CN108909104A - A kind of preparation method of high-low temperature resistant light-weight water-proof coiled material - Google Patents
A kind of preparation method of high-low temperature resistant light-weight water-proof coiled material Download PDFInfo
- Publication number
- CN108909104A CN108909104A CN201810552877.XA CN201810552877A CN108909104A CN 108909104 A CN108909104 A CN 108909104A CN 201810552877 A CN201810552877 A CN 201810552877A CN 108909104 A CN108909104 A CN 108909104A
- Authority
- CN
- China
- Prior art keywords
- modified
- pitch
- sbs
- low temperature
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
Abstract
The invention discloses a kind of preparation methods of high-low temperature resistant light-weight water-proof coiled material, belong to technical field of material, the specific steps are：First prepare asphalt mixture；Then modified SBS, aromatic naphtha, coumarone indene resin are obtained into modified SBS mixture after mixing；Said mixture is added in asphalt mixture, 800 mesh talcum powder, modified hollow glass micropearl waterproofing agent is added, homogeneous modified pitch is obtained after stirring；Bitumen layer is formed in tire cloth two sides using above-mentioned modified pitch, and attaches polyvinyl film layer and aluminum membranous layer respectively；Clot is finally carried out after supercooling, sizing, traction, conveying, cutting, obtains waterproof roll.The waterproof roll being prepared using the method for the invention compared with traditional waterproof roll, have the characteristics that high temperature do not trickle, low temperature flawless, while also having the advantages that low-density, lighting.
Description
Technical field
The invention belongs to technical field of material, and in particular to a kind of preparation side of high-low temperature resistant light-weight water-proof coiled material
Method.
Background technique
Waterproof roll is mainly used for construction wall, roofing and tunnel, highway, subway, refuse landfill etc., rises
To the rollable flexible building material product at web-like of one kind for resisting extraneous rainwater, underground water leakage.Waterproof roll is as engineering base
Ne-leakage connects between plinth and building, is the first barrier of entire engineering waterproofing, plays to entire engineering vital
Effect can be divided into asphalt waterproofing material, modified-high polymer waterproof roll material and synthesis macromolecule according to its main waterproof composition material
Waterproof roll three categories asphalt water-proof coiled material.
Asphalt water-proof coiled material is on base tire (such as body paper, fabric) after dip-coating pitch, then surface dispense powdery or
The isolated material of sheet and manufactured rollable sheet waterproof material, therefore, traditional asphalt waterproof material service life is short, chemistry
Stability is poor, and waterproof effect is undesirable, in actual industrial application, needs to be modified it.
Common modification mode is addition s-B-S (SBS) thermoplastic elastic in asphalt mixture
Body is homogeneously dispersed in SBS in pitch by the methods of shearing, stirring, while a certain proportion of stabilizer is added, and is formed altogether
Mixed material, does modification to pitch using the physical property of SBS, improves the properties of pitch.
For example, application publication number is the Chinese invention patent of CN107266917A, a kind of heat molten type elasticity structural reform is disclosed
Property asphalt water-proof coiled material successively includes：Upper surface separation layer, upper surface modified asphalt layer, tire base, lower surface modified asphalt layer
And lower surface separation layer, the upper surface modified asphalt layer is coated by high compact modified pitch to be formed, and the lower surface is modified
Bitumen layer by the thickness direction in the waterproof roll sectional view in fall isosceles trapezoid high compact modified pitch and
The sectional view of the thickness direction of the waterproof roll alternates coating in the low viscosity modified pitch of isosceles triangle and is formed；
Wherein, the high compact modified pitch is grouped as by the group of following parts by weight：100-140 parts of pitch, 0-10 parts of softening agent,
SBS10-30 parts, 10-20 parts of thickener, 3-8 parts of modifying agent, 1-5 parts of defoaming agent, 20-40 parts of filler；The low viscosity is modified
Pitch is grouped as by the group of following parts by weight：80-120 parts of pitch, 10-30 parts of softening agent, SBS5-15 parts, modifying agent 15-25
Part, 2-6 parts of thinner, 30-60 parts of filler.
This heat molten type elastomer modified asphalt waterproof roll can be laid at the top of house and play preferable waterproof action,
But due to the characteristic of pitch and SBS itself, so that this kind of waterproof roll temperature sensitivity is higher, temperature is excessively high or temperature
In the case where too low, it may appear that situations such as crimping warps, fluidizes, cracking.Whether some improvement can be done to pitch and SBS, gram
Taking the above problem is to be worth the project of research.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of high-low temperature resistant light-weight water-proof coiled material, by right in preparation process
In the modification of pitch and SBS, its original disadvantage is overcome.Make pitch that there is preferably viscosity, while the low temperature, high temperature the case where
Under be able to maintain its intrinsic property (intensity, toughness, water resistant damage, antiskid, anti-aging, antifatigue etc.) and do not reduce, avoid fluidisation, rise
Phenomena such as sticking up, cracking improves the weatherability of product.Further object is so that waterproof roll develops to lighting direction.
