CN106049064B - It is a kind of to solve the tacky method of phosphorous flame-retardant coated fabric moisture absorption - Google Patents
It is a kind of to solve the tacky method of phosphorous flame-retardant coated fabric moisture absorption Download PDFInfo
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- CN106049064B CN106049064B CN201610489315.6A CN201610489315A CN106049064B CN 106049064 B CN106049064 B CN 106049064B CN 201610489315 A CN201610489315 A CN 201610489315A CN 106049064 B CN106049064 B CN 106049064B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/298—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing halogen atoms
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
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Abstract
Solves the tacky method of phosphorous flame-retardant coated fabric moisture absorption the invention discloses a kind of.This method, using the ammoniacal liquor solution in alcohol medium, prepares silica modified colloidal sol using two kinds of silane mixture monomers as modifying agent, then adds 10~20% phosphorus flame retardant, and phosphorus silicon synergistic fire retardant is obtained using sol-gel technique；Finally raising seat-cover fabric is carried out coating (acrylic acid ester emulsion, phosphorus silicon synergistic fire retardant, thickener and water), dries and bakes acquisition product.It is improved using the fabrics flame resistance efficiency and water resistance of the phosphorus silicon synergistic fire retardant of the present invention, combustibility reaches national B1 levels requirement, while the defects of white, feel is satiny and tacky is returned on the surface for improving original phosphorus system.
Description
Technical field
The present invention relates to high-performance high ferro, motor vehicle seat fabric preparation field, and in particular to one kind solves phosphorous flame-retardant and applied
The tacky method of layer fabric moisture.
Background technology
China's high ferro, motor-car pass through the fast development of short nearly 10 year, achieve achievement highly visible, not only greatly
Amplitude improves the trip of 1,300,000,000 populations, and turns into the key product that China's export is earned foreign exchange.The development of bullet train is not
Only it is the process that speed improves constantly, even more comfortableness is updated, reliability is constantly strengthened, and meets socio-economic development demand
Process.
Inner decoration textile fabric is one of material particularly critical in motor-car, high ferro evolution.In the high ferros such as seat webbing, motor-car
Decorations textile do not require nothing more than it is attractive in appearance, and require have good wearability and gas permeability, especially emphasize high safety fire resistance.Wash
Synthetic fibre fiber have the advantages that wear-resisting, tear-proof, it is easy to clean, resistance to go mouldy, preferably elasticity and shape-retaining ability, most of motor-car,
The market of high ferro inner decoration textile fabric is mainly captured by polyester fiber.
Motor-car, high ferro have that speed is fast and transport capacity is strong, are influenceed less feature by surface state and weather conditions, with
The development in epoch, motor-car has become the indispensable vehicles of people's trip.But these are relative in motor-car, high ferro etc.
In the less environment in space, the heavy losses such as personal property will necessarily be brought once interior material catches fire.The visitors such as motor-car, high ferro
In-car decorations textile should have excellent anti-flammability and flame-retarding power, and so just in case car catches fire, passenger just has sufficiently
Time flees from the scene of a fire, so as to ensure the safety of passenger.Assign motor-car, high ferro inner decoration textile fabric fire resistance there are two methods：One
It is to use fire resistance fibre, second, carrying out flame-proof treatment to inner decoration facing.Research finds that the alone fire resistance fibre developed at present is also not
Motor-car, the flame-retardancy requirements of high ferro inner decoration facing can be met, it is necessary to do flame-proof treatment further to improve fire resistance.Therefore,
Study motor-car, the arrangement of high ferro inner decoration textile fabric high-performance refractory is necessary and meaning.
Implement high performance flame-proof treatment, fire retardant must take into consideration first.By fire retardant and by ignition resistant substrate
Relation, fire retardant can be divided into：Addition type and response type.Addition type refers to not chemically react with the other components in base material,
Simply it is scattered in for physically in base material, is used for thermal plasticity high polymer；Response type refers to or the monomer as high polymer,
Or the chemical reaction of synthetic high polymer is participated in as auxiliary reagent, finally as the construction unit of high polymer, it is used for heat
Solidity high polymer.By the species of ignition-proof element, fire retardant is typically often divided into：Halogen system, phosphorus system, nitrogen system, boron system, magnesium system, aluminium system, silicon
System etc..By the type of compound, then it can be divided into inorganic based flame retardant, organic fire-retardant and organic and inorganic three kinds of fire retardant of mixing.
