CN105694665A - Flame-retardant coiled material and preparation method thereof - Google Patents
Flame-retardant coiled material and preparation method thereof Download PDFInfo
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- CN105694665A CN105694665A CN201610060426.5A CN201610060426A CN105694665A CN 105694665 A CN105694665 A CN 105694665A CN 201610060426 A CN201610060426 A CN 201610060426A CN 105694665 A CN105694665 A CN 105694665A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
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- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a flame-retardant coiled material and a preparation method thereof. The flame-retardant coiled material is a laminated structure which is formed by bonding a flame-retardant surface layer and a chopped fiber layer by a flame-retardant paint and carrying out curing. The flame-retardant paint is composed of a component A and a component B in a weight ratio of 10:(2-5). The component A comprises the following ingredients in percentage by mass: an epoxy resin, a flame-retardant resin, a flame-retardant diluter, a toughener, a dispersing agent, a defoaming agent, a leveling agent, a flame-retardant additive, a color paste and the balance of inorganic filler. The component B comprises a curing agent and the balance of curing accelerator. The flame-retardant additive comprises at least one of antimony trioxide, aluminum hydroxide, magnesium hydroxide, melamine cyanurate, chlorinated paraffin, tri(2-chloropropyl) phosphate and dimethyl methylphosphate. The epoxy resin, flame-retardant resin, flame-retardant diluter and flame-retardant additive are utilized to form the compound system, thereby fully displaying the synergistic effects of the components, and greatly enhancing the flame retardancy of the flame-retardant paint.
Description
Technical field
The present invention relates to high-molecular coating and coiled material technical field, particularly relate to a kind of fire-retardant coiled material and preparation method thereof。
Background technology
Along with the continuous progress of science and technology, the anti-flammability of material increasingly comes into one's own, and the flame-retardant coverage of existing ground, metope, desktop etc. is mainly site operation anti-flaming dope and the fire-retardant coiled material of thermoplastic。
Wherein, although anti-flaming dope excellent fireproof performance, but adhesive force and globality are poor, easily occur coming off, the phenomenon such as peeling, the place that frequency is higher is used for ground, desktop workbench etc., its life-span is shorter, poor durability, and the anti-flaming dope of site operation has the environmental pollution problems such as solvent volatilization, abnormal smells from the patient be big。
Thermoplastic flame-proof coiled material, although overall performance is good, also has certain anti-flaming function, can stop the sustained combustion of flame；But, owing to this type of coiled material is thermoplastic, its characteristic determines it once be heated and deforming immediately, causes being continuing with, difference attractive in appearance, as: cigarette end falls on thermoplastic, can cause serious yellowing, wrinkling, deformation, local also result in bulge。
Research currently, with respect to anti-flaming dope and fire-retardant coiled material is reported more, for instance:
The application for a patent for invention document that application publication number is CN103571304A discloses a kind of flame retardant epoxy floor coatings and preparation method thereof, this coating is made up of according to the ratio mixing match of weight ratio 100:20～100:30 host and firming agent, wherein, described host is made up of the raw material of following weight: epoxy resin 40～70 parts, diluent 2～10 parts, fire retardant 30～50 parts, dispersant 0.01～2 part, defoamer 0.01～2 part, levelling agent 0.01～2 part and toner 1～5 part；Described firming agent is made up of the raw material of following weight: polyetheramine 30～90 parts, modified amine 10～70 parts and accelerator 1～10 part。In described host, various components are as follows: described epoxy resin is selected from E-51, E-44, one or more in E-20, described diluent is selected from AGE, BGE, benzyl alcohol, dimethylbenzene, isobutanol, one or more in butanone, described fire retardant is selected from aluminium hydroxide, magnesium hydroxide, antimony oxide, tetrabromobisphenol A, APP, MAP, Diammonium phosphate (DAP), ammonium chloride, boric acid, TCPP, TDCPP, IPPP, DMMP, triphenyl phosphate, one or more in TDE, described dispersant is selected from polyether modified siloxane, BYK-111, BYK-110, one or more in polydimethylsiloxane, described defoamer is selected from polyether modified siloxane, dimethyl siloxane, BYK-A530, one or more in BYK-525, described levelling agent is selected from polyether modified siloxane, polydimethylsiloxane, BYK-315, one or more in BYK-320, described toner is selected from corresponding inorganic toner or organic toner。This flame retardant epoxy floor coatings can reach UL94-V0 fire-protection rating, easy construction, it is easy to operation, low volatilization or non-volatile。