Above-mentioned technical purpose of the invention technical scheme is that, the specific steps are：
Step 1,10# pitch, 100# pitch is taken to be stirred to obtain asphalt mixture, temperature control exists in whipping process
190 DEG C~200 DEG C, abundant shear-mixed keeps asphalt mixture in a molten state；
Step 2, modified SBS and aromatic naphtha are taken, 85~90 DEG C is heated to, is stirred, forms mixture after stirring, then plus
Enter coumarone indene resin, obtain modified SBS mixture after mixing, kept the temperature, temperature is 85~90 DEG C；
Step 3, modified SBS mixture is added in asphalt mixture, temperature promotion is stirred to 190~200 DEG C, and sufficiently
It mixes；
Step 4,800 mesh talcum powder, modified hollow glass micropearl waterproofing agent are added, homogeneous SBS is obtained after stirring
Modified pitch；
Step 5, bitumen layer is formed in tire cloth two sides；
Step 6, polyvinyl film layer and aluminum membranous layer are attached respectively in the bitumen layer of tire cloth two sides；
Step 7, clot is carried out after supercooling, sizing, traction, conveying, cutting, obtains waterproof roll.
Specifically, the method that tire cloth two sides described in step 5 of the present invention form bitumen layer is：By tire cloth in modified pitch
Middle immersion, until tire cloth two sides uniformly attaches pitch and forms bitumen layer.The advantages of this mode, is that pitch is uniform, and disadvantage exists
In the more thorough of infiltration, pitch can be also adhered in the gap of tire cloth, and the pitch of this part is not in fact in actual use
The external world can be touched, corresponding, the furthermore bad control of the thickness of bitumen layer can not be played the role of.
It is further to improve, be in the method that tire cloth two sides form bitumen layer described in step 5：Modified pitch is smeared
On polyester blank cloth, uniformly smears and form bitumen layer.It is very advantageous for the thickness control of bitumen layer in this way, it can
Bitumen layer is adjusted to thickness appropriate by the number smeared, furthermore by the way of smearing, complete wetting tire is not needed
The internal voids of cloth, pitch utilization rate is higher for former approach.Disadvantage is that uniformity is bad.
It is further to improve, be in the method that tire cloth two sides form bitumen layer described in step 5：Modified pitch is sprayed
It spills on polyester blank cloth, uniformly sprinkling forms bitumen layer.In this way, not only uniformity is good, but also thickness is easy to control,
Overcome the respective defect of above two scheme.Also it has been found surprisingly that the thermal stability that product can be improved simultaneously, and
Significantly alleviate the density of product.
More specifically, raw material employed in above-mentioned steps, respective parts by weight are：9~13 parts of 10# pitch；100#
12~17 parts of pitch, 1~3 part of modified SBS, 1~3 part of aromatic naphtha, 8~12 parts of 800 mesh talcum powder, modified hollow glass micropearl are anti-
0.1~0.3 part of aqua, 0.1~0.2 part of coumarone indene resin.
More specifically, the modified SBS obtains by the following method：Tert butyl phenolic resin, activated magnesia are taken, is pressed
Parts by weight weigh, by tert butyl phenolic resin：Activated magnesia=10:1 mixing is added 0.1~0.2 part of N- methyl -2- ratio and coughs up
Alkanone takes with the toluene of tert butyl phenolic resin equivalent as solvent, temperature is controlled at 20~25 DEG C, in solvent as catalyst
6~8h of middle stirring carries out chelatropic reaction, and modifying agent is made；Take SBS, modifying agent, by weight 10:1 takes, and fills at 120 DEG C
Divide stirring, react 4~6h, modified SBS is made.
More specifically, the modification hollow glass micropearl waterproofing agent obtains by the following method：In parts by weight, will
0.1~0.5 part of myristyl cerous phosphate, 2000~5000 parts of hollow glass micropearls, 0.01~0.1 part of 3- amino-4-phenyl thiophene
Pheno -2- methyl formate, 0.1~0.5 part of alkaline thickener, 0.001~0.01 part of tetramethylguanidine trifluoro-methanyl sulfonate are put into and pinch
It is mediated 0.5~4 hour in conjunction machine, kneading temperature is 80 DEG C~120 DEG C, after kneading, and the modification hollow glass containing cerium is made
Microballon waterproofing agent.
Technical solution of the present invention is described in further detail below.
Step 1 is the preparation process of asphalt mixture.
The present invention is using 10# pitch, 100# pitch as matrix pitch, and for matrix pitch, softening point cannot
Excessively high or too low, softening point is excessively high, and pitch is not easy to emulsify, and softening point is too low, then influences coating, is suitably softened using having
The matrix pitch of point carrys out using 10 the present invention with meet demand#Pitch and 100#The mixture of pitch, is entered by needle
It spends higher 10# pitch to be mutually mixed with the lower 100# pitch of needle penetration, to obtain the drip of the needle penetration of suitable softening point
Green mixture.Preferably proportion is：9~13 parts of 10# pitch；12~17 parts of 100# pitch.
Step 2,3,4 be pitch modifying process.
The main component of pitch is oil, colloid, asphalitine, after aromatic naphtha is added in the pitch of molten condition, energy
Enough improve the component of pitch in conjunction with pitch rapidly, can be precipitated to avoid the ingredient in pitch when state change is free.Aromatic naphtha
Arene content have a great impact to the physical property of finished asphalt, the aniline point of aromatic naphtha is higher, i.e., arene content is higher,
The elasticity and toughness of pitch can be improved, higher arene content can also improve the time of pitch oil suction.Benzene, toluene and two
Arene content in toluene is higher, and more aromatic hydrocarbons can be provided using less.Therefore, the present invention is come
It says, aromatic naphtha can be using one or both of benzene, toluene and dimethylbenzene.It is further preferably, using 50% toluene with
The mixture of 50% dimethylbenzene is added in the pitch of melting using said mixture, can make asphalt emulsification, reduce the hard of pitch
Degree increases the needle penetration of pitch, improves the difficulty of processing being coated in coiled work.