Fire retardant decomposition reaction when heated, heat is absorbed by fire retardant and thermal decomposition to produce noninflammability volatile
Heat of gasification, textile temperature in the case of heated is difficult to raise and is prevented the generation of thermal polymer degradation, play fire retardation；
Meanwhile one layer of separation layer can be formed in textile surface during fire retardant burning, it play and prevent heat transfer, reduction imflammable gas from releasing
The effect of thermal discharge and starvation；Fire retardant decomposes under ignition temperature produces a large amount of non-flammable gases, such as water, titanium dioxide
Fuel gas can be diluted to below certain limit by carbon, ammonia etc., these non-flammable compressive gases, even up to combustible concentration scope
Under, so as to play fire-retardant effect；Meanwhile the burning of high polymer be mainly HO produce chain reaction, such material have with
HO reacts the ability of generation hydrone repeatedly, as a result inhibits the chain reaction for producing free radical.
In current high polymer material fire retardant, metal oxide and hydroxide are inexpensive nontoxic, but with the compatibility of material
It is bad, the thermodynamic property of material can be reduced.Halogenated flame retardant particularly brominated flame-retardant, although there is good flame retardant effect,
But it is big smoke amount during their burnings to be present, generation corrosivity, poisonous gas, produces the critical defects such as molten drop.And organophosphor chemical combination
Thing shows preferable fire resistance and less toxic gas and smog is produced than halide-containing.
Phosphorus and phosphorus compound are used as fire retardant very early, its Flame Retardant Mechanism are obtained also more deep.
In differential responses area, phosphorus flame retardant, which plays fire retardation, can be divided into the gentle phase fire retardant mechanism of condensed phase.Mass-spectrometric technique research is sent out
Existing, phosphonium flame retardant has PO to be formed in polymer combustion, can be used as a kind of gaseous phase free radical capturing agent, and in flame
Hydrogen atom combines, and plays a part of suppressing flame.
The fire retardation of phosphorus flame retardant is mainly reflected in the high polymer catabolic phase of Initial Stage of Fire, phosphorus compound decomposable asymmetric choice net
The noninflammability liquid film of phosphoric acid is generated, boiling point is up to 300 DEG C.Phosphoric acid can be dehydrated generation metaphosphoric acid, and metaphosphoric acid further polymerize life
Into poly-metaphosphoric acid.In this process, the coating of phosphoric acid dehydration carbonization effect generation plays blanketing effect, isolation air diffusion
Penetrate into inside combustible substance, so as to change the pattern of polymer combustion；In addition, water caused by phosphorus flame retardant dehydration carbonization
Point, the temperature of condensed phase on the one hand can be reduced, on the other hand can dilute combustible concentration in gas phase, so as to preferably rise
To fire retardation.
However, because cyclic phosphate ester compounds are in itself without crosslinkable active group, it is not easy to even if adding crosslinking agent
Control the satiny tendency of its moisture absorption " oozing out ".And the polyacrylate breast of the film-forming usually used in fabric coating processing
The drawbacks of hot sticky be present in liquid.Therefore the fire retardant, polyacrylate dispersion based on annular phosphate are the fire-retardant painting of adhesive
Layer glue, after cured, can exist and potentially soak satiny feel.
Matte seat-cover fabric Flame-retardant gum coating is to confer to an important means of its fire resistance.Flame retardant coating arranges warp
Go through and cooperateed with from the collaboration of halogen antimony to phosphorus halogen, then arranged to halogen-free expandable cooperative flame retardant.With the improvement of people's environmental awareness, halogen hinders
Fire the progressively disabling of agent, the application of phosphorus flame retardant seems more and more important, but this based flame retardant be also faced with flame retarding efficiency it is not high,
The shortcomings of poor water resistance；In actual application, the defects of coating moistening is tacky be present.Therefore, phosphorus system expandable flame retardant is improved to apply
Layer flame retarding efficiency and water resistance, be solve its tacky defect of flame retardant coating moisture absorption it is basic.Original expandable flame retardant coating side
Method is with the resistance of APP (acid source), pentaerythrite (charcoal source), melamine (source of the gas) compounding polyacrylate (binder)
Combustion system is applied to fabric fire-retardant finishing.But the addition of these materials is generally large, and water resistance is poor；Feel after arrangement
It is harder, fabric face easily occur moisture absorption, it is tacky, whiten, return phenomena such as frost.
The content of the invention
In order to solve the problems, such as that terylene matte seat fabric flame retardant rating and moisture absorption are tacky, the invention provides one kind to solve
The tacky method of phosphorous flame-retardant coated fabric moisture absorption.This method is entered by preparation influence factor to silica modified colloidal sol etc.
Row is inquired into, it is determined that using hydrophobic modification method.The present invention is using two kinds of silane mixture monomers as modifying agent, using colloidal sol-solidifying
Glue technology, prepare SiO2Modification sol, hydrophobically modified phosphorus flame retardant, to reduce its water imbibition, so as to solve to a certain extent
The moisture absorption of coating is tackiness, while improves flame retardant effect.Therefore, this invention removes the fire-retardant effect of phosphorus system expandable flame retardant coating
Contradictory relation between rate and feel, to instruct motor-car, high ferro inner decoration facing, and the production of other draperies.
