CN108589305A - A kind of fibre framework materials dipping solution - Google Patents
A kind of fibre framework materials dipping solution Download PDFInfo
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- CN108589305A CN108589305A CN201810013770.8A CN201810013770A CN108589305A CN 108589305 A CN108589305 A CN 108589305A CN 201810013770 A CN201810013770 A CN 201810013770A CN 108589305 A CN108589305 A CN 108589305A
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- Prior art keywords
- latex
- dipping solution
- polyfunctionality
- framework materials
- rubber
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- 238000007598 dipping method Methods 0.000 title claims abstract description 54
- 239000000835 fiber Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 30
- 229920000126 latex Polymers 0.000 claims abstract description 76
- 239000004816 latex Substances 0.000 claims abstract description 58
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 26
- 238000005470 impregnation Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- 239000002174 Styrene-butadiene Substances 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011115 styrene butadiene Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 3
- -1 Heveatex Polymers 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002916 oxazoles Chemical class 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 24
- 239000003822 epoxy resin Substances 0.000 abstract description 18
- 229920000647 polyepoxide Polymers 0.000 abstract description 18
- 229920001971 elastomer Polymers 0.000 abstract description 17
- 239000005060 rubber Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 8
- 239000004744 fabric Substances 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 11
- 125000005442 diisocyanate group Chemical group 0.000 description 10
- 239000003292 glue Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920006231 aramid fiber Polymers 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229920002955 Art silk Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 238000010073 coating (rubber) Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
-
- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
- 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
-
- 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
- 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
- D06M2101/34—Polyamides
-
- 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
- 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
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Abstract
The invention discloses a kind of fibre framework materials dipping solutions, belong to dipping solution technical field.A kind of fibre framework materials of present invention dipping solution is free of the harmful substances such as resorcinol and formaldehyde, environmentally protective, while not containing epoxy resin, puts not will produce latex skinning and degradation problem for a long time, dipping solution formula system is more stable；The present invention is mixed using polyfunctionality blocked isocyanate with rubber latex, while polyfunctionality blocked isocyanate activated fiber framework material, cross-linked network structure is formed using interaction between polyfunctionality blocked isocyanate and between polyfunctionality blocked isocyanate and rubber latex, realizes the excellent bonds of rubber fabric and rubber；Fibre framework materials after dipping solution impregnation using the present invention have good bond properties with rubber component, can reach or the dipping effect better than traditional RFL.
Description
Technical field
The invention belongs to dipping solution technical fields, specifically more particularly to a kind of fibre framework materials dipping solution.
Background technology
RFL (resorcinol, formaldehyde, latex) formulas are disclosed from DuPont patent US2128635 in 1938, are used for
The bonding of the fabrics such as artificial silk, nylon and rubber.In 1967, DuPont patent US3307966 was disclosed using sealing end
The mixed liquor (everybody is commonly called as D417 formulas at present) of diisocyanate and epoxy resin as a bath, RFL (resorcinol, formaldehyde,
Latex) it is that two baths carry out fiber treatment, it is used for the formula system of polyester PET and rubber adhesion.The above formula, due to economic real
With realizing the excellent bonds of fiber and rubber, be widely used in scholar's research and commercial Application, and be in use to the present.
It is to be put into practice and time-proven, may be used as the fibers such as polyester PET, aramid fiber, nylon, artificial silk, glass and rubber mutually bonds
, effective formula system.
Currently, containing the fiber compared with polyamino, hydroxyl isoreactivity group, such as nylon, artificial silk etc., Ren Menyi for surface
Directly ideal bonding effect is can be obtained using the processing of RFL (resorcinol, formaldehyde, latex) method direct impregnation；And for table
The less fiber of face active group, such as polyester PET, aramid fiber, people generally use a bath dipping to carry out activation process
(processing of D417 formulas) increases the surface active groups of fiber, then reuses RFL (resorcinol, formaldehyde, latex) method
Impregnation is carried out, to obtain and the ideal bonding effect of rubber.Regardless of method, fibre framework materials are carried out with rubber
Before bonding, it is necessary to use a RFL impregnations system (resorcinol, formaldehyde, latex).