The coumarone of liquid condition does not have caking property when being used alone, and pitch can be made to have good bonding after compounding
Property, the effects of including pressure-sensitive or hot melt, coumarone indene resin are added in pitch, can play softening, reinforcement, thickening, dispersion, from
And the viscous stickiness energy of pitch is improved, especially under low temperature environment and hot environment.
Talcum powder has lubricity, fire resistance, acid-resisting, insulating properties, fusing point height, chemical property torpescence, strong adsorption
The features such as.Talcum powder is added in the asphalt mixture of melting, talcum powder can be improved the heat resistance of pitch as filler and glue
Property, reduce the temperature sensitivity of pitch, additionally it is possible to reduce the dosage of asphalt mixture.The strength and stability of pitch is improved,
So that finished asphalt has preferable shear strength.
Modified hollow glass micropearl has that density is low, fusing point is high, electrical insulating property is good, good fluidity, shrinking percentage are small, stability
By force, heat-insulated, sound insulation, high temperature resistant, thermal coefficient and the series of advantages such as Thermal Contraction Coefficient is small, can be improved after being added in pitch
The thermal and insulating performance of waterproof roll, and certain effect for mitigating coil weight can be played.Aluminium film has sunlight preferable
Reflectivity can be emitted onto most of sunlight reflection on waterproof roll surface, be conducive to the heat-insulation and heat-preservation for improving waterproof roll
Performance.
The more importantly modification of SBS for the present invention, SBS belong to phenylethylene hot polymerization elastomer, gather in SBS
Two phase structure is significantly presented in styrene segment and polybutadiene segments, and polybutadiene is continuous phase, and polystyrene is dispersed phase,
Make it have 2 glass transition temperatures, between 2 temperature end group polystyrene flock together to be formed microcell be scattered in it is poly-
Between butadiene continuous phase, play the role of physical crosslinking, fixed segment, the vulcanization anti-cold flow of reinforcing agent, with vulcanized rubber
High resiliency and anti-fatigue performance；When temperature is more than glass transition temperature, polystyrene mutually softens, and can flow, so that SBS
With resin flow processability, this two-phase laminated flow structure enables SBS to form space multistory network with matrix pitch, from
And effectively improve temperature performance, tensile property, elasticity, the cohesion adhesion property, the stability of mixture, resistance to ag(e)ing of pitch
Deng.By modification, the viscosity of SBS under cryogenic can be reinforced.Therefore, the invention also discloses the excellent of above-mentioned modified SBS
Select preparation method：Tert butyl phenolic resin, activated magnesia are taken, is weighed by weight, by tert butyl phenolic resin：Active oxidation
Magnesium=10:1 mixing, is added 0.1 part of N- methyl -2- than pyrrolidone as catalyst, takes the first with tert butyl phenolic resin equivalent
Benzene is controlled as solvent, temperature at 25 DEG C, stirs 8h in a solvent, carries out chelatropic reaction, and modifying agent is made；Take SBS, modification
Agent, by weight 10:1 takes, and is sufficiently stirred at 120 DEG C, reacts 6h, and modified SBS is made.It is prepared using the present invention
Modified SBS can overcome the disadvantage that viscosity is bad under low temperature.
Another improvement of the invention uses modified hollow glass micropearl waterproofing agent and is modified to pitch.It is empty
Heart glass microballoon is after mediating, wherein being enclosed with a large amount of waterproofing agent；Myristyl cerous phosphate in component has good
3- amino-4-phenyl thiophene -2-carboxylic acid methyl esters and tetramethylguanidine trifluoro-methanyl sulfonate can be integrated to hollow glass by adsorptivity
In glass microballon, its hollow glass micropearl is made to have good waterproof performance.Above-mentioned modified hollow glass micropearl is added in pitch,
The waterproof effect of modified pitch can be substantially improved and effectively reduce the density of pitch.Therefore, the invention also discloses above-mentioned
The preferred preparation method of modified hollow glass micropearl waterproofing agent：In parts by weight, by 0.1 part of myristyl cerous phosphate, 3000 parts
Hollow glass micropearl, 0.01 part of 3- amino-4-phenyl thiophene -2-carboxylic acid methyl esters, 0.5 part of alkaline thickener, 0.01 part of tetramethyl
Guanidine trifluoro-methanyl sulfonate is put into kneader and mediates 4 hours, and kneading temperature is 120 DEG C, after kneading, is made containing cerium
Modified hollow glass micropearl waterproofing agent.
Step 5,6 be waterproof roll preparation process.
Tire cloth of the present invention is polyester blank cloth or glass fiber blank cloth.Polyester blank cloth has high-intensitive, high extend and resistance to
The characteristics such as puncture, light-weight, tensile strength is high, good penetrability, high temperature resistant, anti-freezing, while can also be ageing-resistant, corrosion-resistant.Cause
This, for the present invention, preferred polyester blank cloth is more suitable for applying in waterproof roll.Specifically, being formed in tire cloth two sides
Then bitumen layer attaches agglomeration vinyl film layer and aluminum membranous layer by laminating machine respectively in bitumen layer, is combined
Coiled material.It is bonded on roof surface by SBS modified pitch；The structural intergrity of waterproof roll is kept by tire cloth；Aluminium film is made
For the surface of coiled material, the waterproof action on basis is played, and sunlight can be reflected, prevents the illuminated softening of SBS modified asphalt layer.