The application for a patent for invention document that application publication number is CN103881552A discloses a kind of highly effective flame-retardant type color waterproof polyurethane paint, it is made up of host A group and firming agent B group two parts, host A group includes the film forming major ingredient filled the post of by polymer polyatomic alcohol, include liquid flame retardant, nanometer powder fire retardant, cross-linking agent, plasticizer, curing accelerator, defoamer, the auxiliary agent of UV absorbent, with include pigment and filled the post of the powder body adjuvant of inserts by mica powder and/or blanc fixe, described firming agent B group includes polyether polyol, plasticizer, liquid flame retardant and isocyanates。The film gel layer being applied on building surface to produce this coating has reliable waterproof and permanent in function, and also has and meet the feature that naked light is nonflammable, can meet the higher waterproof of building, fire-protection rating requirement, have very strong practicality。
The application for a patent for invention document that application publication number is CN104631765A discloses a kind of flame retardant type coiled material floor, this coiled material floor includes PVC wearing layer, PVC enhancement layer, fabric reinforcement and foamed damping layer from top to bottom successively, wherein, being added with fire retardant at PVC wearing layer, PVC wearing layer includes dioctyl phthalate, PVC paste resin 440, stone powder filler, barium zinc stabilizer, fire retardant stibium oxide。This coiled material floor can produce certain flame retardant effect when indoor laying uses。
Summary of the invention
The invention provides a kind of fire-retardant coiled material and preparation method thereof, the fire resistance of this fire-retardant coiled material is high, has efficient fire resistance, flame retardant rating reaches UL94-V0, reaches the B1 level of GB GB/T8624, and oxygen index (OI) is more than 36, have and namely put out from fire, drip without melt, the feature that smoke toxicity is low。
A kind of fire-retardant coiled material, for layer structure, it is characterised in that be made up of fire retardant surface layers and chopped fibers, both form through the bonding solidification of anti-flaming dope；
Described anti-flaming dope, component A and B component by weight ratio is 10:2～5 form；
Wherein, it is calculated in mass percent, consisting of of component A:
Consisting of of B component:
Firming agent 90～97%；
All the other are curing accelerator；
Described flame-retardant additive is at least one in antimony oxide, aluminium hydroxide, magnesium hydroxide, melamine cyanurate, chlorinated paraffin, tricresyl phosphate (2-chloropropyl) ester, methyl-phosphoric acid dimethyl ester。
It is further preferred that described anti-flaming dope, component A and B component by weight ratio is 10:2～5 form；
Wherein, it is calculated in mass percent, consisting of of component A:
Consisting of of B component:
Firming agent 91～97%；
All the other are curing accelerator；
Described flame-retardant additive is at least one in antimony oxide, aluminium hydroxide, magnesium hydroxide, melamine cyanurate, chlorinated paraffin, tricresyl phosphate (2 chloropropyl) ester, methyl-phosphoric acid dimethyl ester。
Find flame-retarded resin, between fire-retardant diluent and flame-retardant additive, there is mutual cooperative effect through test, the flame-retarded resin of reasonable volume and fire-retardant diluent, it is possible to coordinating flame-retardant additive further, the flame retardant effect making anti-flaming dope is more excellent；Meanwhile, when flame retardant effect is identical, flame-retarded resin, fire-retardant diluent Rational Application the consumption of flame-retardant additive can be greatly lowered, economize in raw materials cost。
As preferably, described epoxy resin is liquid bisphenol A epoxy resin or liquid bisphenol F type epoxy resin, and epoxide equivalent is 150～250g/eq。Aforesaid liquid epoxy resin is without organic solvent；After paint solidification, the hardness of coating and adhesive force are all higher。