Resorcinol and formalin have been the products included in China's hazardous chemical catalogue.Formaldehyde Yi Bei is international
Agency for Research on Cancer (IARC) is classified as known human carcinogen, and possible people is classified as by Environmental Protection Agency USA (EPA)
Class carcinogenic substance.As China is added《It reaches an agreement in Paris》, requirement of the people to environmental protection and occupational health also more value.Ministry of Industry and Information,
The Department of Science and Technology, Chinese Ministry of Environmental Protection's tissue are compiled and edit《Poisonous and harmful raw material (product) substitute catalogue that country encourages》In, also specifically mention
Make great efforts the harmful substances such as resorcinol, formaldehyde being replaced, guiding enterprise continues Green Development, is reduced or avoided from source
The generation of pollutant.Many major companies both domestic and external have appreciated that the importance of environmental protection, carried out research without containing to environment,
To the bonding formula system of the harmful resorcinol of biology and formaldehyde, and disclose related patents.
Patent US5565507, Milliken companies disclose for one kind of polyester fiber and nylon fiber skeleton by three
The impregnation formula system of the above epoxide of degree of functionality, Carboxy and butadiene-vinylpyridine copylymer latex composition.
Patent EP20040002126, Diolen companies disclose one kind for polyester industrial fiber by rubber latex, epoxy
The bonding formula system of compound and polyamines composition.
Patent EP2955268A1, Kordsa companies disclose for nylon, polyester, artificial silk, aramid fiber it is a kind of by
The bonding formula system of rubber latex, sealing end diisocyanate, epoxide and acrylic resin composition.
Patent CN102414362A, bridgestone company disclose for one kind of polyester fiber and nylon fiber by rubber
The impregnation formula system of latex, epoxide and blocked isocyanate/polyamine composition.
Include epoxy resin though not containing resorcinol and formaldehyde in above-mentioned impregnation system, exists in epoxy resin
In the case of, the problem of will appear latex skinning and degradation after dipping solution is put for a long time, therefore existing be free of isophthalic two
The impregnation system stability of phenol and formaldehyde is poor.
Invention content
The invention discloses a kind of impregnation system using rubber latex and water-dispersion type polyfunctionality blocked isocyanate,
In the presence of solving epoxy resin, glue is put cause latex skinning and degradation problem, dipping solution formula system for a long time
It is more stable.
The present invention is implemented by the following technical programs：
A kind of fibre framework materials dipping solution, dipping solution are mixed by rubber latex, polyfunctionality blocked isocyanate and water
It is combined into, the dry weight ratio of wherein rubber latex and polyfunctionality blocked isocyanate is 0.25：1~15:1, consolidating for dipping solution contains
Amount is 5~30%.
The polyfunctionality blocked isocyanate is the compound with multiple terminal isocyanate groups groups, and therein different
Cyanate end moieties are blocked agent and are blocked.
Polyfunctionality blocked isocyanate includes at least three terminal isocyanate groups groups.
End-capping reagent used in terminal isocyanate groups group be phenols, alcohols, oximes Ji oxazole class end-capping reagent one kind or more
Kind.
The rubber latex is butadiene-vinylpyridine copylymer latex, butadiene latex, styrene-butadiene latex, Heveatex, EPDM latex, binary
It is one or more in ethylene propylene rubber latex, NBR latex, carboxylated butadiene-vinylpyridine copylymer latex, carboxylated styrene-butadiene latex or carboxylic acrylonitrile butadiene rubber latex.
After dipping solution dipping fibre framework materials, 0.1-10min is dried under the conditions of 120-200 DEG C, 180-250 DEG C
It is heat-treated 0.1-10min.
Compared with prior art, the beneficial effects of the invention are as follows：
A kind of fibre framework materials of present invention dipping solution is free of the harmful substances such as resorcinol and formaldehyde, environmentally protective,
Epoxy resin is not contained simultaneously, puts not will produce latex skinning and degradation problem for a long time, dipping solution formula system is more
Stablize；The present invention is mixed using polyfunctionality blocked isocyanate with rubber latex, in polyfunctionality blocked isocyanate
While activated fiber framework material, using between polyfunctionality blocked isocyanate and polyfunctionality blocked isocyanate and rubber
Interaction forms cross-linked network structure between glue latex, realizes the excellent bonds of rubber fabric and rubber；Using the present invention
Dipping solution impregnation after fibre framework materials and rubber component there is good bond properties, can reach or better than passing
The dipping effect of system RFL.
