensile bond, modulus after solidification, preferably at one
In polymer molecule averagely exist 1.0 or more 5 bridging property silicon substrates below, be more preferably the presence of 1.1 or more 3 it is below
Bridging property silicon substrate.It is excellent from obtaining from the viewpoint of showing the rubber-like solidfied material of high intensity, high elongation rate and low elastic modulus
The bridging property silicon substrate contained in choosing (A) ingredient averagely has 1.0 or more in an organic polymer molecules, is more preferably the presence of
1.1 or more 5 or less.It should be noted that from the viewpoint of making crosslink density reduce, can also and be contained in molecule
Bridging property silicon substrate 1.0 organic polymers below of quantity average out to.
As the main chain backbone of (A) ingredient, specifically, can enumerate：(methyl) ethyl acrylate, (methyl) acrylic acid
Butyl ester etc. carries out (methyl) acrylic ester polymer obtained from free radical polymerization to monomer.It can be single among (A) ingredient
Solely contain these skeletons, can also block or it is random in containing two or more.
The glass transition temperature of (methyl) acrylic ester polymer is relatively low, and the cold resistance of obtained solidfied material is excellent.
In addition, the penetrability (moisture permeability) of (methyl) acrylic ester polymer is high, liquid type combination is being made
In the case of object, deep curability is excellent.
(methyl) acrylate monomer of main chain as composition (methyl) acrylic ester polymer can use each
Kind monomer.Such as it can enumerate：Acrylic acid etc. (methyl) acrylic monomer；(methyl) methyl acrylate, (methyl) acrylic acid
(methyl) propylene such as ethyl ester, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) stearyl acrylate
Acid alkyl ester system monomer；Ester ring type (methyl) acrylate monomer；Aromatic series (methyl) acrylate monomer；(methyl) third
Olefin(e) acid 2- methoxy acrylates etc. (methyl) acrylate monomer；γ-(methacryloxypropyl) trimethoxy silane, γ-
(methyl) acrylate monomer of the silane-group containings such as (methacryloxypropyl) dimethoxymethylsilane；(methyl) propylene
The derivative of acid；Fluorine-containing (methyl) acrylate monomer etc..
It, can also be by vinyl monomer below and (methyl) acrylate for (methyl) acrylic ester polymer
It is that monomer is copolymerized together.If exemplified vinyl monomer can enumerate：Styrene, maleic anhydride, vinyl acetate
Ester etc..In addition, propylene can also be contained in addition to these as monomeric unit (hereinafter also referred to as other monomers unit)
Acid, glycidyl acrylate.
These can be used alone, and can also be copolymerized multiple.The viewpoints such as the physical property from product consider, preferably by (methyl) third
The polymer that olefin(e) acid system monomer is formed.In addition, one or more kinds of (methyl) alkyl acrylate monomers is more preferably used,
As needed and (methyl) acrylic ester polymer made of other (methyl) acrylic monomers.Moreover, by being used in combination
(methyl) acrylate monomer of silane-group containing, can control the quantity of silicon substrate in (methyl) acrylic ester polymer.By
Methacrylate based polymer good in cementability, therefore particularly preferably being formed by methacrylate monomers.In addition,
In the case of carrying out lowering viscousity, imparting flexibility, imparting adhesiveness, acrylate monomer is preferably suitably used.It needs to illustrate
It is that in the present invention, (methyl) acrylic acid indicates acrylic acid and/or methacrylic acid.
Oneself that Raolical polymerizable is utilized can be used for example in the manufacturing method of (methyl) acrylic ester polymer
By base polymerization.As radical polymerization, can enumerate：Make oneself of defined monomeric unit copolymerization using polymerization initiator
By base polymerization (radical polymerization method), can the controlled locations such as terminad import the control free radical polymerization of reactive silicon alkyl
Method.But, the polymerization obtained using the radical polymerization method using azo compound, peroxide etc. as polymerization initiator
The value of the molecular weight distribution of object is generally increased to 2 or more, and viscosity is got higher.Therefore, to obtain narrow molecular weight distribution, viscosity low, with
At high proportion in the case where molecule chain end has (methyl) acrylic ester polymer of cross-linking functional group, it is preferable to use control
Radical polymerization processed.
As control radical polymerization, the free radical for having used the chain-transferring agent with specific functional group can be enumerated
Polymerization, living radical polymerization.It is preferred that using addition-cracking transfer reaction (Reversible Addition
Fragmentation chain Transfer：Reversible Addition Fragmentation Chain Transfer；RAFT) polymerization, used transition metal network
Close radical polymerization (the Transition Metal Mediated Living Radical Polymerization of object：It crosses
Cross metal mediation active free radical polymerization), Transfer Radical Polymerization (Atom Transfer Radical
Polymerization；ATRP) isoreactivity radical polymerization.It should be noted that being (methyl) as synthesis main chain backbone
Acrylic ester polymer, part of it are the reaction of the polymer (hereinafter referred to as " pseudo- telechelic polymer ") of telechelic polymer,
It can enumerate and use the reaction of the mercaptan compound with reactive silicon alkyl, used the mercaptan with reactive silicon alkyl
The reaction of compound and Metallocenic compound.The present invention can also be not being hindered by these pseudo- telechelic polymer obtained by the reaction
The function of solidification compound and the effect of realization in the range of use.