The technical scheme is that：It is a kind of to solve the tacky method of phosphorous flame-retardant coated fabric moisture absorption, it is characterized in that,
(1) preparation of silica modified colloidal sol
Solvent absolute ethyl alcohol, silicon-containing monomer 1 and silicon-containing monomer 2 are successively added in the reactor, are 9 with ammoniacal liquor regulation pH value
~10, it is warming up to 40~60 DEG C；It is gradually dropped water under agitation again, continues 1~3h of stirring after water droplet is complete, stabilization is made
Silica modified colloidal sol；
Wherein, silicon-containing monomer 2:Silicon-containing monomer 1:The mol ratio of water is 1:(4~6):(2~6), preferably 1:5:4；It is siliceous
Monomer 1 is MTMS, ethyl trimethoxy silane, octadecyl trimethyl silane, phenyltrimethoxysila,e
In one or more；Silicon-containing monomer 2 is the one or more in tetraethyl orthosilicate, methyl silicate, positive silicic acid propyl ester.Its
The addition of middle absolute ethyl alcohol is that 50-80ml absolute ethyl alcohol is added per 0.01mol silicon-containing monomers 2.
(2) prepared by phosphorus-silicon synergistic fire retardant
10~20% are added in the silica modified colloidal sol of above-mentioned preparation (to whole silica modified sol system
Phosphorus flame retardant again), stir (2~3h of high-speed stirred), disperse to substantially uniformity；Then this mixture is dried and (is put into 40
~70 DEG C of thermostatic drying chambers dry 1~2h), make its gel and remove solvent, obtain phosphorus-silicon synergistic fire retardant.
Wherein, phosphorus flame retardant be APP, phosphate toluene diphenyl ester, triphenyl phosphate, IPPP,
Bisphenol-A-bis- (diphenyl phosphoester), tricresyl phosphate, tricresyl phosphate (2- chloropropyls) ester, one kind in annular phosphate or more
Kind.
(3) flame retardant coating of hydrophobization phosphorus system arranges
Flame-proof finishing process flow is：Raising seat-cover fabric → coating (by weight, acrylic acid ester emulsion dosage be 50~
60%, phosphorus-silicon synergistic fire retardant dosage is 30~40%, thickener and water 4~10%, the spread of dacron for 200~
260g/m2) → drying (80~100 DEG C, 1~3min) → bake (160~180 DEG C, 2~3min).Wherein, thickener is propylene
Acid esters emulsion-type thickening agent or polyacrylate emulsion type thickener LM-901, its dosage be 0.5-2% (thickener and water 4~
10%), preferably 0.5-1.0%.
N (H in above-mentioned coating2O):N (silane hydrolyzable groups)=1:2 (mol ratios).
During the dacron use of phosphorous flame-retardant coating, the problem of feel is satiny tacky is produced.Mainly have at present
Three kinds of theoretical explanations：
1. surface chemistry is theoretical：Bibulous plane of crystal has higher surface energy, when moisture in its absorption air
Afterwards, its high energy surface has reformed into low-energy surface, so to solve the hygroscopicity of crystal, key is to change its surface texture,
Surface energy is reduced, improves hydrophobicity.
2. crystal bridging theory：Due to the change of self property and external condition, moisture is constantly from inside to particle surface
Spread (or because of surface moisture absorption), promote particle surface dissolving, recrystallization, built bridge so as to form crystal at particulate interspaces, with
The passage of time, these crystal briges are combined with each other each other, gradually form big agglomerate.And this agglomerate should be particle moisture absorption
External manifestation.Self property includes crystalline nature, chemical composition, granularity, size distribution, the physical dimension of crystal；External condition
Including factors such as humidity, temperature and pressures.
3. capillary absorption is theoretical：Moisture is absorbed more than its critical relative moisture with hygroscopic material, in crystal table
The saturated solution film that face is formed, accelerates capillary absorption, and the saturated vapour pressure of the water on capillary meniscus is full less than outside
And vapour pressure, outside vapor are diffused between particle, so as to moisture absorption deliquescence.
The ester exchange synthesis technique of annular phosphate produces the phosphoric acid oh group of hydrolysis moisture absorption, has similar to phosphoric acid
Can the moisture absorption general character.And acid condition can be catalyzed cyclic phosphate ester hydrolysis, cause flame-retardant system moisture absorption more serious.It is in view of above-mentioned
Theoretical understanding, APP is further specify that in the presence of application process the problem of, and to solve the problems, such as to provide
Direction.
A.R.HORROCKS seminars are once by thermogravimetric test, and research annular phosphate (Antiblaze CU), phosphoric acid are just
Butyl ester (TBP), triphenyl phosphorus (TPP), Triphenylphospine oxide (TPPO) degradation performance.Experimental result find, TBP less than
150 DEG C of polypropylene (150 DEG C of fusing point) and bafta (350 DEG C of burning-point) have obvious weightlessness, thus have stronger volatility.