The obtained waterproof roll of the present invention usually in the planes such as roof in use, aluminum membranous layer upward, aluminium film itself is
With the resistance to positive of good water repellent, the SBS modified asphalt layer thickness attached with aluminium film is relatively thick, in long-term open-air conditions
Under, thicker SBS modified asphalt layer is able to maintain relatively good adhesion, and certain thickness can be maintained in longer time section
The SBS modified asphalt layer of degree.SBS modified asphalt layer thickness close to base membrane layer is relatively thin, can reduce the weight of coiled material entirety
Good waterproof effect is kept while amount, when laying waterproof roll, bakes basement membrane, relatively thin SBS modified asphalt layer first
Surface is heated certain thawing, convenient for being fitted in roof surface.Therefore, the present invention has also carried out preferably the thickness of bitumen layer,
SBS modified asphalt layer between the aluminum membranous layer and tire cloth is with a thickness of 4mm, between the polyvinyl film layer and tire cloth
SBS modified asphalt layer is with a thickness of 3mm.
Step 7 is subsequent process.
In subsequent process single process the specific steps are the technological means that this field usually uses, furthermore do not do and retouch in detail
It states.
In conclusion the invention has the advantages that：
1. the present invention uses the mixing of 10# pitch, 100# pitch, SBS, aromatic naphtha and talcum powder, obtained modified drip
It is green that not only there is good waterproof performance, but also there is preferably viscosity, while neither too hard, nor too soft, there is good processability, be convenient for
It is processed into waterproof roll.
2. the waterproof roll that aluminum membranous layer, SBS modified asphalt layer, tire layer of cloth and polyethylene layer are combined by the present invention is fitted
It closes and is used in roofing.
3. the waterproof roll being prepared using the method for the invention other than having the advantages that routine, also has high temperature
It does not trickle, the characteristics of low temperature flawless.
4. by the change of preparation method and the use of modified hollow glass micropearl, so that the present invention and traditional waterproof
Coiled material is compared, and has the advantages that low-density, lighting.
Specific embodiment
Invention is further described in detail with reference to embodiments.In following embodiments used modified SBS and
Modified hollow glass micropearl is prepared via a method which to obtain：
The preparation of modified SBS：Tert butyl phenolic resin, activated magnesia are taken, is weighed by weight, by tert-butyl phenolic aldehyde tree
Rouge：Activated magnesia=10:1 mixing, is added 0.1 part of N- methyl -2- than pyrrolidone as catalyst, takes and tert-butyl phenolic aldehyde tree
The toluene of rouge equivalent is controlled as solvent, temperature at 25 DEG C, stirs 8h in a solvent, carries out chelatropic reaction, and modifying agent is made；It takes
SBS, modifying agent, by weight 10:1 takes, and is sufficiently stirred at 120 DEG C, reacts 6h, and modified SBS is made.
The preparation of modified hollow glass micropearl waterproofing agent：In parts by weight, by 0.1 part of myristyl cerous phosphate, 3000 parts
Hollow glass micropearl, 0.01 part of 3- amino-4-phenyl thiophene -2-carboxylic acid methyl esters, 0.5 part of alkaline thickener, 0.01 part of tetramethyl
Guanidine trifluoro-methanyl sulfonate is put into kneader and mediates 4 hours, and kneading temperature is 120 DEG C, after kneading, is made containing cerium
Modified hollow glass micropearl waterproofing agent.
Embodiment 1：
9 parts of 10# pitches are taken to be stirred with 12 parts of 100# pitches, temperature is controlled at 190 DEG C~200 DEG C, and sufficiently shearing is mixed
It closes, keeps asphalt mixture in a molten state；
1 part of modified SBS and 1 part of aromatic naphtha are taken, 90 DEG C is heated to, is stirred, formation SBS mixture after stirring, then plus
Enter 0.2 part of coumarone indene resin, modified SBS mixture is kept the temperature at 90 DEG C；
Modified SBS mixture is added in asphalt mixture in several times, temperature is promoted to 200 DEG C, and is sufficiently stirred；
8 part of 800 mesh talcum powder is added portionwise, 0.1 part of modified hollow glass micropearl waterproofing agent obtains homogeneous after stirring
SBS modified asphalt waterproof material.
Embodiment 2：
13 parts of 10# pitches are taken to be stirred with 17 parts of 100# pitches, temperature is controlled at 190 DEG C~200 DEG C, and sufficiently shearing is mixed
It closes, keeps asphalt mixture in a molten state；
3 parts of modified SBSs and 3 parts of aromatic naphtha are taken, 90 DEG C is heated to, is stirred, formation SBS mixture after stirring, then plus
Enter 0.2 part of coumarone indene resin, modified SBS mixture is kept the temperature at 90 DEG C；
Modified SBS mixture is added in asphalt mixture in several times, temperature is promoted to 200 DEG C, and is sufficiently stirred；
12 part of 800 mesh talcum powder is added portionwise, it is equal to obtain quality after stirring for 0.3 part of modified hollow glass micropearl waterproofing agent
Even SBS modified asphalt waterproof material.