For the number-average molecular weight of (methyl) acrylic ester polymer, in (methyl) acrylic ester polymer
In the case that glass transition temperature (Tg) is less than 0 DEG C, such as in (methyl) acrylic ester polymer mainly by acrylic acid fourth
Ester monomer unit constitute in the case of, preferably 20000 or more, more preferably 30000 or more, further preferably 35000 with
On, particularly preferably 40000 or more.In addition, the glass transition temperature (Tg) in (methyl) acrylic ester polymer is 0 DEG C
In the case of above, such as the feelings that are mainly made of methyl methacrylate monomer unit in (methyl) acrylic ester polymer
Under condition, number-average molecular weight be preferably 600 or more 10000 hereinafter, more preferably 600 or more 5000 hereinafter, further preferably
1000 or more 4500 or less.By making number-average molecular weight in the range, in the case of use (C) ingredient, when in (C) ingredient
When containing polyoxy alkylidene based polymer with bridging property silicon substrate, improved with the compatibility of the polyoxy alkylidene based polymer.
(methyl) acrylic ester polymer can be used alone, can also and with two or more.It should be noted that the number of the present invention
Average molecular weight is the molecular weight to convert through polystyrene obtained according to gel permeation chromatography.
[(B) thermally expandable graphite]
(B) thermally expandable graphite is by utilizing inorganic acids and concentrated nitric acid, perchloric acid, the peroxides such as sulfuric acid, nitric acid to graphite
Change the strong oxidizers such as hydrogen to be handled, bedded substance made of the interlayer of the embedded graphite such as acid.(B) interlayer of thermally expandable graphite
Compound gasified by heating, there is the property that is expanded by gasification.In the present invention, from the solidfied material hair for making the present invention
From the viewpoint of the isolation capacity for waving heat and/or flame, before with the volume of the solidfied material after burning can be made to be burning
(B) thermally expandable graphite of 20 times or more of grain size of the volume of solidfied material.It should be noted that in the present invention, grain size is
The grain size of Z8801-1982 " standard screen " according to JIS standards is also marked by " μm " label and by " mesh " sometimes.
The volume bigger of solidfied material after making burning, and keep the thermally expandable graphite in the solidfied material after burning intensive
From the viewpoint of filling, preferred different a variety of thermally expandable graphites of assorted size.Specifically, different using mutual grain size
At least two thermally expandable graphites.Also, it is preferred that the grain size of the thermally expandable graphite of a side and the thermally expandable graphite of another party
Grain size absolute value of the difference be 100 μm or more.In addition, using at least two different thermally expandable graphites of mutual grain size
In the case of, if such as the side that is used in combination grain size small a thermally expandable graphite side big with grain size thermally expandable graphite, can
Improve shape retention.
In addition, the thermally expandable graphite of the small side of grain size there can be the grain size less than 100 μm, but preferably there are 100 μ
The grain size of m or more, more preferably with 150 μm or more of grain size.Moreover, the thermally expandable graphite of the big side of grain size preferably has
200 μm or more of grain size, more preferably with 250 μm or more of grain size, further preferably with 300 μm or more of grain size.
That is, in the case where using two kinds of thermally expandable graphites as an example, using the first thermally expandable graphite and with the
The second different thermally expandable graphite of one thermally expandable graphite grain size.Moreover, as the first thermally expandable graphite for example using
In the case that grain size is the thermally expandable graphite of 150 μm (100mesh), for example it is using grain size as the second thermally expandable graphite
Thermally expandable graphite more than 250 μm (60mesh).Similarly, it is 300 μm using grain size as the first thermally expandable graphite
In the case of the thermally expandable graphite of (50mesh), it is 400 μm or more or 500 μm to use grain size as the second thermally expandable graphite
Thermally expandable graphite more than (30mesh).
It should be noted that the volume bigger of the solidfied material after making burning, and make the heat in the solidfied material after burning
The intensive filling of expansile graphite and from the perspective of further increasing flame and/or the isolation performance of heat, preferable particle size it is big one
The thermally expandable graphite minimum of side has 300 μm or more of grain size (in this case, the grain size of the thermally expandable graphite of another party
It is 200 μm or more), the thermally expandable graphite maximum of the small side of preferable particle size has 400 μm of grain sizes below (in the situation
Under, the grain size of the thermally expandable graphite of another party is 500 μm or less).
In the solidification compound of the present invention, preferably the content ratio of (B) thermally expandable graphite is relative to (A) ingredient
100 mass parts (containing (C) ingredient, (A) ingredient and the total amount of (C) ingredient are 100 mass parts) are 10 mass parts
Above 100 is below mass part.
[(C) contains the organic polymer of at least one bridging property silicon substrate in a molecule]
From the viewpoint of the surface viscosity for suppressing or eliminating solidfied material, solidification compound can also contain (C) ingredient.
(C) ingredient is the organic polymer for averagely containing at least one bridging property silicon substrate in a molecule, and main chain can also contain poly-
The organic polymer of siloxanes.(C) ingredient is different from (A) ingredient, and different from (methyl) acrylic ester polymer is organic poly-
It closes object and constitutes main chain.It should be noted that for the bridging property silicon substrate of (C) ingredient, due to the bridging property silicon substrate phase with (A) ingredient
Detailed description will be omitted together.
As the main chain of (C) ingredient, from the viewpoint of the physical property such as tensile bond, modulus after solidification are good, such as
It can enumerate：The poly (oxyalkylene)s base systems such as polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer are poly-
Close object；Ethylene-propylene based copolymer, polyisobutene, polyisoprene, polybutadiene, these polyolefin polymer hydrogenations and
The hydrocarbon systems polymer such as obtained hydrogenated polyolefins based polymer；Polycondensation by the binary acid such as adipic acid and dihydric alcohol or lactone
Ring-opening polymerisation obtained from polyester based polymer；The monomers such as vinylacetate, acrylonitrile, styrene carry out free radical polymerization and
Obtained vinyl polymers；Graft polymers obtained from vinyl monomer is polymerize in organic polymer；Polysulfide
Compound based polymer；Polyamide-based polymer；Makrolon based polymer；Diallyl phthalate based polymer etc..This
A little skeletons can also contain organosiloxane, can individually contain in (C) ingredient, can also block or it is random in contain two
Kind or more.