When annular phosphate (Antiblaze CU) is applied to flame retardant coating, fabric coating surface is caused to have the defects of tacky；And add
Appropriate TBP can reduce the defects of problems degree.Liquid TBP surface tension is relatively low, can reduce flame-retardant coatings glue
Viscosity and surface tension, increase its permeability, the annular phosphate of liquid is penetrated into fabric, reduce cyclic phosphate
Influence of the ester to coating adhesive film forming；The TBP of remaining surface reduces the viscosity of coating, has to the tacky defect of coating moisture absorption and necessarily changes
It is kind.
Original expandable flame retardant coating process is with APP (acid source), pentaerythrite (charcoal source), melamine (gas
Source) compounding polyacrylate (binder) flame-retardant system be applied to fabric fire-retardant finishing.But the addition of these materials is general
It is larger, and water resistance is poor；Feel is harder after arrangement, fabric face easily occur moisture absorption, it is tacky, whiten, return phenomena such as frost.
Its reason is：When the steam partial pressure in outside air is more than coating surface steam partial pressure, the vapor in air
It can assemble in coating surface and condense, and the hygroscopicity of fire retardant then accelerates scattering and permeating of the moisture to glued membrane.Local is water-soluble
Liquid is swelled to glued membrane and is plasticized, and the hydrogen bond and Van der Waals force for causing glued membrane are destroyed, and form the polyacrylate containing fire retardant
Height concentrated solution.The presence of polar group on polymer and flame retardant molecule, produce its contactant surface coarse to polarity
Raw cementation.Thus, by surface chemistry is theoretical, crystal bridging theory and capillary absorption theory to APP moisture absorption, return
The defects of white, is analyzed, and the present invention proposes that the phosphorus flame retardant surface hydrophobicity of silane monomer is modified to improve poly- phosphorus flame retardant application
The problem of generation.
Silicon dioxide gel has reinforcement and fire retardation concurrently, and inorganic silicon compound surface energy is relatively low, and is readily migrate into combustion
Burn body surface face, form high temperature resistant, oxidation resistant silica covering during high-temp combustion, play adiabatic and shielding double action,
The volatile matter of burning generation is prevented to escape, blocking oxygen contacts with matrix, prevents textile melt from dripping, fire-retardant so as to reach
Purpose.
When phosphorus-silicon fire retardant is in use, in high-temp combustion, phosphorus system, silicon dioxide gel not only each play itself
Fire resistance, influence each other, mutually promote simultaneously so that flame retardant effect performs to most preferably.Under high temperature, phosphorus, which can be catalyzed, facilitates charcoal
Formed, and silica covering can prevent the oxidation of layer of charcoal, strengthen the heat endurance of these layer of charcoal, prevent fuel gas from entering
Burning gas phase, so that flameout, and then play phosphorus-silicon cooperative flame retardant effect；Compared to general phosphorus-silicon synergistic fire retardant, sheet
The two cooperative flame retardant synergy is apparently not the effect superposition in simple meaning in invention.The flame retardant effect of the present invention improves, moisture absorption
Tacky defect is improved.
The silicon dioxide gel preparation principle that the present invention applies：By taking tetraethyl orthosilicate as an example.
Under alkalescence condition, the hydrolytic condensation of tetraethyl orthosilicate is in two steps：
1st step, hydrolysis, teos hydrolysis form hydroxylated product and corresponding alcohol；
2nd step, condensation reaction occurs between silicic acid or between silicic acid and tetraethyl orthosilicate.
Hydrolysis：(C2H5O)3Si-OC2H5+H2O→(C2H5O)3Si-OH+C2H5OH
Dehydration polycondensation：(C2H5O)3Si-OH+HO-Si(C2H5O)3→(C2H5O)3Si-O-Si(C2H5O)3+H2O
Lose alcohol polycondensation：(C2H5O)3Si-OC2H5+HO-Si(C2H5O)3→(C2H5O)3Si-O-Si(C2H5O)3+C2H5OH
Under the conditions of base catalysis, [the OH of minor radius-] directly start nucleophilic attack to complete hydrolysis, with alkoxy
Remove, the electropositive increase on silicon atom, and space factor is advantageously, and nucleophilic attack becomes more easy, therefore in alkali
Property catalytic condition under, the hydrolysis of tetraethyl orthosilicate is more complete, polycondensation hydrolyze it is substantially complete under the conditions of on multi-dimensional direction
Carry out.
The present invention using in alcohol medium ammonia hydrolyzing tetraethoxy orthosilane synthesize the method for single dispersing silicon dichloride.Using this
Particle monodispersity that the method for invention not only obtains is good, size is controllable, and due to silica surface silicone hydroxyl very
Modified bridge is suitable as, makes its functionalization.