Embodiment 3：
11 parts of 10# pitches are taken to be stirred with 15 parts of 100# pitches, temperature is controlled at 190 DEG C~200 DEG C, and sufficiently shearing is mixed
It closes, keeps asphalt mixture in a molten state；
2 parts of modified SBSs and 2 parts of aromatic naphtha are taken, 90 DEG C is heated to, is stirred, formation SBS mixture after stirring, then plus
Enter 0.2 part of coumarone indene resin, modified SBS mixture is kept the temperature at 90 DEG C；
Modified SBS mixture is added in asphalt mixture in several times, temperature is promoted to 200 DEG C, and is sufficiently stirred；
10 part of 800 mesh talcum powder is added portionwise, it is equal to obtain quality after stirring for 0.2 part of modified hollow glass micropearl waterproofing agent
Even SBS modified asphalt waterproof material.
Embodiment 4：
10 parts of 10# pitches are taken to be stirred with 13 parts of 100# pitches, temperature is controlled at 190 DEG C~200 DEG C, and sufficiently shearing is mixed
It closes, keeps asphalt mixture in a molten state；
1 part of modified SBS and 1 part of aromatic naphtha are taken, 90 DEG C is heated to, is stirred, formation SBS mixture after stirring, then plus
Enter 0.2 part of coumarone indene resin, modified SBS mixture is kept the temperature at 90 DEG C；
Modified SBS mixture is added in asphalt mixture in several times, temperature is promoted to 200 DEG C, and is sufficiently stirred；
9 part of 800 mesh talcum powder is added portionwise, 0.2 part of modified hollow glass micropearl waterproofing agent obtains homogeneous after stirring
SBS modified asphalt waterproof material.
Embodiment 5：
12 parts of 10# pitches are taken to be stirred with 16 parts of 100# pitches, temperature is controlled at 190 DEG C~200 DEG C, and sufficiently shearing is mixed
It closes, keeps asphalt mixture in a molten state；
2 parts of modified SBSs and 2 parts of aromatic naphtha are taken, 90 DEG C is heated to, is stirred, formation SBS mixture after stirring, then plus
Enter 0.2 part of coumarone indene resin, modified SBS mixture is kept the temperature at 90 DEG C；
Modified SBS mixture is added in asphalt mixture in several times, temperature is promoted to 200 DEG C, and is sufficiently stirred；
11 part of 800 mesh talcum powder is added portionwise, it is equal to obtain quality after stirring for 0.2 part of modified hollow glass micropearl waterproofing agent
Even SBS modified asphalt waterproof material.
Comparative example 1：
For embodiment 1, lack aromatic naphtha, using 2 parts of thermoplastic styrene butadiene rubber creams, 1 part of rubber oil.
Comparative example 2：
For embodiment 1, not pitch containing 10#, using 21 parts of 100# pitches.
1~embodiment of above-described embodiment 5 and comparative example 1, the preparation-obtained asphalt waterproofing material of comparative example 2 are examined
It surveys, detection method is as follows：
(1) impermeability：The sample of long 300mm, width 90mm is taken to be kept for the fluid-tight time under the hydraulic pressure of 0.3MPa
At 30 minutes or more；
(2) hot air aging：The sample for taking long 300mm, width 90mm, sample is placed in air oven aging test case, examination
Tryoff meets the following conditions：
A) 105 DEG C of temperature in chamber
B) temperature fluctuation ± 1 DEG C
C) 0.5~1.0m/s of mean wind speed
D) 10~100 times/h of ventilation rate
E) swept volume of a single chamber is 0.1~0.3m3；
(3) peeling strength test：
A) testing equipment：Cupping machine, has at least load-carrying ability of 2000N and enough stretching distances, and fixture is drawn
Stretching speed is 100 ± 10mm/min, and gripping width is no less than 50mm；
B) sample：The sample of 50 ± 1mm of width is taken, and vertical with the connector of cupping machine, length should ensure that sample
Both ends are packed into fixture, and complete lamination portion can be tested, and sample is in 23 ± 2 DEG C and the item of relative humidity 30%~70%
At least 20h is placed under part；
C) test procedure：Entire distance is 100 ± 5mm between fixture, is not subject to load, and test is carried out at 23 ± 2 DEG C, is stretched
100 ± 10mm/min of speed, generating pulling force should continuously record until sample separation, carries out 5 groups of tester average values.
Testing result is as shown in the table：
| Sample | Impermeability | Hot air aging | Peel strength test |
| Embodiment 1 | It does not seep water | It does not melt | 1.7N/mm |
| Embodiment 2 | It does not seep water | It does not melt | 1.7N/mm |
| Embodiment 3 | It does not seep water | It does not melt | 1.8N/mm |
| Embodiment 4 | It does not seep water | It does not melt | 1.8N/mm |
| Embodiment 5 | It does not seep water | It does not melt | 1.9N/mm |
| Comparative example 1 | Slight infiltration | It does not melt | 1.1N/mm |
| Comparative example 2 | It does not seep water | Slight fusing | 0.8N/mm |
As seen from the above table, SBS modified asphalt waterproof material obtained has good viscosity through the invention, is provided simultaneously with
Impermeable feature for a long time, and it is resistant to the hot air aging of long period, it in actual use can be in annual
The higher region of temperature carry out using, waterproof performance can be kept in use for a long time outdoors, have good weatherability.