Moreover, the excellent consideration of the cold resistance of solidfied material that is relatively low from glass transition temperature, obtaining and it is preferred that polyisobutene,
The saturated hydrocarbons such as hydrogenated polyisoprene, hydrogenated butadiene polymer based polymer or polyoxy alkylidene based polymer etc..In addition, from moisture-inhibiting
Property it is high, in the case where a liquid type composition is made, the excellent consideration of deep curability and it is preferred that polyoxy alkylidene based polymer.
These organic polymers with bridging property silicon substrate can be used alone, can also and with two or more.It is specific and
Speech can also use mixing selected from by the polyoxy alkylidene based polymer with bridging property silicon substrate and satisfying with bridging property silicon substrate
Two or more organic polymers in the group constituted with hydrocarbon system polymer.
Main chain backbone be oxyalkylene based polymer and end have the functional groups such as hydrolization group polymer (hereinafter,
Referred to as " polyoxy alkylidene based polymer ") it is the polymer with the repetitive unit indicated by general formula (2).
-R7-O-···(2)
In general formula (2), R7For the straight-chain or sub-branched alkyl of carbon atom number 1~14, preferably carbon atom number 1~14
Straight-chain or sub-branched alkyl, the further preferably straight-chain or sub-branched alkyl of carbon atom number 2~4.
As the concrete example of the repetitive unit indicated by general formula (2), can enumerate：-CH2O-、-CH2CH2O-、-CH2CH
(CH3)O-、-CH2CH(C2H5)O-、-CH2C(CH3)2O-、-CH2CH2CH2CH2O- etc..The main chain bone of polyoxy alkylidene based polymer
Frame can be formed only by a kind of repetitive unit, can also be formed by two or more repetitive units.Particularly preferably by with oxygen Asia third
Base (oxypropylene) makees the main chain backbone that polymer as main component is formed.
For the molecular weight of the polyoxy alkylidene based polymer with bridging property silicon substrate, in order to reduce as solidfied material
Incipient extension characteristic stretch modulus, increase fracture when elongation and it is preferred that high molecular weight.In the present invention, as polyoxy Asia
The lower limit of the number-average molecular weight of alkyl based polymer, preferably 15000, further preferably 18000 or more, more preferably
20000 or more.If molecular weight increases, the viscosity of polymer rises, and the viscosity of solidification compound also rises, therefore it is also preferred that
For the polymer for the polymer for being 20000 or more containing some number-average molecular weight.In addition, the upper limit of number-average molecular weight is
50000, further preferably 40000.It should be noted that the number-average molecular weight of the present invention is to be obtained according to gel permeation chromatography
The molecular weight to convert through polystyrene arrived.From being stretched when the stretch modulus of the solidfied material for substantially ensuring solidification compound, fracture
From the viewpoint of long rate, preferred number average molecular weight be 15000 or more, from make the viscosity of solidification compound in proper range,
From the viewpoint of ensuring good workability, preferred number average molecular weight is 50000 or less.
If in polyoxy alkylidene based polymer, the content of bridging property silicon substrate is set moderately to reduce, then the crosslinking of solidfied material is close
Degree reduces, therefore is initially becoming more soft solidfied material, elongation characteristic increase when modulus properties reduce and are broken.Poly-
In oxyalkylene based polymer, preferably bridging property silicon substrate in a Molecularly Imprinted Polymer averagely exist 1.2 or more 2.8 with
Under, 1.3 or more 2.6 are more preferably the presence of hereinafter, further preferably there are 1.4 or more 2.4 or less.It is sufficient from ensuring
From the viewpoint of curability, the quantity of the bridging property silicon substrate preferably contained in molecule is more than one, from as suitable density
Mesh configuration and from the viewpoint of ensuring good mechanical property, preferably the quantity of bridging property silicon substrate is specified quantity or less.And
And in the case where main chain backbone is the polymer of difunctionality of straight chain, preferably the bridging property silicon substrate of the polymer is at one point
Averagely there are 1.2 or more in sub- polymer and less than 1.9, is more preferably the presence of 1.25 or more 1.8 hereinafter, further excellent
Choosing is there are 1.3 or more and is less than 1.7.
Polyoxy alkylidene based polymer with bridging property silicon substrate can be that straight-chain can also be with branch.It is drawn from reducing
From the viewpoint of stretching modulus, preferably the polyoxy alkylidene based polymer with bridging property silicon substrate is the polymer of straight-chain.In addition,
The molecular weight distribution (Mw/Mn) of polyoxy alkylidene based polymer with bridging property silicon substrate be 2 hereinafter, particularly preferably 1.6 with
Under.
As the synthetic method of polyoxy alkylidene based polymer, such as the basic catalyst using KOH etc can be enumerated
Polymerization, such as using the polymerization etc. of bimetallic cyanide complex catalyst, but and be not particularly limited.It is double golden according to utilizing
The polymerization for belonging to cyanide complex catalyst, can obtain that number-average molecular weight is 6000 or more, Mw/Mn is 1.6 height below
The polyoxy alkylidene based polymer of molecular weight and narrow molecular weight distribution.
The other compositions such as urethane bond ingredient can also be contained in the main chain backbone of polyoxy alkylidene based polymer.
As urethane bond ingredient, such as can enumerate：Toluene (toluylene) diisocyanate, two isocyanide of diphenyl methane
The aromatic systems polyisocyanate such as acid esters；By the fatty families such as isophorone diisocyanate polyisocyanate and with hydroxyl
Ingredient obtained from the reaction of polyoxy alkylidene based polymer.
