CN1380368A - Expanding fire-proof paint - Google Patents
Expanding fire-proof paint Download PDFInfo
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- CN1380368A CN1380368A CN 02110297 CN02110297A CN1380368A CN 1380368 A CN1380368 A CN 1380368A CN 02110297 CN02110297 CN 02110297 CN 02110297 A CN02110297 A CN 02110297A CN 1380368 A CN1380368 A CN 1380368A
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Abstract
The expansive fire-resisting paint contains the components of acrylic resin, catalyst, carbon-forming agent, foaming agent, fire-resisting agent, reinforcing agent, pigment filling material, adjuvant and smoke inhibiting agent, and is characterized by that it utilizes the modification of acrylic resin, surface treatment of catalyst and addition of smoke inhibiting agent to raise comprehensive property of paint. When the paint film is heated and expanded, it can be formed into fire-resistant carbonized layer with three-D space structure, and can release fire-resisting gas to prevent flame from spreading. Said paint is suitable for steel structure, and material and electric cable, etc.
Description
Technical field
The present invention relates to frie retardant coating, particularly expanding fire-proof paint can be used as steel structure fire-proof paint, finishing fire retardant paint, cable fire-refractory coating.
Background technology
Frie retardant coating generally is divided into expanded polystyrene veneer and non-expansion type two classes from fire prevention mechanism.The non-expansion type frie retardant coating is that the flameproof effect that wants to reach good must be coated with very thickly by high-leveled and difficult combustion of himself or the uninflammability purpose that reaches fire-retardant fireproof, adds fire retardants such as halogen-containing in a large number, nitrogen, phosphorus, produces a large amount of toxic gases.The expanding fire-proof paint expanded by heating of filming exactly forms cellular charring layer, flame heat regulating is isolated and reduce or slow down transmission ground, coating decomposites non-flammable gas when high temperature simultaneously, isolated and diluted air, thereby a series of physics that take place in when fire prevention of coating and chemical reaction have absorbed a large amount of heats and play fire-retardant and delay the flame expansion, spread in addition, and the time of fire extinguishing is provided for people.Behind the expanding fire-proof paint expanded by heating, the porous foam defence layer that produces, than former thick coating tens even hundred times, and the thermal conductivity ratio end of the back foam layer that expands low at least order of magnitude of coating before expanding, be coated with to such an extent that very thinly just can reach good flameproof effect.U.S. Pat .6054513 has introduced a kind of frie retardant coating, produces the carbonization sealing coat when meeting fire, excellent storage stability under hygrothermal environment, but do not relate to the problem of smoke treated.
Summary of the invention
The expanding fire-proof paint that the purpose of this invention is to provide a kind of high comprehensive performance.Particularly use the catalyzer of modification and add smog inhibitor and strengthening agent makes coating be suitable for the application of some special purpose.Expanding fire-proof paint of the present invention is made up of following ingredients:
Weight percentages
Resin 10～30
Catalyzer 10～30
Char-forming agent 5～15
Whipping agent 5～15
Fire retardant 3～10
Strengthening agent 5～10
Color stuffing 5～15
Auxiliary agent 1～8
Solvent 20-30
Smog inhibitor is an amount of
Resin in the above-mentioned prescription has great effect to the performance of expanding fire-proof paint, and it and other component compatibility had both guaranteed that coating had various use propertieies under normal operation, can have excellent expanded foamed effect again under flame calcination or high temperature action.The present invention is main resin binder with acrylic resin, because the monomer of synthesizing propylene acid resin differs bigger, thereby its decomposition temperature, melt temperature differ greatly, and the sticking power of charring layer under final charring layer compactness extent, intensity, carbide output and the high temperature to ground is also had a significant impact.Acrylic resin of the present invention has also been considered the content of aromatic nucleus and having or not of ignition-proof element in the molecular resin except the molecular weight of considering resin, wetting ability, solvability, package stability.The acrylic resin that preferred molecular weight of the present invention is big, wetting ability is low, solvability is good, the amount of being fuming is few, contain aromatic nucleus and contain ignition-proof element is made base-material.
Also can add aminoresin, Resins, epoxy, resol, HCPE, chlorinated rubber, chlorinated polyether resin etc. in the prescription acrylic resin is carried out modification.In these resins resinamines and chlorine-containing resins particularly highly-chlorinated polyethylene, chlorinated rubber, chlorinated polyether resin the over-all properties of coating is greatly improved, Resins, epoxy and resol are then significantly helpful to the ultimate production of the compactness of charring layer and carbide.