Embodiment 6
Polyester blank cloth is being filled modified pitch by the modified asphalt material being prepared using 1 the method for embodiment
It is impregnated in material pond, until tire cloth two sides uniformly attaches pitch and forms bitumen layer, it is 3mm that bitumen layer, which controls side, and the other side is
4mm；Then the tire cloth with bitumen layer is subjected to overlay film in laminating machine, the side that asphalt thickness is 4mm covers aluminum membranous layer, drip
Cyan layer covers polyvinyl film layer with a thickness of the side of 3mm, is then beaten after supercooling, sizing, traction, conveying, cutting
Volume, obtains waterproof roll.
Embodiment 7
The modified asphalt material being prepared using 1 the method for embodiment, modified pitch is applied on polyester blank cloth,
The control so that it is convenient to asphalt thickness is smeared in layers, and it is 3mm, other side 4mm that bitumen layer, which controls side,；Then will
Tire cloth with bitumen layer carries out overlay film in laminating machine, and the side that asphalt thickness is 4mm covers aluminum membranous layer, and asphalt thickness is
The side of 3mm covers polyvinyl film layer, and clot is then carried out after supercooling, sizing, traction, conveying, cutting, obtains waterproof
Coiled material.
Embodiment 8
The modified asphalt material being prepared using 1 the method for embodiment is sprayed modified pitch in the state of melting
It spills in the control asphalt thickness that on polyester blank cloth, not only can be convenient, but also pitch distribution is more uniform, bitumen layer control one
Side is 3mm, other side 4mm；Then the tire cloth with bitumen layer is subjected to overlay film in laminating machine, asphalt thickness is 4mm's
Side cover aluminum membranous layer, asphalt thickness be 3mm side cover polyvinyl film layer, then through supercooling, sizing, traction,
Clot is carried out after conveying, cutting, obtains waterproof roll.
The waterproof roll that 6~embodiment of embodiment, 8 the method is prepared is tested for the property, as a result such as following table institute
Show：
It can be seen that 8 products obtained therefrom of embodiment in low temperature flexibility, size changing rate, mass loss etc. from above-mentioned test data
The performance of aspect is more excellent.
Further, since the addition of bitumen layer and hollow glass micropearl is formed on polyester blank cloth by the way of sprinkling,
So that the overall weight of waterproof material mitigates, develop to lighting direction, there is important shadow to the improvement direction of traditional product
It rings.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology
Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as
All by the protection of Patent Law in scope of the presently claimed invention.
Claims (7)
1. a kind of preparation method of high-low temperature resistant light-weight water-proof coiled material, it is characterised in that include the following steps：
Step 1,10# pitch, 100# pitch is taken to be stirred to obtain asphalt mixture, in whipping process temperature control 190 DEG C ~
200 DEG C, abundant shear-mixed keeps asphalt mixture in a molten state；
Step 2, modified SBS and aromatic naphtha are taken, 85 ~ 90 DEG C is heated to, is stirred, form mixture after stirring, add Gu
The grand resin of horse, obtains modified SBS mixture after mixing, is kept the temperature, and temperature is 85 ~ 90 DEG C；
Step 3, modified SBS mixture is added in asphalt mixture, temperature is promoted to 190 ~ 200 DEG C, and is sufficiently stirred；
Step 4,800 mesh talcum powder, modified hollow glass micropearl waterproofing agent are added, it is modified that homogeneous SBS is obtained after stirring
Pitch；
Step 5, bitumen layer is formed in tire cloth two sides；
Step 6, polyvinyl film layer and aluminum membranous layer are attached respectively in the bitumen layer of tire cloth two sides；
Step 7, clot is carried out after supercooling, sizing, traction, conveying, cutting, obtains waterproof roll.
2. the preparation method of high-low temperature resistant light-weight water-proof coiled material according to claim 1, it is characterised in that described in step 5
Tire cloth two sides formed bitumen layer method be：Tire cloth is impregnated in modified pitch, until tire cloth two sides uniformly attaches drip
Blueness simultaneously forms bitumen layer.
3. the preparation method of high-low temperature resistant light-weight water-proof coiled material according to claim 1, it is characterised in that described in step 5
Tire cloth two sides formed bitumen layer method be：Modified pitch is applied on polyester blank cloth, uniformly smears and forms bitumen layer.
4. the preparation method of high-low temperature resistant light-weight water-proof coiled material according to claim 1, it is characterised in that described in step 5
Tire cloth two sides formed bitumen layer method be：Modified pitch is sprayed on polyester blank cloth, uniformly sprinkling forms bitumen layer.
5. the preparation method of high-low temperature resistant light-weight water-proof coiled material described in any one according to claim 1 ~ 4, it is characterised in that
Used raw material, respective parts by weight are：9 ~ 13 parts of 10# pitch, 12 ~ 17 parts of 100# pitch, 1 ~ 3 part of modified SBS, aromatic hydrocarbons
1 ~ 3 part of oil, 8 ~ 12 parts of 800 mesh talcum powder, modified 0.1 ~ 0.3 part of hollow glass micropearl waterproofing agent, coumarone indene resin 0.1 ~ 0.2
Part.