Specific implementation mode
It is described in detail with reference to embodiment is most further to the present invention：
A kind of fibre framework materials dipping solution, dipping solution are mixed by rubber latex, polyfunctionality blocked isocyanate and water
It is combined into, the dry weight ratio of wherein rubber latex and polyfunctionality blocked isocyanate is 0.25：1~15:1, consolidating for dipping solution contains
Amount is 5~30%.
The polyfunctionality blocked isocyanate is the compound with multiple terminal isocyanate groups groups, the master of compound
Body structure can be aliphatic, aromatic compound, or be high molecular polymer, and polyfunctionality blocked isocyanate includes at least
Three terminal isocyanate groups groups, and terminal isocyanate groups group therein is blocked agent and is blocked.
The structure of blocked isocyanate end moieties is as follows：Wherein R ' is end-capping reagent.
End-capping reagent used in terminal isocyanate groups group be phenols, alcohols, oximes Ji oxazole class end-capping reagent one kind or more
Kind.
The rubber latex is butadiene-vinylpyridine copylymer latex, butadiene latex, styrene-butadiene latex, Heveatex, EPDM latex, binary
It is one or more in ethylene propylene rubber latex, NBR latex, carboxylated butadiene-vinylpyridine copylymer latex, carboxylated styrene-butadiene latex or carboxylic acrylonitrile butadiene rubber latex.
After dipping solution dipping fibre framework materials, 0.1-10min is dried under the conditions of 120-200 DEG C, 180-250 DEG C
It is heat-treated 0.1-10min.
Examples 1 to 7
In Examples 1 to 7, using polyester tire cord fabric thread (polyester PET industrial filament, 1670dtex/2,370 twists/m)
As fibre framework materials, and carry out double bath impregnations, a bath using widely known D417 (sealing end diisocyanate CBI-50,
Ke Ying synthetic materials Co., Ltd of Ma'an Mountain, epoxy resin G1701, EMS-Griltech companies of Switzerland, solid content 3.5%),
Two baths use dipping solution of the present invention (polyfunctionality blocked isocyanateThe limited public affairs of polymer are created in XL 6366, Cohan
Department, butadiene-vinylpyridine copylymer latex PliocordVP106S are purchased from Shanghai Ou Nuo forensic chemistries Co., Ltd outside).In Examples 1 to 7, carry out respectively
For latex with polyfunctionality blocked isocyanate dry weight than the experiment from 0.25~15, dipping solution total solid content is 20%.
The gum dipping process that Examples 1 to 7 uses is as follows：One 150 DEG C of drying temperature of bath, drying time 1min；Heat treatment temperature
230 DEG C of degree, heat treatment time 1min；Two 150 DEG C of drying temperatures of bath, drying time 1min；230 DEG C of heat treatment temperature, heat treatment
Time 1min.
Comparative example 1 is using tradition RFL (Resorcin-Formaldehyde-Latex) as two bath glues.
Examples 1 to 7 and comparative example 1 are tested, test method：H bonding forces are surveyed by GB/T 19390-2014 methods
Examination, stripping surface adhesion are tested by ASTM-D4393 methods, and test result is as shown in table 1.
Table one：
It can be seen that, change the dry ratio of latex and polyfunctionality blocked isocyanate from table 1, can obtain various
The dipping solution of bonding effect.Peel adhesion, the stripping of the fibre framework materials and rubber of the dipping solution dipping of embodiment 2~5
It is good to cover glue grade, H bonding force results, has reached and 1 comparable level of adhesion of comparative example；It can be in 1,6,7 result of embodiment
It was found that using the dipping solution of too low or excessively high latex and polyfunctionality blocked isocyanate ratio, it is unfavorable for reaching effective
Bonding effect.
The dipping solution that result illustrates the present invention in table 1 realizes good with rubber without resorcinol, formaldehyde
Good bonding effect, has reached the identical level of adhesion of traditional RFL (Resorcin-Formaldehyde-Latex system).
Comparative example 2~5
In comparative example 2~5, using polyester tire cord fabric thread (polyester PET industrial filament, 1670dtex/2,370 twists/m)
As fibre framework materials, and double bath impregnations are carried out, a bath is using D417 (sealing end diisocyanate CBI-50, section of Ma'an Mountain English
Synthetic material Co., Ltd, epoxy resin G1701, EMS Company, Switzerland), two bath formulas are shown in Table 2.Gum dipping process is as follows：One bath is dried
Dry 150 DEG C of temperature, drying time 1min；230 DEG C of heat treatment temperature is heat-treated 1min；Two 150 DEG C of drying temperatures of bath, when drying
Between 1min；230 DEG C of heat treatment temperature, heat treatment time 1min.