As preferably, described flame-retarded resin is at least one in brominated epoxy resin, bisphenol A-type novolac epoxy resin。
It is preferred that, the epoxide equivalent of described brominated epoxy resin is 350～480g/eq, and softening point is 50～95 DEG C, and bromine content is 40～55%, this brominated epoxy resin have excellence from anti-flammability, excellent caking property, thermostability and ageing resistance。
It is preferred that, average >=3 of the epoxide group quantity that described bisphenol A-type novolac epoxy resin contains, epoxide number is 0.4～0.65eq/100g；This bisphenol A-type novolac epoxy resin has temperature tolerance, thermostability, good flame resistance, and activity is big, and crosslink density is big, close structure, mechanical strength high。
As preferably, described fire-retardant diluent is at least one in dibromo cresylglycidylether, dibromo phenyl glycidyl ether, this type of fire-retardant Diluent Viscosity is low, dilution capacity strong, and has preferably from anti-flammability, it is possible to produce cooperative flame retardant effect with flame-retardant additive。
Above-mentioned flame-retarded resin is the high-temperature-resistant epoxy resin containing bromo element, and fire-retardant diluent contains bromo element too；If burning occurs for fire-retardant coiled material containing above-mentioned flame-retarded resin and fire-retardant diluent, the hydrogen bromide of vapor phase can be generated, and the generation of free radical when hydrogen bromide can stop flame combustion, thus suppressing flame, reach fire-retardant effect。Inorganic compound in above-mentioned flame-retardant additive is the material that fusing point, boiling point are all higher, it is difficult to when burning gasify, and it is compounded with the flame-retarded resin of bromo element and fire-retardant diluent makes it produce the bromide that fusing point is bigger compared with low activity in combustion reaction process, in ignition temperature gasified, absorbing and cooling temperature, promotion carbonization, thus effectively stoping spreading of burning。It addition, the high molecular weight flame retardant in above-mentioned flame-retardant additive inorganic-containing compound, phosphorus-nitrogen collaboration system, muriatic compound mixture, the amount of smoke produced when burning can be greatly lowered, the drop effectively generated during containment burning and the drippage preventing charred ashes。
The combination of multiple flame-retardant additive can improve the fire resistance of coating, according to suitable consumption proportion, carries out the combination of multiple flame-retardant additive, it is possible to allows the fire resistance of coating perform to optimum。
As preferably, being calculated in mass percent, described flame-retardant additive includes following components: antimony oxide 50～70%；Chlorinated paraffin 20～30%；All the other are at least one in aluminium hydroxide, magnesium hydroxide, melamine cyanurate, tricresyl phosphate (2 chloropropyl) ester, methyl-phosphoric acid dimethyl ester。
As preferably, being calculated in mass percent, described flame-retardant additive includes following components: aluminium hydroxide 30～50%；Methyl-phosphoric acid dimethyl ester 10～30%；Melamine cyanurate 10～20%；All the other are at least one of antimony oxide, magnesium hydroxide, tricresyl phosphate (2 chloropropyl) ester, chlorinated paraffin。
It is further preferred that described flame-retardant additive also comprises the silane coupler of 1～2%。
Specifically, the preparation method of described flame-retardant additive includes: after described component being mixed, it is thus achieved that mixture；In mixture, add silane coupler again, after mixing, mixing obtain described flame-retardant additive。
In flame-retardant additive, add the silane coupler of certain consumption, flame retardant effect can not only be increased, additionally it is possible to improve the intensity of flame retardant epoxy system。
Further, the particle diameter of described flame-retardant additive is 5～25 μm。
The preparation method that present invention also offers described anti-flaming dope, including:
(1) epoxy resin, flame-retarded resin, fire-retardant diluent are proportionally heated mixing, after cooling, add toughener, wetting dispersing agent, defoamer, levelling agent, flame-retardant additive, mill base and inorganic filler, after stirring, filter, obtain component A；
(2), after firming agent and curing accelerator being mixed, B component is obtained；
(3), after component A and B component being mixed in proportion, described anti-flaming dope is obtained。