6. the preparation method of high-low temperature resistant light-weight water-proof coiled material described in any one according to claim 1 ~ 4, it is characterised in that
The modified SBS obtains by the following method：Tert butyl phenolic resin, activated magnesia are taken, is weighed by weight, by tertiary fourth
Base phenolic resin：Activated magnesia presses 10:1 mixing, be added 0.1 ~ 0.2 part of N- methyl -2- than pyrrolidone as catalyst, take and
As solvent, temperature is controlled at 20 ~ 25 DEG C the toluene of tert butyl phenolic resin equivalent, is stirred 6 ~ 8h in a solvent, is chelated
Modifying agent is made in reaction；Take SBS, modifying agent, by weight 10:1 takes, and is sufficiently stirred at 120 DEG C, reacts 4 ~ 6h, is made
Modified SBS.
7. the preparation method of high-low temperature resistant light-weight water-proof coiled material described in any one according to claim 1 ~ 4, it is characterised in that
The modification hollow glass micropearl waterproofing agent obtains by the following method：In parts by weight, by 0.1 ~ 0.5 part of myristyl phosphorus
Sour cerium, 2000 ~ 5000 parts of hollow glass micropearls, 0.01 ~ 0.1 part of 3- amino-4-phenyl thiophene -2-carboxylic acid methyl esters, 0.1 ~ 0.5 part
Alkaline thickener, 0.001 ~ 0.01 part of tetramethylguanidine trifluoro-methanyl sulfonate are put into kneader and mediate 0.5 ~ 4 hour, mediate
Temperature is 80 DEG C~120 DEG C, after kneading, and the modification hollow glass micropearl waterproofing agent containing cerium is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810552877.XA CN108909104A (en) | 2018-05-31 | 2018-05-31 | A kind of preparation method of high-low temperature resistant light-weight water-proof coiled material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810552877.XA CN108909104A (en) | 2018-05-31 | 2018-05-31 | A kind of preparation method of high-low temperature resistant light-weight water-proof coiled material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108909104A true CN108909104A (en) | 2018-11-30 |
Family
ID=64409642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810552877.XA Pending CN108909104A (en) | 2018-05-31 | 2018-05-31 | A kind of preparation method of high-low temperature resistant light-weight water-proof coiled material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108909104A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113123163A (en) * | 2021-04-28 | 2021-07-16 | 山东恒旺新材料科技有限公司 | Preparation method of waterproof coiled material based on high polymer modified asphalt |
| CN116178972A (en) * | 2022-12-28 | 2023-05-30 | 北京东方雨虹防水技术股份有限公司 | Microcapsule modified asphalt, preparation method, waterproof coiled material and coating thereof |
| CN117565501A (en) * | 2023-10-24 | 2024-02-20 | 德州宇诺建筑材料有限公司 | Asphalt waterproof coiled material and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10314361A1 (en) * | 2003-03-31 | 2004-10-28 | Vedag Gmbh | Roof cover and sealing sheet comprises a middle layer of an organic carrier material impregnated with modified/polymer bitumen, and bottom and top layers of variously modified polymer bitumen |
| CN101481931A (en) * | 2009-01-20 | 2009-07-15 | 北京市建国伟业防水材料有限公司 | Sticking modified asphalt waterproof coiled material and adhesive, as well as preparation method and application thereof |
| CN102391424A (en) * | 2011-09-01 | 2012-03-28 | 上海交通大学 | Method for modifying styrene-butadiene-styrene (SBS) block copolymer |
| CN102993756A (en) * | 2012-09-29 | 2013-03-27 | 北京东方雨虹防水技术股份有限公司 | Low-density polymer modified asphalt waterproof roll material |
| CN103302918A (en) * | 2013-06-13 | 2013-09-18 | 于天功 | Reaction-type cross lamination macromolecule self-adhesion waterproof coiled material and preparation method thereof |
| CN104553130A (en) * | 2015-01-23 | 2015-04-29 | 唐山东方雨虹防水技术有限责任公司 | Fusible high-performance elastomer modified asphalt waterproof roll |
| CN105153986A (en) * | 2015-10-20 | 2015-12-16 | 湖南金化科技集团有限公司 | Polyurethane modified SBS (styrene-butadiene-styrene) adhesive and preparation method thereof |
| CN105176443A (en) * | 2015-10-13 | 2015-12-23 | 广东三和化工科技有限公司 | Solvent type rubber adhesive and preparation method thereof |
| CN105238084A (en) * | 2015-09-24 | 2016-01-13 | 天长市金牛防水防腐材料有限公司 | Heat-resistance and saline-alkaline-resistance type elastomer modified bitumen waterproof coil material |
| CN106926526A (en) * | 2017-02-13 | 2017-07-07 | 北京中联天晟工程材料有限责任公司 | A kind of pitch thermo-insulating water-proof coiled material and preparation method thereof |
| CN207403289U (en) * | 2017-10-25 | 2018-05-25 | 湖北滴盾防水科技有限公司 | Modified asphalt waterproof coiled material with aluminium foil surface |
-
2018
- 2018-05-31 CN CN201810552877.XA patent/CN108909104A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10314361A1 (en) * | 2003-03-31 | 2004-10-28 | Vedag Gmbh | Roof cover and sealing sheet comprises a middle layer of an organic carrier material impregnated with modified/polymer bitumen, and bottom and top layers of variously modified polymer bitumen |
| CN101481931A (en) * | 2009-01-20 | 2009-07-15 | 北京市建国伟业防水材料有限公司 | Sticking modified asphalt waterproof coiled material and adhesive, as well as preparation method and application thereof |