The bath of comparative example 2 two is free of blocked isocyanate only with latex；The latex and sealing end that the bath of comparative example 3 two uses are different
Cyanate ratio is 4/1, wherein blocked isocyanate select conventional caprolactam blocking diisocyanate MDI (CBI-50,
Ke Ying synthetic materials Co., Ltd of Ma'an Mountain)；Comparative example 4 two bath using latex, epoxy resin (G1701, EMS Company, Switzerland) and
Block the mixed aqueous solution of diisocyanate (CBI-50, Ke Ying synthetic materials Co., Ltd of Ma'an Mountain)；The bath of comparative example 5 two uses
The mixed aqueous solution of latex and epoxy resin (G1701, EMS-Griltech companies of Switzerland).
Comparative example 2~5 is tested, test method：H bonding forces are tested by GB/T 19390-2014 methods, remove table
Face bonding force is tested by ASTM-D4393 methods；Skinning and precipitated form after glue is placed are observed simultaneously.The results are shown in Table 1.
Table two：
It can see from table 2 as a result, in comparative example 2, only do two baths with latex, cannot get good bonding effect；Than
Formula rate same as Example 3 is used compared with example 3, difference lies in comparative examples 3 using bis- isocyanides of MDI of caprolactam blocking
The mixed liquor of acid esters (trade mark CBI-50) and rubber latex, compared with comparative example 2, stripping rubber coating rate grade is 2 grades, and peeling force is omited
There is raising, H bonding forces slightly increase, but bond properties is still bad, and comparative example 3 reflects from result using the envelope being commercialized at present
Diisocyanate is held, the network structure of high intensity can not be formed due to blocking diisocyanate and rubber latex, cause bonding strong
Degree does not reach requirement, and cannot get the bonding effect that dipping solution of the present invention generates.
Comparative example 4 is using sealing end diisocyanate (trade mark CBI-50), rubber latex and epoxy resin (trade mark G1701)
Mixed liquor removes rubber coating rate class 4 grade as two bath formulas, and peeling force and H bonding forces bonding index are good, and comparative example 4 glues
Heshui is flat suitable with embodiment 2~5 in table 1, shows to form certain network between sealing end diisocyanate and epoxy resin
Structure improves adhesive strength；In comparative example 5, bathed as two using the mixed aqueous solution of epoxy resin and latex, after impregnation
The peeling force of fibre framework materials and rubber, stripping rubber coating rate, H bonding forces are all poor.
Glue, which stores, parks estimation of stability, in table 2, after the glue containing epoxy resin is put during comparative example 4,5 is formulated
Skinning will be generated, reacts to each other with epoxy resin the reason is that latex stablizes required alkaline environment, both destroys ring in this way
The activity of oxygen resin, and the stable system of latex is reduced, it is unfavorable for the stability that dipping solution is put.
Embodiment 8~9
In embodiment 8, using Armaid Cord Filament (disactivation type p-aramid fiber long filament, Di Ren companies, 1680dtex/2,315
Twist/m) fibre framework materials are used as, double bath impregnation experiments are carried out, a bath uses epoxy resin aqueous solution (G1701, Switzerland EMS-
Griltech companies), two baths use dipping solution of the present invention (polyfunctionality blocked isocyanateXL 6366, Cohan
Create polymer Co., Ltd, butadiene-vinylpyridine copylymer latex Pliocord VP106S, Shanghai Ou Nuo forensic chemistries Co., Ltd).Gum dipping process is such as
Under：One 150 DEG C of drying temperature of bath, drying time 1min；230 DEG C of heat treatment temperature, heat treatment time 1min；Two bath drying temperatures
150 DEG C, drying time 1min；230 DEG C of heat treatment temperature, heat treatment time 1min.
In embodiment 9, fiber reinforcement is used as using nylon66 fiber cord fabric thread (refreshing horse industry, 1400dtex/2,370 twists/m)
Material, using dipping solution of the present invention (polyfunctionality blocked isocyanateXL 6366, it is limited that polymer is created in Cohan
Company, butadiene-vinylpyridine copylymer latex Pliocord VP106S, Shanghai Ou Nuo forensic chemistries Co., Ltd) carry out mono bath impregnation experiment.Gum dipping process
It is as follows：150 DEG C of drying temperature, drying time 1min；225 DEG C of heat treatment temperature, heat treatment time 2min.