As preferably, in step (1), the temperature of described heating is 80～100 DEG C, and the rotating speed of stirring is 50～80 revs/min, and the time of stirring is 20～40 minutes。
As preferably, described chopped fibers is made up of the glass chopped silk of middle alkali or alkali-free。Adopt glass chopped silk as strengthening skeleton, not only increase the fire resistance of coiled material, also substantially increase the mechanical property of coiled material。
As preferably, the length of described glass chopped silk is 3～80mm。
Present invention also offers a kind of method preparing described fire-retardant coiled material, including:
(1) described anti-flaming dope is coated on mould release membrance, after solidification, forms fire retardant surface layers；
(2) on described fire retardant surface layers be coated with anti-flaming dope, then on anti-flaming dope the glass chopped silk of spreading, be then covered by mould release membrance, after solidification, formed chopped fibers；
(3) cooling, trimming rolling, obtain described fire-retardant coiled material。
As preferably, in step (1), the temperature of described solidification is 70～80 DEG C, and the time of solidification is 20～35 minutes。
As preferably, in step (2), the temperature of described solidification is 70～80 DEG C, and the time of solidification is 30～45 minutes。
Compared with prior art, the method have the advantages that
(1) present invention adopts epoxy resin, flame-retarded resin, fire-retardant diluent and flame-retardant additive to form compound system, gives full play to the cooperative effect between component so that the anti-flammability of anti-flaming dope increases substantially；
(2) adopt the fire-retardant coiled material not only fire resistance that anti-flaming dope of the present invention prepares good, and mechanical property such as surface pencil hardness, pliability etc. are also higher；
(3) preparation of the fire-retardant coiled material of the present invention adopts production line balance, both ensure that stablizing of material property, and the environmental nonpollution to construction and installation coiled material, has no adverse effects again。
Detailed description of the invention
Below in conjunction with being embodied as case, the present invention will be further described。
Material source involved in the following example is: epoxy resin 128, epoxy resin 170 (South Asia, Kunshan)；Bisphenol A-type novolac epoxy resin F-51 (Jiangsu three wood Chemical Co., Ltd.)；Brominated epoxy resin KM400 (Kaimei Chemical Science and Technology (Nantong) Co., Ltd.)；Dibromo cresylglycidylether, dibromo phenyl glycidyl ether (the happy Industrial Co., Ltd. of Shanghai Jin Jin)；Toughener ZR-05 (Shenzhen Fei Shengda new material company limited)；Wetting dispersing agent BYK181, defoamer BYK550, levelling agent KH354 (Bi Ke auxiliary agent company limited)；Mill base (Trade Co., Ltd. of Shanghai Zhengan County)；Glass chopped silk (Nanjing Xing Xing fiberglass products company limited)；Antimony oxide, aluminium hydroxide, magnesium hydroxide (Shanghai Xu Fan fire proofing company limited)；Melamine cyanurate, chlorinated paraffin, tricresyl phosphate (2 chloropropyl) ester, methyl-phosphoric acid dimethyl ester (being famous in Tian Zhu Science and Technology Ltd.)；Polyamide 200 firming agent, polyetheramine Y33 firming agent, curing accelerator K54 (Shanghai Yu Fan Chemical Industry Science Co., Ltd)。
Embodiment 1
One, the preparation of anti-flaming dope
(1) preparation of component A: by 128,10 parts of bromine contents of epoxy resin that 50 parts of epoxide equivalents are 185g/eq be 48%, softening point be 68 DEG C, epoxide equivalent be the brominated epoxy resin KM400 of 390g/eq；5 parts of fire-retardant diluent dibromo cresylglycidylethers are placed in the reactor of temperature 80 DEG C, stir 30 minutes under the revolution of 70 revs/min, it is cooled below 40 DEG C, 4 parts of toughener ZR-05,0.5 part of dispersant B YK181,0.3 part of defoamer BYK550 are added in reactor, 0.2 part of levelling agent BYK354,25 parts of flame-retardant additives, 3 parts of mill bases, 2 parts of inorganic filler glass powder；After stirring, it is filtrated to get component A；
Wherein, consisting of of flame-retardant additive: 13.7 parts of antimony oxides, 7.5 parts of chlorinated paraffins, 3.5 parts of aluminium hydroxide, 0.3 part of methyl-phosphoric acid dimethyl ester；The particle diameter of flame-retardant additive is 20 μm；
The preparation method of flame-retardant additive is: after said components being mixed, it is thus achieved that mixture；With the quality of mixture for benchmark, then in mixture, add 1% silane coupler KH560, after mixing, mixing obtain described flame-retardant additive。