By keeping the polyoxy in the molecule with functional groups such as unsaturated group, hydroxyl, epoxy group or isocyanate group sub-
Alkyl based polymer with reacting compound of the functional group with reactive functional group and bridging property silicon substrate, can be to poly-
Oxyalkylene based polymer imports bridging property silicon substrate (hereinafter referred to as high molecular weight reactive method).
As the example of high molecular weight reactive method, the hydrosilanes with bridging property silicon substrate of sening as an envoy to can be enumerated, with bridging property
The sulfhydryl compound of silicon substrate acts on the polyoxy alkylidene based polymer containing unsaturated group and it is hydrosilylation, Thiolation, obtain
To the method for the polyoxy alkylidene based polymer with bridging property silicon substrate.For the poly (oxyalkylene) base system polymerization containing unsaturated group
For object, the organic polymer with functional groups such as hydroxyls can be made and had to show reactive active group to the functional group
The organic compound reaction of group and unsaturated group, and obtain the polyoxy alkylidene based polymer containing unsaturated group.
In addition, the other examples as high molecular weight reactive method, can enumerate：Make end that there is the poly (oxyalkylene) base system of hydroxyl
Method that polymer is reacted with the compound with isocyanate group and bridging property silicon substrate keeps end poly- with isocyanate group
The method that oxyalkylene based polymer is reacted with the compound with hydroxyl, amino isoreactivity hydrogen group and bridging property silicon substrate.If
Using isocyanate compound, then may be easy to obtain the polyoxy alkylidene based polymer with bridging property silicon substrate.
Polyoxy alkylidene based polymer with bridging property silicon substrate can be used alone, can also and with two or more.
In (C) ingredient of the solidification compound of the present invention, preferably bridging property silicon substrate is in a molecule organic polymer
In averagely exist more than one, be more preferably the presence of two or more.In addition, the present invention solidification compound in, from inhibit or
From the viewpoint of the surface viscosity for eliminating solidfied material, unit of (C) ingredient relative to (A) ingredient in preferred consolidation composition
Mass parts contain 0.4 times or more, further preferably twice or more.
[epoxy resin]
As epoxy resin, various epoxy resin can be used.For example, bisphenol A type epoxy resin, Bisphenol F can be enumerated
Type epoxy resin, bisphenol-A D-ring oxygen resin, bisphenol-s epoxy resin or by these epoxy resin, glycidols after hydrogenating
Ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, novolac type ring
Oxygen resin, the urethane-modified epoxy resin with urethane bond, fluorinated epoxy resin, rubber modified epoxy resin
(such as by any one of polybutadiene, styrene butadiene ribber (SBR), nitrile rubber (NBR) and CTBN modified rubbers after
Epoxy resin etc.), fire-retardant epoxy resins such as the glycidol ether of tetrabromobisphenol A etc..These epoxy resin can individually make
With, can also and with two or more.Epoxy resin can help to the shape retention after the solidfied material burning of solidification compound.
Among these epoxy resin, from workability, curability, adhesive strength, adherend versatility, water resistance, durable
From the viewpoint of the balance of property etc., preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring oxygen resin,
Bisphenol-s epoxy resin, by these epoxy resin after hydrogenating, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy tree
Fat, most preferably bisphenol A type epoxy resin.
The molecular weight of epoxy resin is simultaneously not particularly restricted, but preferred number average molecular weight be 300 or more 1000 hereinafter, more preferably
It is 350 or more 600 or less.In addition, it is preferable to use being the asphalt mixtures modified by epoxy resin of liquid at normal temperatures from the aspect of operational ease
Fat.
In the solidification compound of the present invention, the mixing ratio of epoxy resin relative to 100 mass parts of (A) ingredient (
In the case of (C) ingredient, (A) ingredient and the total amount of (C) ingredient are 100 mass parts) it is 0.5 mass parts or more, 20 mass parts
Hereinafter, more than preferably 1 mass parts 15 below mass part.
[phenolic resin]
As phenolic resin, linear phenol-aldehyde resin (Novolak type phenolic resin), resol type can be used
The various phenolic resin such as phenolic resin.As phenolic resin, from the viewpoint of indoor air quality pollution measure, it is preferable to use
It can prevent the linear phenol-aldehyde resin etc. of formaldehyde.Phenolic resin can help to solidification compound solidfied material burning after it is residual
The shape of slag is kept.
In the solidification compound of the present invention, the mixing ratio of phenolic resin relative to 100 mass parts of (A) ingredient (
In the case of (C) ingredient, (A) ingredient and the total amount of (C) ingredient are 100 mass parts) it is 0.01 mass parts or more, 20 mass
Part hereinafter, more than preferably 3 mass parts 10 below mass part.
[other complexs]
Effect of the solidification compound of the fire resistance of the present invention in the fireproof construction body for the structure for not hindering the present invention
In the range of, it can further coordinate inorganic filler, age resister, water-absorbent material, tackifier (then paying drug), solidification to urge
Agent, filler, diluent, ultra-violet absorber, antioxidant, physical property conditioning agent, plasticizer, thixotropic agent, fire retardant, thickening
Agent (drug is paid in adhesion), anti-sagging agent, radical polymerization initiator, colorant etc. and/or the various objects such as toluene, alcohol equal solvent
Matter, in addition it is also possible to mix the other polymers to mix.
[tackifier]
The solidification compound of the present invention can make solidfied material each relative to metal, plastics, glass etc. by coordinating tackifier
The cementability of kind adherend improves.