The present invention advantage be：
(1) silicon dioxide gel and its modified advantage that prepared by the present invention
Raw material：The range of choice of predecessor is big, is not limited solely to the tetraethyl orthosilicate generally used, and raw material is more common
Cheap and wide material sources, while the energy has been saved by adjusting material adding proportion, greatly reduce production cost.
Preparation method：Ludox preparation method has elemental silicon dissolution method, ion-exchange, electrolytic electro-dialysis method, machinery point
Arching pushing, sol-gel process.The present invention uses sol-gel process, and reaction time 1-3h, more general 7h reaction time, reaction
Time is short, efficiently convenient.
Modified phosphorus flame retardant advantage：Flame retardant effect, which improves and moisture absorption will not occur, returns white phenomenon.It is specific as follows：It is unmodified
Phosphorus flame retardant can absorb moisture in air and dissolve, the phosphorus flame retardant inside coating adhesive body is gradually dissolved, absorption
When vapor can not discharge in time, saturated vapor starts to condense in particle surface, dissolves part phosphorus flame retardant particle
Top layer, form phosphorus flame retardant saturated solution.As temperature raises, solubility increase, the fluid viscosity increase of dissolving saturation, powder change
For viscous liquid, dissolving and heat absorbing and lasting progress, system temperature is caused to decline, saturation phosphorous flame-retardant agent solution starts to separate out knot
Crystalline substance, constantly reduced with temperature, part phosphorus flame retardant crystal persistently separates out, and " frost is returned in whiting " for producing coating surface immediately is existing
As.Silane reduces its solubility in phosphorus flame retardant surface gel film forming；Si-OH keys existing for surface, condition is baked in high temperature
Under, it can be chemically reacted with the carboxyl in acrylic acid ester emulsion, promote chemical crosslinking, phosphorus flame retardant is preferably closed
Inside colloid, so-called " returning frost " defect of surface generation is moved to so as to reduce it；The increase of chemical crosslinking degree, improve combustion
Char forming ability during burning, closely knit layer of charcoal can close the effusion of imflammable gas and reduce the heat radiation of flame；The gas of closing
Foaming and intumescing produces stomata, and the intumescent layer of charcoal of formation reduces heat transfer, flame is conducted to the heat of burning transition region and enters one
Step reduces, so as to reduce the intensity of a fire.
Product sol system：It is controllable and for high-purity that the present invention provides a kind of resistance to hygroscopicity and excellent in stability, size
Silicon dioxide gel.Hydrophobically modified phosphorus flame retardant processing textile is used it for, can solve solve phosphorus system coated fabric very well
The problem of moisture absorption is tacky, it is not only economical, safe but also environmentally friendly.The silicon dioxide gel of the present invention is characterised by, under satisfaction
State the high-purity of important document (1)~(3) silicon dioxide granule be dispersed in liquid it is inorganic/medium of organic media in, and described two
Silica sol contains organo-alkali compound.Products characteristics：1. size is controllable, its average particle size range can lead in 30~260nm
Nano ZS nano particle size instrument is crossed to measure.2. hygroscopic capacity≤0.5mg/m of silicon dioxide granule per surface area2.(3) titanium dioxide
Silicon particle is substantially free of organic alkali cpd inside it.
(2) this patent coated fabric performance advantage
It has been investigated that：Changed using phosphorus silicon cooperative flame retardant system, more single phosphorous flame-retardant system, flame retardant effect
It is kind；Spread is controlled, up to preferable fire resistance, while the defects of white, feel is satiny and tacky is returned on the surface of original phosphorus system
Substantially improve；In addition, the concentration and denseness of control flame-retardant coatings glue so that gum it is just right through the back side to matte, fully
Reach good flame resistance, matte style is unaffected, and many-sided effect of wearability and excellent durability.
(3) other advantages of this patent
The tacky solution method ecological, environmental protective of this patent phosphorus system coated fabric moisture absorption, safe and efficient, simple and easy to do, cost is low
It is honest and clean, industry development trend is complied with, profit margin is considerable after large-scale industrial production, and this is also the characteristic creativeness of this patent
One.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Acrylic acid ester emulsion that the present embodiment uses, thickener (acrylic acid ester emulsion type) are by the limited public affairs of Zhejiang section peaking work
Department provides.Wherein, the solid content of acrylic acid ester emulsion is 25%, and pH value is 7~8.Thickener (acrylic acid ester emulsion type)
Dosage be 0.5-1.0% (in terms of the gross mass of coating).
Fire-retardant film water absorption rate according to《FZT 10019-2011 textile sizings polyacrylic size test method serous coat
Water absorption rate determines》Regulation carry out.The preparation process of wherein flame-retardant coatings glue is：It is by certain processing compound that acrylate is newborn
Liquid, prepared fire retardant, thickener, water are added in mediation container, and speed lapping is uniformly dispersed, and flame-retardant coatings glue is made.