(2) preparation of B component: by 91 parts of polyamide 200 firming agent, 9 parts of curing accelerator K54 mix, after stirring, prepares B component。
(3) A, B component press the weight ratio mixing of 10:3, after stirring, prepare anti-flaming dope。
Two, the preparation of fire-retardant coiled material
Specifically comprise the following steps that
(1) being uniformly coated on mould release membrance by anti-flaming dope, at 80 DEG C, baking solidifies for 25 minutes, after cooling, obtains fire retardant surface layers；
(2) being coated with anti-flaming dope on fire retardant surface layers, more uniform spreading length is the alkali-free glass fibre chopped silk of 30mm on anti-flaming dope, is then covered by mould release membrance, at 80 DEG C, baking solidifies for 25 minutes, obtains chopped fibers；
(3) cooling, trimming rolling, obtain fire-retardant coiled material。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V0, building materials flame retardant rating is B1 level (standard GB/T8624), and oxygen index (OI) is 36 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Embodiment 2
(1) preparation of component A: by the average bisphenol A-type novolac epoxy resin F-51 that epoxide number is 0.51eq/100g containing 3.6 epoxide groups of epoxy resin 170,5 parts that 52 parts of epoxide equivalents are 165g/eq；8 parts of fire-retardant diluent dibromo phenyl glycidyl ethers are placed in the reactor of temperature 80 DEG C, stir 35 minutes under the revolution of 60 revs/min, it is cooled below 40 DEG C, 4 parts of toughener ZR-05,0.5 part of dispersant B YK181,0.2 part of defoamer BYK550 are added in reactor, 0.3 part of levelling agent BYK354,24 parts of flame-retardant additives, 3 parts of mill bases, 3 parts of inorganic filler silica flours；After stirring, it is filtrated to get component A；
Wherein, consisting of of flame-retardant additive: 9 parts of aluminium hydroxide, 5 parts of methyl-phosphoric acid dimethyl esters, 5 parts of melamine cyanurates, 5 parts of magnesium hydroxide, the particle diameter of flame-retardant additive is 20 μm；
The preparation method of flame-retardant additive is: after said components being mixed, it is thus achieved that mixture；With the quality of mixture for benchmark, then add in mixture 1% silane coupler KH560, after mixing, mixing obtain described flame-retardant additive。
(2) preparation of B component: by 95 parts of polyetheramine Y33 firming agent, 5 parts of curing accelerator K54 mix, after stirring, prepares B component。
(3) A, B component press the weight ratio mixing of 10:2, after stirring, prepare anti-flaming dope。
Two, the preparation of fire-retardant coiled material
Specifically comprise the following steps that
(1) being uniformly coated on mould release membrance by anti-flaming dope, at 75 DEG C, baking solidifies for 35 minutes, after cooling, obtains fire retardant surface layers；
(2) being coated with anti-flaming dope on fire retardant surface layers, more uniform spreading length is the alkali-free glass fibre chopped silk of 50mm on anti-flaming dope, is then covered by mould release membrance, at 80 DEG C, baking solidifies for 30 minutes, obtains chopped fibers；
(3) cooling, trimming rolling, obtain fire-retardant coiled material。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V0, building materials flame retardant rating is B1 level (standard GB/T8624), and oxygen index (OI) is 38 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Embodiment 3
(1) preparation of component A: by 170,6 parts of bromine contents of epoxy resin that 45 parts of epoxide equivalents are 165g/eq be 48%, epoxide equivalent is 390g/eq, softening point is the brominated epoxy resin KM400 of 68 DEG C；7 parts of fire-retardant diluent dibromo phenyl glycidyl ethers are placed in the reactor of temperature 80 DEG C, stir 35 minutes under the revolution of 70 revs/min, it is cooled below 40 DEG C, 4 parts of toughener ZR-05,0.5 part of dispersant B YK181,0.2 part of defoamer BYK550 are added in reactor, 0.3 part of levelling agent BYK354,20 parts of flame-retardant additives, 3 parts of mill bases, 14 parts of silica flours；After stirring, it is filtrated to get component A；
Wherein, consisting of of flame-retardant additive: 10 parts of aluminium hydroxide, 2 parts of methyl-phosphoric acid dimethyl esters, 4 parts of melamine cyanurates, 4 parts of tricresyl phosphate (2-chloropropyl) esters, the particle diameter of flame-retardant additive is 15 μm；
The preparation method of flame-retardant additive is: after said components being mixed, it is thus achieved that mixture；With the quality of mixture for benchmark, then add in mixture 2% silane coupler KH560, after mixing, mixing obtain described flame-retardant additive。