Catalyzer is one of crucial composition of expanding fire-proof paint, it promotes and improves the thermal decomposition process of coating, the amount of the flammable tar that produces when minimizing or the thermolysis of prevention organism, aldehyde, ketone etc. promotes the generation of non-flammable gases to reach the formation of at high temperature stable three-dimensional structure charring layer.As long as can be under proper temperature (it is generally acknowledged 150～250 ℃), the material that the composition that decomposites can dewater to the material of hydroxyl all can be as catalyzer.Optionally material has: primary ammonium phosphate, urea phosphate, ammonium polyphosphate, ammonium polyphosphate potassium, Potassium tripolyphosphate, melamine phosphate, the two trimeric cyanamides of phosphoric acid, melamine pyrophosphate, organophosphate, borate, ester and derivative, sulphonate and derivative etc.The preferred ammonium polyphosphate of the present invention, melamine phosphate or its mixture as catalyst.
Its solubleness was 62% to general commercially available ammonium polyphosphate (polymerization degree is many 20～30) when its solubleness was 8.2%, 60 ℃ in the time of 25 ℃, contained the weather resistance of ammonium polyphosphate frie retardant coating under wet, thermal environment in order to improve, and must reduce the water-soluble of ammonium polyphosphate.The present invention preferably carries out surface treatment to ammonium polyphosphate, with exotic materials the surface of ammonium polyphosphate is wrapped up, the available material has: silane coupling agent, titanate coupling agent, methyl-silicone oil, dimethyl silicone oil, containing hydrogen silicone oil, Zinic stearas, aminoresin, Resins, epoxy, resol etc.Surface treated ammonium polyphosphate is compared with the ammonium polyphosphate of not handling: water-soluble obvious reduction, obviously improve with the consistency of resin, dispersiveness obviously improves.
The present invention most preferably adopts silicone oil series that ammonium polyphosphate is carried out making catalyzer after the surface treatment.
Char-forming agent is the basic substance that coating at high temperature forms the foam carburization zone of nonflammable three-D space structure, and the foam carburization zone is played skeleton function.Char-forming agent will be complementary with catalyzer on decomposition temperature, the validity of char-forming agent depends on the content of hydroxyl and carbon atom in the molecule, the quantity of hydroxyl is big, the dehydrated speed of char-forming agent is very fast relatively, but the wetting ability height of char-forming agent itself, so and the quantity of non-hydroxyl is high more good more, carbon content height, molecule are big, and be favourable to the intensity and the compactness of the charring layer of final formation.The kind of char-forming agent has a lot, as starch, Mierocrystalline cellulose and derivative, sucrose, sorbyl alcohol, tetramethylolmethane and derivative, Resins, epoxy, resol etc.It is main char-forming agent that the present invention adopts tetramethylolmethane and the derivative that wetting ability is low, thermostability is high.As tetramethylolmethane, Dipentaerythritol etc.
Whipping agent discharges non-flammable gases-----hydrogen halide, ammonia, nitrogen and compound thereof, steam in certain temperature.Whipping agent commonly used has: the phosphoric acid salt of Dyhard RU 100, trimeric cyanamide, clorafin, urea, trimeric cyanamide and borate etc.In order to prolong foamed time, make the height of charring layer better, generally all adopt a plurality of whipping agents to share, it is whipping agent that system of the present invention adopts trimeric cyanamide and clorafin, and also can adopt melamine salt/ester (as melamine phosphate) and clorafin is whipping agent.
Because acrylic resin itself is a combustible matl, about 180 ℃, just begin to decompose, the temperature that catalyzer that the present invention is selected and whipping agent play a role is more than 200 ℃.Therefore, must add fire retardant in addition and below 200 ℃ coating carried out the fire-retardant of initial stage.In order to reduce the consumption of fire retardant material in whole formulation for coating material, should select the kind of one-object-many-purposes as far as possible.Fire retardant commonly used has: clorafin, phosphoric acid ester, phosphorous acid ester, bromide, resin that chlorinity is high etc., preferred fire retardant is a clorafin, because it can not only bring into play tangible fire retardation to acrylic resin, also have the effect of whipping agent concurrently, and helpful to neat coal amout.
For expanding fire-proof paint, owing to added a large amount of fire-proof additives, so color stuffing should not be added, surpassing 10% (weight percentage) promptly influences its expansion effect greatly.When selecting color stuffing, select as far as possible tinting strength height, hot reflection coefficient height, thermal conductivity low, can play mineral dye, the filler of skeleton function to charring layer, pigment dyestuff adds less or does not add as far as possible.Generally make tinting pigment with titanium white, zinc oxide etc.