Fabrics flame resistance test according to《GBT 5454-1997 textile combustion performance test oxygen index methods》With《GBT
The measure that 5455-2014 textile combustion performance verticals direction char length glows with after flame time》Regulation carry out.
The adhesive of the whole fabric of coating according to《The measure of FZT 01063-2008 coated fabric resistance to blockings》Regulation enter
OK.
Embodiment 1
(1) preparation of silica modified colloidal sol
50mL absolute ethyl alcohols, 0.05mol MTMSs, the positive silicic acid of 0.01mol are successively added in the reactor
Tetra-ethyl ester, it is 9~10 with ammoniacal liquor regulation pH value, is warming up to 50 DEG C；It is gradually dropped 0.04mol water, water droplet under agitation again
Continue to stir 2h after complete, stable, homogeneous, transparent silicon dioxide gel is made.
(2) prepared by phosphorus-silicon synergistic fire retardant
10% APP is added in the colloidal sol of above-mentioned preparation, high-speed stirred 2h, is disperseed to substantially uniformity.Then will
This mixture is put into 50 DEG C of thermostatic drying chambers and dries 2h, makes its gel and removes solvent, obtains phosphorus-silicon synergistic fire retardant.
(3) hydrophobization phosphorous flame-retardant top finish
Flame-proof finishing process flow is：(acrylic acid ester emulsion dosage is for motor-car, high ferro terylene raising seat-cover fabric → coating
60%, phosphorus-silicon synergistic fire retardant dosage is 36%, thickener and the total dosage 4% of water, mol ratio n (H2O):N (silane hydrolyzables
Group)=1:2；The spread of dacron is 200g/m2) → drying (100 DEG C, 2min) → bake (180 DEG C, 2min).
Compareed before improving：Only with phosphorus fire retardant (APP), other are same as above for flame-proof treatment.
Correlated performance is tested by foregoing detection method, it the results are shown in Table 1.
Table 1 before modified after test result table
Note：Without adhesion --- when separating sample, coating surface does not have the sign of any adhesion.
Slight adhesion --- when separating sample, adhesion to a certain degree occurs for coating surface, but coating is without damage.
Adhesion --- coating surface is difficult to separate, and separation process floating coat or partial coating are damaged.
It can to sum up obtain：It is improved using the fabrics flame resistance efficiency and water resistance of phosphorus-silicon synergistic fire retardant of the present invention,
Combustibility reaches national B1 levels requirement, and its tacky defect of flame retardant coating moisture absorption is improved very well.That is phosphorus-silicon synergistic fire retardant
The defects of frost is returned on the surface that original phosphorus system is improved while imparting fabric good flame retardant type, feel is satiny and tacky.
Embodiment 2
(1) preparation of silica modified colloidal sol
60mL absolute ethyl alcohols, 0.05mol ethyl trimethoxy silane and the positive silicon of 0.01mol are successively added in the reactor
Sour tetra-ethyl ester, it is 9~10 with ammoniacal liquor regulation pH value, is warming up to 50 DEG C；It is gradually dropped 0.04mol water under agitation again,
Continue to stir 2h after water droplet is complete, stable, homogeneous, transparent silicon dioxide gel is made.
(2) prepared by phosphorus-silicon synergistic fire retardant
15% phosphate toluene diphenyl ester is added in the colloidal sol of above-mentioned preparation, high-speed stirred 2h, is disperseed to substantially uniformity.
Then this mixture is put into 50 DEG C of thermostatic drying chambers and dries 1h, made its gel and remove solvent, obtain phosphorus-silicon cooperative flame retardant
Agent.
(3) flame retardant coating of hydrophobization APP arranges
Flame-proof finishing process flow is：(acrylic acid ester emulsion dosage is for motor-car, high ferro terylene raising seat-cover fabric → coating
55%, phosphorus-silicon synergistic fire retardant dosage is 40%, thickener and the total dosage 5% of water, mol ratio n (H2O):N (silane hydrolyzables
Group)=1:2；The spread of dacron is 220g/m2) → drying (80 DEG C, 3min) → bake (170 DEG C, 2min).Before pressing
State detection method and test correlated performance, it the results are shown in Table 2.
Compareed before improving：Only with phosphorus fire retardant (phosphate toluene diphenyl ester), other are same as above for flame-proof treatment.
Table 2 before modified after test result table
Note：Without adhesion --- when separating sample, coating surface does not have the sign of any adhesion.
Slight adhesion --- when separating sample, adhesion to a certain degree occurs for coating surface, but coating is without damage.
Adhesion --- coating surface is difficult to separate, and separation process floating coat or partial coating are damaged.