| CN102391424A (en) * | 2011-09-01 | 2012-03-28 | 上海交通大学 | Method for modifying styrene-butadiene-styrene (SBS) block copolymer |
| CN102993756A (en) * | 2012-09-29 | 2013-03-27 | 北京东方雨虹防水技术股份有限公司 | Low-density polymer modified asphalt waterproof roll material |
| CN103302918A (en) * | 2013-06-13 | 2013-09-18 | 于天功 | Reaction-type cross lamination macromolecule self-adhesion waterproof coiled material and preparation method thereof |
| CN104553130A (en) * | 2015-01-23 | 2015-04-29 | 唐山东方雨虹防水技术有限责任公司 | Fusible high-performance elastomer modified asphalt waterproof roll |
| CN105238084A (en) * | 2015-09-24 | 2016-01-13 | 天长市金牛防水防腐材料有限公司 | Heat-resistance and saline-alkaline-resistance type elastomer modified bitumen waterproof coil material |
| CN105176443A (en) * | 2015-10-13 | 2015-12-23 | 广东三和化工科技有限公司 | Solvent type rubber adhesive and preparation method thereof |
| CN105153986A (en) * | 2015-10-20 | 2015-12-16 | 湖南金化科技集团有限公司 | Polyurethane modified SBS (styrene-butadiene-styrene) adhesive and preparation method thereof |
| CN106926526A (en) * | 2017-02-13 | 2017-07-07 | 北京中联天晟工程材料有限责任公司 | A kind of pitch thermo-insulating water-proof coiled material and preparation method thereof |
| CN207403289U (en) * | 2017-10-25 | 2018-05-25 | 湖北滴盾防水科技有限公司 | Modified asphalt waterproof coiled material with aluminium foil surface |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113123163A (en) * | 2021-04-28 | 2021-07-16 | 山东恒旺新材料科技有限公司 | Preparation method of waterproof coiled material based on high polymer modified asphalt |
| CN113123163B (en) * | 2021-04-28 | 2022-03-22 | 山东恒旺新材料科技有限公司 | Preparation method of waterproof coiled material based on high polymer modified asphalt |
| CN116178972A (en) * | 2022-12-28 | 2023-05-30 | 北京东方雨虹防水技术股份有限公司 | Microcapsule modified asphalt, preparation method, waterproof coiled material and coating thereof |
| CN116178972B (en) * | 2022-12-28 | 2024-03-22 | 北京东方雨虹防水技术股份有限公司 | Microcapsule modified asphalt, preparation method, waterproof coiled material and coating thereof |
| CN117565501A (en) * | 2023-10-24 | 2024-02-20 | 德州宇诺建筑材料有限公司 | Asphalt waterproof coiled material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108729561A (en) | A kind of SBS modified asphalt waterproof coiled materials and its processing technology | |
| CN108909104A (en) | A kind of preparation method of high-low temperature resistant light-weight water-proof coiled material | |
| KR101790695B1 (en) | Energy save of elastic waterproof paint composition, energy save of elastic waterproof layer and multi construction method | |
| CN109705590B (en) | Self-healing self-adhesive rubber asphalt, preparation method thereof and self-adhesive rubber asphalt waterproof coiled material | |
| US6398976B1 (en) | Coated roofing insulation and roofing systems including such insulations | |
| KR101657927B1 (en) | composition self adhesive asphalt waterproofing sheet waterproofing sheet manufacturing method and composite waterproof construction | |
| CN113388336B (en) | TPO thermoplastic polyolefin polymer non-asphalt-based self-adhesive film waterproof coiled material and preparation method thereof | |
| EP2264094B1 (en) | Waterproofing membrane based on bitumen modified with polymers containing hollow glass microspheres. | |
| CN109385102A (en) | Adhesive waterproof coil cementitious matter, preparation method and waterproof roll prepared therefrom | |
| CN114891451B (en) | Compound thermoplastic polymer TPO waterproofing membrane | |
| CA1246264A (en) | Coating compositions for a polymer-modified roofing and waterproofing sheet | |
| CN111923531A (en) | Vulcanized cross-linked asphalt waterproof coiled material | |
| CN114456612A (en) | Modified asphalt, preparation method thereof and modified asphalt waterproof coiled material | |
| CN103612429A (en) | Dry-and-wet neutral detergent fiber (NDF) macromolecular self-adhesive waterproof coiled material, as well as production process and equipment thereof | |
| CN103554678A (en) | Adhesive ethylene propylene diene monomer rubber waterproof coiled material | |
| CN115594873B (en) | Composite waterproof coiled material, heat-insulating composite waterproof coiled material and preparation method thereof | |
| CN112457498A (en) | High-temperature-resistant modified lignin epoxy resin and carbon fiber composite material thereof | |
| CN116496711A (en) | High-strength variable waterproof coiled material and preparation method thereof | |
| CN115353820A (en) | Asphalt waterproof coiled material and preparation method thereof | |
| RU2718882C1 (en) | Lightweight filler for waterproof bitumen membranes | |
| KR100655032B1 (en) | Waterproof sheet using ethylene-vinylacetate copolymer and its manufacturing method | |
| KR101964444B1 (en) | PVC waterproof sheet and manufacturing method thereof and waterproof method using thereof | |
| CN110387206A (en) | Two-component bonding agent and preparation method thereof | |
| EP0442896A1 (en) | Laminate and process for producing same. | |
| CN208762441U (en) | A kind of novel Polymer Materials ' Structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181130 |