The inventor proves that through test of many times foaming height also not exclusively is directly proportional with fire endurance, if expanding layer is loose, high more its fire endurance that foams is poor more, and the intensity that therefore increases expanding layer is one of key that improves the frie retardant coating fire endurance.The inventor finds that by a large amount of tests some powders and fibrous material can be used as strengthening agent, and the preferred titanium white of the present invention, aluminum oxide, wollastonite, slag wool, rock wool, glass wool and various fire-resistant cotton make strengthening agent.
Toxic gas such as carbon monoxide and hydrogen halide is murderous first reason in the fire.In order to reduce the generating capacity of toxic smog, the present invention has also added smog inhibitor specially, and smog inhibitor commonly used has: aluminium hydroxide, magnesium hydroxide, aluminum oxide, lime carbonate, zinc borate, zinc molybdate etc.For the purpose of the present invention, preferably zinc borate, aluminum oxide.
Auxiliary agent of the present invention comprises an amount of dispersion agent and antisettling agent.Dispersion agent and antisettling agent have improved the homogeneity of execution of coating performance and package stability and foaming.
Solvent of the present invention should select toxicity low as far as possible, and human body is stimulated the little mixed solvent with suitable evaporation rate.The propylene glycol ethers that preferred security is higher, smell is less is a main solvent, is thinner with aliphatic hydrocarbons such as 200# gasoline.
Expanding fire-proof paint of the present invention prepares with this area method in common, for example use following method: it is standby to have dissolved resin earlier, weigh up each component by formula ratio then, add in the material-compound tank, stir, going up three-roll grinder then, to be ground to fineness qualified, is uniformly dispersed with homogenizer, filters and packages discharging.
Expanding fire-proof paint of the present invention has that fire insulation performance is good, bonding force is good, intensity is high, can stand high low temperature round-robin influence, the water tolerance of coating, acid resistance, salt tolerant corrodibility are good, difficult drop-off, shelf-stable, good decorative property, characteristics such as easy construction, non smoke or few smog produce during burning.Be particularly suitable for doing super-thin steel structure fire-proof paint, finishing fire retardant paint and cable fire-refractory coating.
Specific embodiment
Following examples are used for further specifying the present invention.Umber used in the example is parts by weight.The title of the raw material among the embodiment and trade names and manufacturer are as follows:
HHCPE: highly-chlorinated polyethylene, Zhejiang Yue Loong chemical industry company limited;
Acrylic resin: Shenyang three ring fine chemistry industry company acrylic resins;
MP: melamine phosphate, Holland; DPE: Switzerland, Dipentaerythritol;
Chlorinated polyether resin: German BASF AG product;
Other is the commercial goods.
Catalyst modification embodiment
Embodiment 1
Get 7 parts of methyl-silicone oils, 100 parts of sherwood oils, 80 parts of ammonium polyphosphates kept 1～1.5 hour down for 60～100 ℃ at reflux temperature, steaming petroleum ether, drying is about 1 hour under 110 ℃, gets the free-running property powder-product.In the time of 25 ℃ its solubleness when not handling 1/20, solubleness greatly reduces.
Embodiment 2
Get 7.5 parts of dimethyl silicone oils, 100 parts of sherwood oils, 80 parts of ammonium polyphosphates kept 1～1.5 hour down 60～100 ℃ of reflux temperatures, steaming petroleum ether, about 1 hour of 110 ℃ of dryings, the free-running property powder-product.Its solubleness is 1/20 before not handling in the time of 25 ℃.
Embodiment 3 to 12 is formulation for coating material examples.
Embodiment 3
12 parts of acrylic resins, 35 parts of common ammonium polyphosphates, 10 parts of trimeric cyanamides, 10 parts of tetramethylolmethanes, 8 parts of titanium dioxides, 7 parts of clorafins, solvent and thinner are an amount of.The preparation method: earlier acrylic resin is used solvent and thinner dissolving and above-mentioned other component to add together in the material-compound tank, stirred, it is qualified to be ground to fineness with three-roll grinder, is uniformly dispersed with homogenizer, gets frie retardant coating.Adopt spread coating to be applied on the ground.
Embodiment 4 to 12 preparation methods and constructional method only are raw materials used differences with embodiment 3.