It can to sum up obtain：Carried using the flame retarding efficiency and water resistance of the fabric of phosphorus-silicon synergistic fire retardant of the present invention
Height, combustibility reach national B1 levels requirement, and its tacky defect of flame retardant coating moisture absorption is improved very well.That is phosphorus-silicon collaboration resistance
The defects of frost is returned on the surface that combustion agent improves original phosphorus system while imparting fabric good flame retardant type, feel is satiny and tacky.
Embodiment 3
(1) preparation of silica modified colloidal sol
50mL absolute ethyl alcohols, 0.05mol octadecyl trimethyls silane and the positive silicon of 0.01mol are successively added in the reactor
Sour tetra-ethyl ester, it is 9~10 with ammoniacal liquor regulation pH value, is warming up to 50 DEG C；It is gradually dropped 0.04mol water under agitation again,
Continue to stir 2h after water droplet is complete, stable, homogeneous, transparent silicon dioxide gel is made.
(2) prepared by phosphorus-silicon synergistic fire retardant
10% IPPP, high-speed stirred 2h, to substantially uniformity point are added in the colloidal sol of above-mentioned preparation
Dissipate.Then this mixture is put into 50 DEG C of thermostatic drying chambers and dries 1.5h, made its gel and remove solvent, obtain phosphorus-silicon collaboration
Fire retardant.
(3) flame retardant coating of hydrophobization APP arranges
Flame-proof finishing process flow is：(acrylic acid ester emulsion dosage is for motor-car, high ferro terylene raising seat-cover fabric → coating
60%, phosphorus-silicon synergistic fire retardant dosage is 36%, thickener and the total dosage 4% of water, mol ratio n (H2O):N (silane hydrolyzables
Group)=1:2；The spread of dacron is 220g/m2) → drying (100 DEG C, 2min) → bake (180 DEG C, 2min).Press
Foregoing detection method tests correlated performance, and it the results are shown in Table 3.
Compareed before improving：Only with phosphorus fire retardant (IPPP), other are same as above for flame-proof treatment.
Table 3 before modified after test result table
Note：Without adhesion --- when separating sample, coating surface does not have the sign of any adhesion.
Slight adhesion --- when separating sample, adhesion to a certain degree occurs for coating surface, but coating is without damage.
Adhesion --- coating surface is difficult to separate, and separation process floating coat or partial coating are damaged.
It can to sum up obtain：Carried using the flame retarding efficiency and water resistance of the fabric of phosphorus-silicon synergistic fire retardant of the present invention
Height, combustibility reach national B1 levels requirement, and its tacky defect of flame retardant coating moisture absorption is improved very well.That is phosphorus-silicon collaboration resistance
The defects of frost is returned on the surface that combustion agent improves original phosphorus system while imparting fabric good flame retardant type, feel is satiny and tacky.
Embodiment 4
(1) preparation of silica modified colloidal sol
60mL absolute ethyl alcohols, 0.05mol MTMSs and the positive silicic acid of 0.01mol are successively added in the reactor
Propyl ester, it is 9~10 with ammoniacal liquor regulation pH value, is warming up to 50 DEG C；It is gradually dropped 0.04mol water, water droplet under agitation again
Continue to stir 3h after complete, stable, homogeneous, transparent silicon dioxide gel is made.
(2) prepared by phosphorus-silicon synergistic fire retardant
20% tricresyl phosphate (2- chloropropyls) ester, high-speed stirred 3h, to substantially uniformity are added in the colloidal sol of above-mentioned preparation
It is scattered.Then this mixture is put into 60 DEG C of thermostatic drying chambers and dries 1h, made its gel and remove solvent, obtain phosphorus-silicon collaboration
Fire retardant.
(3) flame retardant coating of hydrophobization APP arranges
Flame-proof finishing process flow is：(acrylic acid ester emulsion dosage is for motor-car, high ferro terylene raising seat-cover fabric → coating
55%, phosphorus-silicon synergistic fire retardant dosage is 35%, thickener and the total dosage 10% of water, mol ratio n (H2O):N (silane hydrolyzables
Group)=1:2；The spread of dacron is 240g/m2) → drying (100 DEG C, 2min) → bake (180 DEG C, 2min).Press
Foregoing detection method tests correlated performance, and it the results are shown in Table 4.
Compareed before improving：Only with phosphorus fire retardant (tricresyl phosphate (2- chloropropyls) ester), other are same as above for flame-proof treatment.
Table 4 before modified after test result table
Note：Without adhesion --- when separating sample, coating surface does not have the sign of any adhesion.
Slight adhesion --- when separating sample, adhesion to a certain degree occurs for coating surface, but coating is without damage.
Adhesion --- coating surface is difficult to separate, and separation process floating coat or partial coating are damaged.
It can to sum up obtain：It is improved using the fabrics flame resistance efficiency and water resistance of phosphorus-silicon synergistic fire retardant of the present invention,
Combustibility reaches national B1 levels requirement, and its tacky defect of flame retardant coating moisture absorption is improved very well.That is phosphorus-silicon synergistic fire retardant
The defects of frost is returned on the surface that original phosphorus system is improved while imparting fabric good flame retardant type, feel is satiny and tacky.