Tackifier can be used as the various silane coupling agents of the silane containing alkoxy.It is, for example, possible to use 3- amino
Propyl trimethoxy silicane, 3-aminopropyltriethoxysilane, 3- aminopropylmethyldimethoxysilanes, N- (2- amino
Ethyl) -3- TSL 8330s, N- (2- amino-ethyls) -3-aminopropyltriethoxysilane, N- (2- amino
Ethyl) the amino-containing silane such as -3- aminopropylmethyldimethoxysilanes, 1,3- diamino isopropyltri-methoxysilanes
Class；The silanes of the bases containing ketimide such as 3- trimethoxy silane bases-N- (1,3- dimethyl-butylidene) propylamine；3- mercaptopropyis
The various silane coupling agents such as the silanes containing sulfydryl such as trimethoxy silane.
The mixing ratio of tackifier is simultaneously not particularly restricted, but (is containing (C) ingredient relative to 100 mass parts of (A) ingredient
In the case of, the total amount of (A) ingredient and (C) ingredient is 100 mass parts) it is preferably that 0.2 mass parts or more 20 are below mass part, it is more excellent
It is below mass part to be selected as 0.3 mass parts or more 15, more than further preferably 0.5 mass parts 10 is below mass part.These thickeninies
Agent can be used alone, can also and with two or more.
[curing catalysts]
As curing catalysts, dibutyl tin laurate, dibutyltin diacetate, oxidation dioctyl can be used for example
The organo-tin compounds such as the reactant of the reactant of tin and silicate compound, dibutyltin oxide and phthalic acid ester；Carboxylic
The carboxylic metallic salts such as sour tin, bismuth carboxylate, ferric carboxylate；Aliphatic amine, aromatic amine；The carboxylic acids such as versatic acid；Bis- (acetoacetates
Ethyl ester) metal alkoxides such as titanium compounds, the aluminium compound class such as metatitanic acid diisopropyl ester；Inorganic acid；Boron trifluoride ethylamine complex compound
Equal boron trifluoride complexes；Single acetyl acetone two (ethyl acetoacetate) closes metallo-chelates such as aluminium etc..Among those preferably
Organo-tin compound.
In the case where adding epoxy resin into solidification compound, the solidification that can further add epoxy resin is urged
Agent.In addition, as curing catalysts, such as can select to use one or more epoxy curing agents.As such
Curing catalysts, such as can enumerate：The primary amine such as cycloaliphatic amines, the aliphatic amine containing aromatic rings, aromatic amine, modified amine；Directly
The secondary amine such as chain secondary amine；The anhydrides such as aromatic anhydride, annular aliphatic acid anhydrides, aliphatic anhydride；Polyamide, organic acid acyl
Other curing agent such as the initial condensation polymer of hydrazine, synthetic resin, polyvinylphenol；The compound after ketimide is carried out to amino
Deng.
Using curing catalysts, relative to 100 mass parts of (A) ingredient (containing (C) ingredient the case where
Under, the total amount of (A) ingredient and (C) ingredient is 100 mass parts) it is that 0.5 mass parts or more 20 are below mass part, preferably in 1 mass
Part or more use in 15 ranges below mass part.
The solidification compound of the present invention may be a liquid type or two-liquid type.The solidification compound of the present invention can be used
It is required the purposes of fire resistance, such as may be used as bonding agent, Embedding Material, coating material, sealing material, jointing material, painting
Material, putty material and/or subbing etc..In addition, for the solidification compound of the present invention, it can be by the curability group
It closes object and itself serves as refractory material, or the solidification compound of the present invention can also be used as combining the curability of the present invention
Object is set to refractory material made of the component with fire resistance.The solidification compound of the present invention is for example applicable to various build
Build the structures such as object use, automobile, building are used, various electrical/electronic fields are used etc..
[fireproof construction body forming method]
Fireproof construction body can be formed using the solidification compound of the present invention.That is, the fireproof construction bodily form of the present invention
Have at method：The solidification compound of the present invention is coated on at least part on the surface of structure by painting process；And
Curing process makes solidification compound be solidified to form solidfied material.As an example, it is combined by the way that the curability of the present invention will be contained
The sealing material of object is combined with the wall material with fire resistance, can be formed in the fire resisting of the V-0 grades recorded in flammability UL94 standards
The qualified fireproof construction body of energy in experiment.
Painting process is, such as the solidification compound of the present invention is coated on to the first construction component with fire resistance
The work of (for example, constituting the wall structure of wall) and the second matched part of construction component for being matched with the first construction component
Sequence.In addition, in the case where constructing component with opening portion, the solidification compound of the present invention can also be coated on opening portion
Inside.By after painting process, solidification compound being made to cure, the solidfied material of fire resistance is set to the first construction component
With the second matched part of construction component.It should be noted that the solidification compound of the present invention can also be pre-coated with
It is combined with the region of the second construction component in the first construction component, and makes its solidification.In this case, with across the first construction
The region for being provided with solidfied material of component, cooperation first construction component with second construct component and it is integrated.
(effect of embodiment)
The fireproof construction body of the structure of present embodiment is in the case where being exposed to flame, high temperature, solidification compound
Solidfied material formed as heat insulation layer carburization zone and the carburization zone be expanded to 20 of the volume before being exposed to flame, high temperature
Times or more volume.The fireproof construction body of structure according to the present embodiment as a result, between constituting between the component of structure
The be cured combustion residue of object such as gap, opening or hole blocks, and can completely cut off by flame, heat, cigarette and/or the gas etc. for generation of burning.
Therefore, the fireproof construction Giving play to physical strength of the structure of present embodiment excellent fire resistance and flame, heat, cigarette and/or gas
The isolation performance of body etc..