Comparative example 6~7
In comparative example 6, using Armaid Cord Filament (disactivation type p-aramid fiber long filament, Di Ren companies, 1680dtex/2,315
Twist/m) fibre framework materials are used as, carry out double bath impregnation experiments.One bath uses epoxy resin aqueous solution (G1701, Switzerland EMS-
Griltech companies), two baths use routine RFL (Resorcin-Formaldehyde-Latex) impregnation system.Gum dipping process is as follows：One bath is dried
Dry 150 DEG C of temperature, drying time 1min；230 DEG C of heat treatment temperature, heat treatment time 1min；Two 150 DEG C of drying temperatures of bath, dry
Dry time 1min；230 DEG C of heat treatment temperature, heat treatment time 1min.
In comparative example 7, fiber reinforcement is used as using nylon66 fiber cord fabric thread (refreshing horse industry, 1400dtex/2,370 twists/m)
Material carries out mono bath impregnation experiment using conventional RFL (Resorcin-Formaldehyde-Latex) impregnation system.Gum dipping process is as follows：It dries
Dry 150 DEG C of temperature, drying time 1min；225 DEG C of heat treatment temperature, heat treatment time 2min.
Embodiment 8~9 and comparative example 6~7 are tested for the property, test method：H bonding forces press GB/T19390-2014
Method is tested, and stripping surface adhesion is measured and graded by ASTM-D4393 methods, the results are shown in Table 3.
Table three：
In table 3, embodiment 8 has reached the level of adhesion of comparative example 6, and embodiment 9 has reached the level of adhesion of comparative example 7,
Show that dipping solution of the present invention has reached the level of adhesion of traditional RFL (Resorcin-Formaldehyde-Latex) impregnation system.
In conclusion being only the relatively embodiment of the present invention, not it is used for limiting the scope of implementation of the present invention, Fan Yiben
The equivalent changes and modifications carried out by shape, construction, feature and spirit described in invention right, should all be included in this hair
In bright right.
Claims (6)
1. a kind of fibre framework materials dipping solution, it is characterised in that：Dipping solution blocks isocyanic acid by rubber latex, polyfunctionality
Ester and water mixing composition, the dry weight ratio of wherein rubber latex and polyfunctionality blocked isocyanate is 0.25：1~15:1, impregnation
The solid content of liquid is 5~30%.
2. a kind of fibre framework materials dipping solution according to claim 1, it is characterised in that：The polyfunctionality sealing end
Isocyanates is the compound with multiple terminal isocyanate groups groups, and terminal isocyanate groups group therein is blocked agent
It is blocked.
3. a kind of fibre framework materials dipping solution according to claim 1, it is characterised in that：Polyfunctionality blocks isocyanide
Acid esters includes at least three terminal isocyanate groups groups.
4. a kind of fibre framework materials dipping solution according to claim 1, it is characterised in that：Terminal isocyanate groups group
End-capping reagent used be phenols, alcohols, oximes Ji oxazole class end-capping reagent it is one or more.
5. a kind of fibre framework materials dipping solution according to claim 1, it is characterised in that：The rubber latex is fourth
Pyrrole latex, butadiene latex, styrene-butadiene latex, Heveatex, EPDM latex, binary ethylene propylene rubber latex, NBR latex, carboxylated
It is one or more in butadiene-vinylpyridine copylymer latex, carboxylated styrene-butadiene latex or carboxylic acrylonitrile butadiene rubber latex.
6. a kind of fibre framework materials dipping solution according to claim 1, it is characterised in that：The dipping solution dipping is fine
After tieing up framework material, 0.1-10min, 180-250 DEG C of heat treatment 0.1-10min are dried under the conditions of 120-200 DEG C.
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| CN112832030A (en) * | 2020-12-29 | 2021-05-25 | 北京化工大学 | Environment-friendly gum dipping solution, preparation method and application |
| CN113614306A (en) * | 2019-03-01 | 2021-11-05 | 大陆轮胎德国有限公司 | Aqueous impregnating composition |
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