(2) preparation of B component: by 96 parts of polyetheramine Y33 firming agent, 4 parts of curing accelerator K54 mix, after stirring, prepares B component。
(3) A, B component press the weight ratio mixing of 10:2, after stirring, prepare anti-flaming dope。
Two, the preparation of fire-retardant coiled material
Specifically comprise the following steps that
(1) being uniformly coated on mould release membrance by anti-flaming dope, at 80 DEG C, baking solidifies for 35 minutes, after cooling, obtains fire retardant surface layers；
(2) being coated with anti-flaming dope on fire retardant surface layers, more uniform spreading length is the alkali-free glass fibre chopped silk of 40mm on anti-flaming dope, is then covered by mould release membrance, at 80 DEG C, baking solidifies for 30 minutes, obtains chopped fibers；
(3) cooling, trimming rolling, obtain fire-retardant coiled material。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V0, building materials flame retardant rating is B1 level (standard GB/T8624), and oxygen index (OI) is 35 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Embodiment 4
One, the preparation of anti-flaming dope
(1) preparation of component A: by 128,5 parts of bromine contents of epoxy resin that 52 parts of epoxide equivalents are 185g/eq be 48%, epoxide equivalent is 390g/eq, softening point is the brominated epoxy resin KM400 of 68 DEG C；5 parts of average bisphenol A-type novolac epoxy resin F-51 that epoxide number is 0.51eq/100g containing 3.6 epoxide groups；6 parts of fire-retardant diluent dibromo cresylglycidylethers are placed in the reactor of temperature 80 DEG C, stir 30 minutes under the revolution of 70 revs/min, it is cooled below 40 DEG C, 4 parts of toughener ZR-05,0.5 part of dispersant B YK181,0.2 part of defoamer BYK550 are added in reactor, 0.3 part of levelling agent BYK354,21 parts of flame-retardant additives, 3 parts of mill bases, 3 parts of inorganic filler glass powder；After stirring, it is filtrated to get component A；
Wherein, consisting of of flame-retardant additive: 10.5 parts of antimony oxides, 4 parts of chlorinated paraffins, 1 part of aluminium hydroxide, 3.5 parts of tricresyl phosphate (2-chloropropyl) esters, 2 parts of methyl-phosphoric acid dimethyl esters；The particle diameter of flame-retardant additive is 25 μm；
The preparation method of flame-retardant additive is: after said components being mixed, it is thus achieved that mixture；With the quality of mixture for benchmark, then in mixture, add 1% silane coupler KH560, after mixing, mixing obtain described flame-retardant additive。
(2) preparation of B component: by 95 parts of polyamide 200 firming agent, 5 parts of curing accelerator K54 mix, after stirring, prepares B component。
(3) A, B component press the weight ratio mixing of 10:4, after stirring, prepare anti-flaming dope。
Two, the preparation of fire-retardant coiled material
Specifically comprise the following steps that
(1) being uniformly coated on mould release membrance by anti-flaming dope, at 70 DEG C, baking solidifies for 35 minutes, after cooling, obtains fire retardant surface layers；
(2) being coated with anti-flaming dope on fire retardant surface layers, more uniform spreading length is the alkali-free glass fibre chopped silk of 30mm on anti-flaming dope, is then covered by mould release membrance, at 80 DEG C, baking solidifies for 25 minutes, obtains chopped fibers；
(3) cooling, trimming rolling, obtain fire-retardant coiled material。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V0, building materials flame retardant rating is B1 level (standard GB/T8624), and oxygen index (OI) is 39 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Comparative example 1
One, the preparation of anti-flaming dope
This comparative example is except the flame-retardant additive in the antimony oxide alternate embodiment 1 adopting 25 parts, and all the other steps are identical with embodiment 1。
Two, the preparation method of fire-retardant coiled material is identical with embodiment 1。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V2, building materials flame retardant rating is B2 level (standard GB/T8624), and oxygen index (OI) is 30 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Comparative example 2
One, the preparation of anti-flaming dope
This comparative example is except the fire-retardant interpolation diluent in the simple diluents dimethylbenzene alternate embodiment 1 adopting 5 parts, and all the other steps are identical with embodiment 1。