In addition, in the present embodiment, since solidfied material has defined hardness and flexibility, even if having from outside
Applied force only spends deformation and restores the property of original-shape if removing power.Therefore, even if there are bumps in structure
In the case of, being set to the solidfied material of the solidification compound of the present embodiment of the structure can also keep corresponding to concave-convex shape
Shape.The fireproof construction physical efficiency of the structure of present embodiment maintains prolonged fire resistance as a result,.
Embodiment
Hereinafter, the solidification compound using the fireproof construction body of the embodiment structure that the present invention will be described in detail and solidification
Object.
(embodiment 1)
The solidification compound of the fire resistance of embodiment 1 is prepared as described below.First, as shown in table 1, to (A) at
Point, (B) ingredient, inorganic filler mixed with curing catalysts by the amount that table 1 is recorded.Then, mix by stirring object and
It is prepared for the solidification compound of the fire resistance of embodiment 1.Then, the solidification compound to the fire resistance of embodiment 1 and solid
The characteristic of compound is evaluated.It the results are shown in table 1.It should be noted that in table 1, each use level for coordinating substance
Unit be " g ".In addition, the detailed content of cooperation substance is as described below.
[(A) ingredient]
* 1 contains (methyl) acrylic ester polymer of at least one bridging property silicon substrate in a molecule：ProductName
" SE-09 " (acrylate copolymer with the end silylation (silyl group)), Soken Chemical & Engineering Co., Ltd.'s manufacture
[(B) ingredient]
* 2 thermally expandable graphite B1：(grain size is big for ProductName " expanded graphite 9532400A "：+ 32mesh75% or more, quite
In 500 μm of grain size), the manufacture of itoite ink Industrial Co., Ltd
* 3 thermally expandable graphite B2：(grain size is small for ProductName " expanded graphite 9950200 "：80% or more+50mesh, quite
In 300 μm of grain size), the manufacture of itoite ink Industrial Co., Ltd
[(C) ingredient]
Organic polymer that is * 4 different from (A) ingredient, containing in a molecule at least one bridging property silicon substrate：Product
Name " Silyl EST280 " (polymer of silylation sealing end), Co., Ltd. KANEKA manufactures
[epoxy resin]
* 5 epoxy resin：ProductName " DER331 " (bisphenol A type epoxy resin), DOW CHEMICAL Amada Co., Ltd.s system
It makes
[phenolic resin]
* 6 phenolic resin：ProductName " PR-HF-3 " (linear phenol-aldehyde resin), 80 DEG C of softening point, SUMITOMOBAKELITE
Co., Ltd. manufactures
[inorganic filler]
* 7 aluminium hydroxides：ProductName " ALMORIXB350 ", Tomoe Engineering Co., Ltd.'s manufacture
[curing catalysts]
* 8 curing catalysts：(dibutyltin oxide reacts production to ProductName " NEOSTANNU-700ES " with ethyl orthosilicate
Object), Nitto Kasei Co., Ltd manufacture
* 9 curing catalysts：ProductName " X12-812H " (methyl iso-butyl ketone (MIBK) (MIBK) and 3- aminopropyl trimethoxies
The reactant of silane), Shin-Etsu Chemial Co., Ltd manufacture
[table 1]
The characteristic of the solidification compound of the fire resistance of embodiment 1 is evaluated as described below.
1) viscosity
The viscosity of the solidification compound of embodiment 1 utilizes rotor × 20 BS type viscosimeter No.7 at 23 DEG C of 50%RH
Rotation is determined.
2) hardness of solidfied material
To the hardness foundation JIS of solidfied material obtained from making the solidification compound in embodiment 1 cure by condition of cure 1
K6253-3 is determined using A type hardness tester meters.
3) shape retention after burning
The solidification compound of embodiment 1 is set to cure by condition of cure 1, it is length 10mm × width 10mm to have obtained size
The solidfied material of × thickness 1.6mm.Then, which is placed in electric furnace (big and science Co. Ltd. system moulding number：FO300
Type) in, so that it has been burnt 20 minutes in air, under 400 DEG C of atmosphere.After burning, it is positioned in electric furnace and keeps 12 at 23 DEG C
Hour.Later, the state of solidfied material (hereinafter referred to as " combustion residue ") is confirmed with range estimation at 23 DEG C of 50%RH.Confirm item
Mesh is the shape and volume of combustion residue.The volume of combustion residue at 23 DEG C of 50%RH by using scale to measure combustion residue
Size (length, width and thickness) and be calculated.It should be noted that in the case where combustion residue has concave-convex, it will
The average value of recess portion and convex portion is as measurement result.
Then, combustion residue 5.0cm is picked up along vertical direction with the speed of 2.0mm/s with finger, confirms out of shape be easy
Degree.Moreover, measuring the size of the combustion residue after picking up by using scale, the volume after combustion residue is picked up is calculated.So
Afterwards, the ratio of the volume of the combustion residue after picking up relative to the volume of the combustion residue before picking up is calculated.It needs to illustrate
It is that the finger strength in the case where picking up combustion residue with finger is not make the degree that combustion residue is substantially deformed by the power
Power.
Shape retention is evaluated according to benchmark below.
◎：Shape after burning is not out of shape, i.e., picked up using finger it is also not out of shape, residual volume be 95% or more.
○：Shape after burning is not out of shape, i.e., picked up using finger it is also not out of shape, residual volume be 80% less than
95%.
Δ：Although the shape after burning is not out of shape, occur during pick up out of shape, residual volume is less than 80%.
×：Shape after burning occurs out of shape.