Claims (9)
1. a kind of solve the tacky method of phosphorous flame-retardant coated fabric moisture absorption, it is characterized in that,
（1）The preparation of silica modified colloidal sol
Solvent absolute ethyl alcohol, silicon-containing monomer 1 and silicon-containing monomer 2 are added in the reactor, are 9 ~ 10 with ammoniacal liquor regulation pH value；Exist again
Water is gradually dropped under stirring condition, continues stirring after water droplet is complete to stable, obtained stable silica modified colloidal sol；
Wherein, silicon-containing monomer 2 in molar ratio:Silicon-containing monomer 1:Water=1:（4~6）:（2~6）；Silicon-containing monomer 1 is methyl trimethoxy oxygen
One or more in base silane, ethyl trimethoxy silane, octadecyl trimethyl silane, phenyltrimethoxysila,e；Contain
Silicon monomer 2 is the one or more in tetraethyl orthosilicate, methyl silicate, positive silicic acid propyl ester；
（2）It is prepared by phosphorus-silicon synergistic fire retardant
In step（1）The phosphorus flame retardant of its weight 10 ~ 20% is added in the silica modified colloidal sol prepared, is stirred to complete
It is dispersed；Then this mixture is put into 40 ~ 70 DEG C of thermostatic drying chambers and dries 1 ~ 2h, made its gel and remove solvent, obtained
Phosphorus-silicon synergistic fire retardant；
（3）Flame retardant coating arranges
Raising seat-cover fabric is carried out coating, dries and bakes acquisition product, component and the weight ratio of the coating are：Acrylic acid
Ester emulsion 50 ~ 60%, phosphorus-silicon synergistic fire retardant 30 ~ 40%, thickener and water 4 ~ 10%；The spread of fabric is 200 ~ 260g/m2。
2. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as claimed in claim 1, it is characterized in that, the step
Suddenly（3）Drying be：80 ~ 100 DEG C of 1 ~ 3min of drying；Bake for：160 ~ 180 DEG C bake 2 ~ 3min.
3. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as claimed in claim 1, it is characterized in that, the phosphorus
Flame retardant is APP, phosphate toluene diphenyl ester, triphenyl phosphate, IPPP, bisphenol-A-bis-（Diphenyl
Phosphate）, tricresyl phosphate, tricresyl phosphate（2- chloropropyls）One or more in ester, annular phosphate.
4. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as claimed in claim 1, it is characterized in that, the step
Suddenly（1）The addition of absolute ethyl alcohol is that 50-80ml absolute ethyl alcohol is added per 0.01mol silicon-containing monomers 2.
5. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as described in any one in claim 1-4, its
It is characterized in, the step（1）After tune pH value is 9 ~ 10,40 ~ 60 DEG C are warming up to.
6. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as claimed in claim 5, it is characterized in that, the step
Suddenly（1）Continue the h of stirring reaction 1 ~ 3 after water droplet is complete.
7. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as described in any one in claim 1-4, its
It is characterized in, the step（1）In molar ratio, silicon-containing monomer 2:Silicon-containing monomer 1:Water=1:5:4.
8. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as described in any one in claim 1-4, its
It is characterized in, the thickener is acrylic acid ester emulsion type thickener or polyacrylate emulsion type thickener, dosage 0.5-2%.
9. a kind of tacky method of solution phosphorous flame-retardant coated fabric moisture absorption as described in any one in claim 1-4, its
It is characterized in, the step（3）In coating, n (H in molar ratio2O):N (silane hydrolyzable groups)=1:2.
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| CN107916068A (en) * | 2017-12-05 | 2018-04-17 | 合肥师范学院 | The garment material and its processing method of fabric water proof fire retardant coating adhesive, water proof fire retardant |
| CN111576041B (en) * | 2020-06-02 | 2022-06-21 | 安美桥（南宫）羊绒制品有限公司 | Production process of flame-retardant fluff product |
| CN112252026A (en) * | 2020-09-23 | 2021-01-22 | 浙江桐星纺织科技发展股份有限公司 | Production process of environment-friendly phosphorus-based low-weight-gain flame-retardant fabric |
| KR102601266B1 (en) * | 2021-04-19 | 2023-11-13 | 주식회사 액시드 | Flame retardant film and coating composition for the flame retardan film |
| CN114855445B (en) * | 2022-04-25 | 2023-10-03 | 武汉大学中南医院 | Super-hydrophobic flame-retardant textile and preparation method thereof |
| CN115011229B (en) * | 2022-06-27 | 2023-05-26 | 清远高新华园科技协同创新研究院有限公司 | Nano silicon dioxide sol modified polyurethane phosphorus paint and preparation method thereof |
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