Embodiment 4
10 parts of acrylic resins, 2 parts of chlorinated polyether resins, 28 parts of the catalyzer of the modification of embodiment 2, MP15 part, 8 parts of Dipentaerythritols, 5 parts of titanium dioxides, 3 parts of clorafins, 2 parts of zinc borates, 2 parts of wollastonites
Embodiment 5
10 parts of acrylic resins, 2 parts of HHCPE, 2 parts in glass powder, 2 parts in aluminum oxide, 4 parts of titanium dioxides, 28 parts of the catalyzer of the modification of embodiment 2, MP15 part, 8 parts of Dipentaerythritols, 3 parts of clorafins
Embodiment 6
10 parts of acrylic resins, 2 parts of chlorinated rubbers, 2 parts of slag wools, 2 parts in aluminum oxide, 4 parts of titanium dioxides, 28 parts of the catalyzer of the modification of embodiment 2, MP18 part, 6 parts of Dipentaerythritols, 3 parts of clorafins
Embodiment 7
10 parts of acrylic resins, 2 parts in aminoresin, 2 parts of wollastonites, 2 parts in aluminum oxide, 4 parts of titanium dioxides, 30 parts of the catalyzer of the modification of embodiment 2, MP16 part, 6 parts of Dipentaerythritols, 5 parts of clorafins
Embodiment 8
14 parts of acrylic resins, 2 parts of wollastonites, 2 parts in aluminum oxide, 4 parts of titanium dioxides, 28 parts of the catalyzer of the modification of embodiment 2, MP20 part, 6 parts of Dipentaerythritols, 5 parts of clorafins, 2 parts of glass wools
Embodiment 9
10 parts of acrylic resins, 2 parts of Resins, epoxy, 2 parts of wollastonites, 2 parts in aluminum oxide, 4 parts of titanium dioxides, 30 parts of the catalyzer of the modification of embodiment 1, MP18 part, 5 parts of Dipentaerythritols, 7 parts of clorafins
Embodiment 10
10 parts of acrylic resins, 2 parts in resol, 2 parts of wollastonites, 2 parts in aluminum oxide, 4 parts of titanium dioxides, 30 parts of the catalyzer of the modification of embodiment 1, MP18 part, 5 parts of Dipentaerythritols, 7 parts of clorafins
Embodiment 11
14 parts of acrylic resins, 7 parts of clorafins, 35 parts of the catalyzer of the modification of embodiment 1, trimeric cyanamide 8 minutes, 8 parts of tetramethylolmethanes, 5 parts of titanium dioxides, 1 part of stibium trioxide, 1.5 parts of wollastonites, 1 part of zinc molybdate, 1 part of rock wool
Embodiment 12
14 parts of acrylic resins, 27 parts of the catalyzer of the modification of embodiment 1, MP17 part, 10 parts of tetramethylolmethanes, 5 parts of titanium dioxides, 1 part of organobentonite, 5 parts of clorafins, fire-resistant cotton 1 part, 2 parts in aluminum oxide
The resulting frie retardant coating performance index of above embodiment:
| Reference standard | Technical indicator | The result | |
| Condition in container | ??GB/T6753.3-86 | There is not caking, viscous fluid | There is not caking, viscous fluid |
| Surface drying time | ??GB/T1728-89 | Be not more than 3 hours | 1 hour |
| Water tolerance | ??GB/T1733-93 | 24 hours, no wrinkling, do not have and to peel off | Above 120 hours |
| Oil-proofness | ??GA181-98?5.7 | Soaked 7 days, no wrinkling, do not have and to peel off | Soaked 30 days, no wrinkling, nothing is peeled off |
| Cold-resistant thermal cycling | ??GA181-98?5.10 | 15 the circulation, no wrinkling, the nothing peel off | 30 circulations, no wrinkling, nothing is peeled off |
| Sticking power | ??GB/T1720-89 | Be not more than 3 grades | 2 grades～1 grade |
| Shock-resistance | ??GB/T1732-93 | Be not less than 20kg.cm | ?30～50kg.cm |
| Snappiness | ??GB/T1731-93 | Be not more than 3mm | ?2mm |
The contrast of fire resistance laboratory: filming of the foregoing description 3 to embodiment 12, toast apart from coating 5cm with alcohol blast burner flame, coat-thickness 1mm is subjected to fire time 5min.The result: more than film and all can form the charring layer of comparison even compact, 9 embodiment of embodiment 3 wherein and other compare, charring layer intensity is relatively poor, occurs the phenomenon that charring layer is burnt down the earliest, the smog of generation is more.This explanation is to the acrylic resin modification, catalyst surface handled and added smog inhibitor the over-all properties of coating is improved a lot.