4) expansion rate after burning
The solidification compound of embodiment 1 is set to cure by condition of cure 1, it is length 10mm × width 10mm to have obtained size
The solidfied material of × thickness 1.6mm.Then, which is placed in electric furnace (big and science Co. Ltd. system moulding number：FO300
Type) in, so that it has been burnt 20 minutes in air, under 400 DEG C of atmosphere.After burning, it is positioned in electric furnace and keeps 12 at 23 DEG C
Hour.Later, the volume of combustion residue is calculated.Volume at 23 DEG C of 50%RH by using scale to measure the ruler of combustion residue
Very little (length, width and thickness) and be calculated.It should be noted that in the case where combustion residue has concave-convex, by recess portion
Divide the average value with convex portion as measurement result.Then, it is shown below, passes through the volume (combustion of the solidfied material after burning
Burn residue volume) divided by burning before solidfied material volume, calculate burning after expansion rate (again).
The volume of solidfied material before volume/burning of the solidfied material after expansion rate (again)=burning after burning
In addition, the expansion rate after burning is evaluated according to benchmark below.
◎：Expansion rate after burning is 25 times or more.
○：Expansion rate after burning is 20 times less than 25 times.
Δ：Expansion rate after burning is 15 times less than 20 times.
×：Expansion rate after burning is less than 15 times.
5) resistance against compression
Using the solidification compound of embodiment 1, make its solidification by condition of cure 1, prepares length 12mm × width
The solidfied material of 12mm × thickness 4.5mm.Then, on the solidfied material, load is applied to the side of the area of 12mm × 12mm
Formula places the counterweight of 500g, and placed 30 seconds.In the state of placed counterweight, it confirmed the change of solidfied material using scale
Shape.Resistance against compression is evaluated according to benchmark below.
〇：The thickness of solidfied material does not change (0mm deformations).
Δ：The thickness deformation 0mm of solidfied material is less than 0.2mm.
×：The thickness deformation 0.2mm or more of solidfied material.
6) sticky
For solidfied material obtained from making the solidification compound of embodiment 1 cure by condition of cure 1, according to JIS
A1439 (5.19 inviscid experiment (tack-free test)) determines viscosity (in order to evaluate the viscosity of solidfied material without measuring
Time needed for solidification).Then, the surface for touching solidfied material with finger at 23 DEG C of 50%RH, confirms tacky.Sticky basis
Benchmark below is evaluated.
○：Surface is not tacky.
Δ：Surface is slightly tacky.
×：Surfaces of tacky.
(embodiment 2~9, comparative example 1~4)
Compared with Example 1 other than replacing with and coordinating substance shown in table 1, it is prepared for reality similarly to Example 1
Apply the solidification compound of example 2~9 and comparative example 1~4.Then, characteristic is had rated similarly to Example 1.By these results
It is shown in table 1.
If with reference to table 1, known to the solidification compound of embodiment all show and have both good viscosity, appropriate hard
Shape retention, the big expansion rate after burning, excellent resistance against compression and excellent viscosity after degree, excellent burning.It is another
Aspect, in a comparative example, then different from embodiment, there is no the examples for having both these characteristics completely.In addition, for example in comparative example
In 1, the expansion generated by burning is not observed and combustion residue is out of shape, and can not measure volume, in comparative example 2, after burning,
Combustion residue is defeated and dispersed one after another.
More than, embodiments of the present invention and embodiment are illustrated, but the embodiment of above-mentioned record and implementation
Example is not limited to the technical solution of claims.Again, it should be noted that：The feature illustrated in embodiment and embodiment owns
Combination is not necessarily necessary to the scheme for solving the problems, such as to invent, without departing from the technological thought of the present invention, so that it may with
Carry out various modifications.
Claims (11)
1. a kind of fireproof construction body of structure, has：
Structure；And
The solidfied material of solidification compound is set at least part on the surface of the structure,
The solidification compound has mobility at normal temperatures,
For the solidfied material,
It is 40 or more according to the JIS K6253-3 A type hardness tester meter hardness acquired,
In the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, the volume of the solidfied material after burning
The solidfied material for 20 times or more of the volume of the solidfied material before burning and after burning has shape retention.
2. the fireproof construction body of structure according to claim 1, wherein picked up with speed 2.0mm/s make it is described solid
In the case of the combustion residue that compound has been burnt after twenty minutes in air, under 400 DEG C of atmosphere, the burning after picking up is residual
The volume of slag is 80% or more relative to the volume of the combustion residue before picking up.
3. the fireproof construction body of structure according to claim 1 or 2, wherein
The solidification compound contains：
(A) in a molecule containing at least one bridging property silicon substrate (methyl) acrylic ester polymer and
(B) thermally expandable graphite.
4. the fireproof construction body of structure according to claim 3, wherein the solidification compound contain with it is described
(A) different (C), (A) are that (methyl) acrylic ester containing at least one bridging property silicon substrate is poly- in a molecule
Object is closed, (C) is the organic polymer for containing at least one bridging property silicon substrate in a molecule.
5. the fireproof construction body of structure according to claim 3 or 4, wherein (B) thermally expandable graphite contains phase
Mutual at least two different thermally expandable graphites of grain size and the grain size of the thermally expandable graphite of a side and the thermal expansion of another party
Property graphite grain size absolute value of the difference be 100 μm or more.
6. the fireproof construction body of structure according to any one of claims 1 to 5, wherein the solidification compound
At least containing either one in epoxy resin or phenolic resin.
7. a kind of solidification compound of fire resistance has mobility, for the solidfied material after solidification at normal temperatures before solidification
Speech,
It is 40 or more according to the JIS K6253-3 A type hardness tester meter hardness acquired,
In the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, the volume of the solidfied material after burning
The solidfied material for 20 times or more of the volume of the solidfied material before burning and after burning has shape retention.