Two, the preparation method of fire-retardant coiled material is identical with embodiment 1。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V1, building materials flame retardant rating is B2 level (standard GB/T8624), and oxygen index (OI) is 31 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Comparative example 3
One, the preparation of anti-flaming dope
This comparative example is except the flame-retarded resin in epoxy resin 128 alternate embodiment 1 that 10 parts of epoxide equivalents of employing are 185g/eq, and all the other steps are identical with embodiment 1。
Two, the preparation method of fire-retardant coiled material is identical with embodiment 1。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V1, building materials flame retardant rating is B1 level (standard GB/T8624), and oxygen index (OI) is 33 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Comparative example 4
One, the preparation of anti-flaming dope
This comparative example is except the flame-retardant additive adopted in 25 parts of Pulvis Talci alternate embodiments 1, and all the other steps are identical with embodiment 1。Two, the preparation method of fire-retardant coiled material is identical with embodiment 1。
After tested: the flame retardant rating of fire-retardant coiled material is UL94-V3, building materials flame retardant rating is C level (standard GB/T8624), and oxygen index (OI) is 26 (GB/T8924), and surface pencil hardness is 3H, and pliability is(examination criteria GB1731)。
Claims (9)
1. a fire-retardant coiled material, for layer structure, it is characterised in that be made up of fire retardant surface layers and chopped fibers, and both form through the bonding solidification of anti-flaming dope；
Described anti-flaming dope, component A and B component by weight ratio is 10:2～5 form；
Wherein, it is calculated in mass percent, consisting of of component A:
Consisting of of B component:
Firming agent 90～97%；
All the other are curing accelerator；
Described flame-retardant additive is at least one in antimony oxide, aluminium hydroxide, magnesium hydroxide, melamine cyanurate, chlorinated paraffin, tricresyl phosphate (2-chloropropyl) ester, methyl-phosphoric acid dimethyl ester。
2. fire-retardant coiled material as claimed in claim 1, it is characterised in that described epoxy resin is liquid bisphenol A epoxy resin or liquid bisphenol F type epoxy resin, and epoxide equivalent is 150～250g/eq。
3. fire-retardant coiled material as claimed in claim 1, it is characterised in that described flame-retarded resin is at least one in brominated epoxy resin, bisphenol A-type novolac epoxy resin。
4. fire-retardant coiled material as claimed in claim 3, it is characterised in that the epoxide equivalent of described brominated epoxy resin is 350～480g/eq, softening point is 50～95 DEG C, and bromine content is 40～55%。
5. fire-retardant coiled material as claimed in claim 3, it is characterised in that average >=3 of the epoxide group quantity that described bisphenol A-type novolac epoxy resin contains, epoxide number is 0.4～0.65eq/100g。
6. fire-retardant coiled material as claimed in claim 1, it is characterised in that described fire-retardant diluent is at least one in dibromo cresylglycidylether, dibromo phenyl glycidyl ether。
7. fire-retardant coiled material as claimed in claim 1, it is characterised in that being calculated in mass percent, described flame-retardant additive is composed of the following components: antimony oxide 50～70%；Chlorinated paraffin 20～30%；All the other are at least one in aluminium hydroxide, magnesium hydroxide, melamine cyanurate, tricresyl phosphate (2 chloropropyl) ester, methyl-phosphoric acid dimethyl ester；
Or, it being calculated in mass percent, described flame-retardant additive is composed of the following components: aluminium hydroxide 30～50%；Methyl-phosphoric acid dimethyl ester 10～30%；Melamine cyanurate 10～20%；All the other are at least one of antimony oxide, magnesium hydroxide, tricresyl phosphate (2 chloropropyl) ester, chlorinated paraffin。
8. fire-retardant coiled material as claimed in claim 1, it is characterised in that described chopped fibers is made up of the glass chopped silk of middle alkali or alkali-free。
9. the method preparing the arbitrary described fire-retardant coiled material of claim 1～8, it is characterised in that including:
(1) described anti-flaming dope is coated on mould release membrance, after solidification, forms fire retardant surface layers；
(2) on described fire retardant surface layers be coated with anti-flaming dope, then on anti-flaming dope the glass chopped silk of spreading, be then covered by mould release membrance, after solidification, formed chopped fibers；
(3) cooling, trimming rolling, obtain described fire-retardant coiled material。
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