When coating is used for wood substrate as finishing paint,, carry out the fire resistance test with reference to GB12442.1-95, when above paint formulation is 0.5mm when build, behind spirit lamp baking 30min, coating expansion height 1-2cm, carbonization does not take place or slight carbonization takes place in wood substrate.
When coating is used for the steel construction ground, carry out the fire resistance test according to GB14907-94, substantially exceed the index that requires in the GB.
When as cable fire-refractory coating, carry out the fire resistance test according to GA181-1998, reach category-A frie retardant coating index.
Claims (10)
1. an expanding fire-proof paint is characterized in that, comprises following ingredients:
Weight percentages
Resin 10～30
Catalyzer 10～30
Char-forming agent 5～15
Whipping agent 5～15
Fire retardant 3～10
Strengthening agent 5～10
Color stuffing 5～15
Auxiliary agent 1～8
Solvent 20～30
Smog inhibitor is an amount of
2. according to the expanding fire-proof paint of claim 1, it is characterized in that, described resin preferred acrylic resins, and add following one or more materials acrylic resin is carried out modification: aminoresin, Resins, epoxy, resol, HCPE, chlorinated rubber, chlorinated polyether resin.
3. according to the expanding fire-proof paint of claim 1, it is characterized in that described catalyzer preferably phosphoric acid ammonium dihydrogen, urea phosphate, ammonium polyphosphate, ammonium polyphosphate potassium, Potassium tripolyphosphate, melamine phosphate, the two trimeric cyanamides of phosphoric acid, melamine pyrophosphate, organophosphate, borate, ester and derivative, sulphonate and derivative.
4. according to the expanding fire-proof paint of claim 3, it is characterized in that, can carry out surface treatment to described catalyzer with one or more of following material: silane coupling agent, titanate coupling agent, methyl-silicone oil, dimethyl silicone oil, containing hydrogen silicone oil, Zinic stearas, aminoresin, Resins, epoxy, resol.
5. according to the expanding fire-proof paint of claim 4, it is characterized in that the present invention preferably adopts silicone oil series that ammonium polyphosphate is carried out making catalyzer after the surface treatment.
6. according to the expanding fire-proof paint of claim 1, it is characterized in that described char-forming agent is selected from starch, Mierocrystalline cellulose and derivative, sucrose, sorbyl alcohol, tetramethylolmethane and derivative, Resins, epoxy, resol.
7. according to the expanding fire-proof paint of claim 1, it is characterized in that described whipping agent is the material that discharges non-flammable gases-----hydrogen halide, ammonia, nitrogen and compound thereof, steam in certain temperature.
8. according to the expanding fire-proof paint of claim 7, it is characterized in that described whipping agent is selected from: the phosphoric acid salt of Dyhard RU 100, trimeric cyanamide, clorafin, urea, trimeric cyanamide and borate etc.
9. according to the expanding fire-proof paint of claim 1, it is characterized in that the preferred titanium white of described strengthening agent, aluminum oxide, wollastonite, asbestos, slag wool, rock wool, glass wool and various fire-resistant cotton.
10. according to the expanding fire-proof paint of claim 1, it is characterized in that the preferred aluminium hydroxide of described smog inhibitor, magnesium hydroxide, aluminum oxide, lime carbonate, zinc borate, zinc molybdate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB02110297XA CN1164701C (en) | 2002-04-11 | 2002-04-11 | Expanding fire-proof paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02110297XA CN1164701C (en) | 2002-04-11 | 2002-04-11 | Expanding fire-proof paint |
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| CN1380368A true CN1380368A (en) | 2002-11-20 |
| CN1164701C CN1164701C (en) | 2004-09-01 |
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| CNB02110297XA Expired - Fee Related CN1164701C (en) | 2002-04-11 | 2002-04-11 | Expanding fire-proof paint |
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| CN114874652A (en) * | 2022-06-18 | 2022-08-09 | 马海群 | Additive for fireproof coating, fireproof coating and preparation method of fireproof coating |
| CN114874652B (en) * | 2022-06-18 | 2023-09-01 | 马海群 | Additive for fireproof coating, fireproof coating and preparation method of fireproof coating |
| CN116836574A (en) * | 2023-07-24 | 2023-10-03 | 福建省金通建设集团有限公司 | Environment-friendly alkali slag or nickel slag tunnel fireproof paint and preparation method thereof |
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