8. the solidification compound of fire resistance according to claim 7, contains：
(A) in a molecule containing at least one bridging property silicon substrate (methyl) acrylic ester polymer and
(B) thermally expandable graphite.
9. the solidification compound of fire resistance according to claim 7 or 8 further contains different from (A)
(C), described (A) is (methyl) acrylic ester polymer for containing at least one bridging property silicon substrate in a molecule, described
(C) it is the organic polymer for containing at least one bridging property silicon substrate in a molecule.
10. a kind of refractory material has the solidfied material of solidification compound, before the solidification compound solidification at normal temperatures
With mobility,
For the solidfied material,
It is 40 or more according to the JIS K6253-3 A type hardness tester meter hardness acquired,
In the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, the volume of the solidfied material after burning
The solidfied material for 20 times or more of the volume of the solidfied material before burning and after burning has shape retention.
11. a kind of fireproof construction body forming method, has：
Solidification compound at normal temperatures with mobility is coated at least one of the surface of structure by painting process
Point；And
Curing process makes the solidification compound be solidified to form solidfied material,
For the solidfied material,
It is 40 or more according to the JIS K6253-3 A type hardness tester meter hardness acquired,
In the case where making it burn 20 minutes in air, under 400 DEG C of atmosphere, the volume of the solidfied material after burning
The solidfied material for 20 times or more of the volume of the solidfied material before burning and after burning has shape retention.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-043872 | 2016-03-07 | ||
| JP2016043872 | 2016-03-07 | ||
| PCT/JP2017/009086 WO2017154931A1 (en) | 2016-03-07 | 2017-03-07 | Fire prevention structure for structures, curable composition, refractory material, and method for forming fire prevention structures |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108778424A true CN108778424A (en) | 2018-11-09 |
| CN108778424B CN108778424B (en) | 2019-12-17 |
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| CN201780015555.5A Active CN108778424B (en) | 2016-03-07 | 2017-03-07 | Fireproof structure for structure, and fire-resistant curable composition |
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| Country | Link |
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| JP (1) | JP6825618B2 (en) |
| KR (1) | KR102407426B1 (en) |
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| KR102407426B1 (en) * | 2016-03-07 | 2022-06-10 | 세메다인 가부시키 가이샤 | Fire protection structure of structure, curable composition, fire resistant material, and method of forming fire protection structure |
| JP2019104817A (en) * | 2017-12-12 | 2019-06-27 | 積水化学工業株式会社 | Fire-resistant epoxy resin composition |
| WO2019146565A1 (en) * | 2018-01-25 | 2019-08-01 | セメダイン株式会社 | Formation method, and flame-resistant, single-component, ambient-temperature-and-humidity-curable reactive hot melt composition |
| JP7065682B2 (en) * | 2018-04-26 | 2022-05-12 | 積水化学工業株式会社 | Refractory materials and their manufacturing methods, fittings |
| JP7221733B2 (en) * | 2019-02-28 | 2023-02-14 | 積水化学工業株式会社 | refractory material |
| JP6697173B1 (en) * | 2019-07-12 | 2020-05-20 | 株式会社 静科 | Nonflammable sound absorbing panel |
| JP6914405B1 (en) * | 2020-07-31 | 2021-08-04 | デンカ株式会社 | Refractory material |
| JP7323677B1 (en) | 2022-05-26 | 2023-08-08 | デンカ株式会社 | Thermally expandable putty composition and joint material |
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| JP2006087819A (en) * | 2004-09-27 | 2006-04-06 | Denki Kagaku Kogyo Kk | Joint filling material and gasket for fire prevention |
| WO2014162718A1 (en) * | 2013-03-31 | 2014-10-09 | 積水化学工業株式会社 | Thermally expandable fire-resistant material and fireproof construction of resin sash using same |
| JP5779435B2 (en) * | 2011-07-15 | 2015-09-16 | 積水化学工業株式会社 | Fireproof compartment penetration structure |
| JP5855350B2 (en) * | 2010-04-23 | 2016-02-09 | 国立大学法人三重大学 | Curable composition having improved storage stability adhesion |
| WO2017154931A1 (en) * | 2016-03-07 | 2017-09-14 | セメダイン株式会社 | Fire prevention structure for structures, curable composition, refractory material, and method for forming fire prevention structures |
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2017
- 2017-03-07 KR KR1020187025709A patent/KR102407426B1/en active IP Right Grant
- 2017-03-07 WO PCT/JP2017/009086 patent/WO2017154931A1/en active Application Filing
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006087819A (en) * | 2004-09-27 | 2006-04-06 | Denki Kagaku Kogyo Kk | Joint filling material and gasket for fire prevention |
| JP5855350B2 (en) * | 2010-04-23 | 2016-02-09 | 国立大学法人三重大学 | Curable composition having improved storage stability adhesion |
| JP5779435B2 (en) * | 2011-07-15 | 2015-09-16 | 積水化学工業株式会社 | Fireproof compartment penetration structure |
| WO2014162718A1 (en) * | 2013-03-31 | 2014-10-09 | 積水化学工業株式会社 | Thermally expandable fire-resistant material and fireproof construction of resin sash using same |
| WO2017154931A1 (en) * | 2016-03-07 | 2017-09-14 | セメダイン株式会社 | Fire prevention structure for structures, curable composition, refractory material, and method for forming fire prevention structures |
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| KR102407426B1 (en) | 2022-06-10 |
| JP6825618B2 (en) | 2021-02-03 |
| CN108778424B (en) | 2019-12-17 |
| KR20180132624A (en) | 2018-12-12 |
| JPWO2017154931A1 (en) | 2019-01-31 |
| WO2017154931A1 (en) | 2017-09-14 |
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