CN108004780A - Surface treatment of carbon fibers agent for cyanate ester resin matrix and preparation method thereof - Google Patents
Surface treatment of carbon fibers agent for cyanate ester resin matrix and preparation method thereof Download PDFInfo
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- CN108004780A CN108004780A CN201711220379.7A CN201711220379A CN108004780A CN 108004780 A CN108004780 A CN 108004780A CN 201711220379 A CN201711220379 A CN 201711220379A CN 108004780 A CN108004780 A CN 108004780A
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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
- D06M15/37—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
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- 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
- D06M15/55—Epoxy resins
-
- 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
- D06M2101/40—Fibres of carbon
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
The invention discloses a kind of surface treatment of carbon fibers agent for cyanate ester resin matrix and preparation method thereof.The surface conditioning agent is made of the DMF solution of DMPA, the epoxy resin of 3 11 parts by weight, the triethylamine of 5 10 parts by weight, the DET of 26 parts by weight and the acetone of 10 20 parts by weight that the mass fraction of the polyester polyol of 20 40 parts by weight, the IPDI of 5 12 parts by weight, the DBTDL of 0.1 0.3 parts by weight, the stannous octoate of 0.05 0.1 parts by weight, 10 50 parts by weight is 3%, and each component quality sum is 100%.The present invention prepares the surface treatment of carbon fibers agent for the purpose of improving carbon fiber and cyanate ester resin interfacial combined function, the problem of compensate for there is no such commercially available carbon fiber inorganic agent product at present, and then improves the overall mechanical properties of composite material.
Description
Technical field
The present invention relates to sizing agent technical field, is specifically a kind of surface treatment of carbon fibers for cyanate ester resin matrix
Agent and preparation method thereof.
Background technology
Carbon fiber/polymer matrix composites are because having the advantages that high specific strength, high ratio modulus, designability are strong etc. unique wide
It is general to be applied to aerospace industry.And reinforcement material is used as, high modulus carbon fiber is since surface is smooth, surface active groups
Few, chemical inertness is strong, low with the adhesion strength of resin matrix, makes the mechanical property of material be extremely difficult to be expected.And due to carbon
Fiber enbrittles, and easily produces lousiness and single wire fracture phenomenon in process of production, this can not only reduce the mechanical property of material
Energy, can also reduce the wetting property of carbon fiber and resin.The method usually handled by surface size can be in carbon fiber and resin
Good transition zone is introduced between matrix, protective film is formed in fiber surface, strengthens the protection to carbon fiber, improve fiber surface
Active group type and quantity, improve the surface property of fiber, fiber is tightly combined with resin matrix, and enhancing composite material is whole
Body, while also strengthen the mechanical property of composite material.Such as Application No. 201280051642.3 and 201210463139.0
Patent proposes different sizing agent preparation methods respectively for thermoplastic resin for the fiber reinforced composite material of matrix resin,
The adhesive property of fiber and resin matrix is improved to varying degrees, improves the interlaminar shear strength of composite material.And
A kind of water-based sizing agent for epoxy based carbon fiber that the patent of Application No. 201510870331.5 proposes, is answered after making starching
Wearability, tensile strength and the bending strength of condensation material are improved.And the specific aim of these sizing agents is all relatively strong, in face of new
The resin system of research and development, starch finishing effect are often not ideal enough.
High-performance cyanate ester resin (CE) is because with high temperature resistant, hydroscopicity is low, craftsmanship is good, and dielectric properties are splendid etc.
Feature, becomes the another research hotspot in spacecraft high-performance composite materials field, but commercially available carbon fiber life both at home and abroad at present
Used surface size agent is directed to the resin systems such as epoxy, phenolic aldehyde, polyester, vinyl esters and double maleic amides mostly during production,
And it is less to the carbon fiber sizing agent report of cyanate ester resin system, so research is using cyanate ester resin as on the carbon fiber of matrix
Prepared by the research of slurry agent seems particularly significant.
The content of the invention
In view of the deficiencies of the prior art, the technical problem that the present invention intends to solve is to provide one kind and is used for cyanate resin base
Surface treatment of carbon fibers agent of body and preparation method thereof.
The technical solution of the present invention solution surface conditioning agent technical problem is to provide one kind and is used for cyanate resin base
The surface treatment of carbon fibers agent of body, it is characterised in that the surface conditioning agent by polyester polyol, IPDI, DBTDL, stannous octoate,
DMF solution, epoxy resin, triethylamine, DETA and the acetone composition of DMPA.
The surface conditioning agent is by the polyester polyol of 20-40 parts by weight, IPDI, 0.1-0.3 parts by weight of 5-12 parts by weight
The stannous octoates of DBTDL, 0.05-0.1 parts by weight, the mass fraction of 10-50 parts by weight be 3% DMPA DMF solution, 3-
The epoxy resin of 11 parts by weight, the triethylamine of 5-10 parts by weight, 2-6 parts by weight DET and 10-20 parts by weight acetone composition,
Each component quality sum is 100%.
The technical solution that the present invention solves the method technical problem is to provide a kind of carbon for cyanate ester resin matrix
The preparation method of fiber surface treatment agent, it is characterised in that this method comprises the following steps：
1) IPDI and polyester polyol are added in reaction kettle, and adds DBTDL and stannous octoate, risen under nitrogen protection
When warm to 85-90 DEG C reaction 2-2.5 is small；
2) 50-55 DEG C is cooled to, the DMF solution for the DMPA that mass fraction is 3% is added and is warming up to 80-85 DEG C of reaction
When 1-1.5 is small, epoxy resin is then added, the prefabricated of surface conditioning agent is made when reaction 5-6 is small at a temperature of 80-85 DEG C
Body；
3) precast body is cooled to 20-30 DEG C, adds acetone, after addition triethylamine is neutralized, be stirred for reaction 30-40
Minute；
4) add distilled water to be disperseed, DETA, chain extension 20-25 minutes, decompression are added after forming uniform and stable lotion
Acetone is distilled off, filters, that is, obtains the surface conditioning agent.
Compared with prior art, beneficial effect of the present invention is：
(1) present invention prepares the carbon fiber surface for the purpose of improving carbon fiber and cyanate ester resin interfacial combined function
Inorganic agent, the problem of compensate for there is no such commercially available carbon fiber inorganic agent product at present, and then improves the integrated machine of composite material
Tool performance.
(2) this surface conditioning agent makes carbon fiber surface add-NCO- and-NH- etc. and cyanate ester resin molecular structure phase
As characteristic group, in addition, inorganic agent also makes the oxygen content of carbon fiber surface add 8%-13%, be conducive to improve carbon fine
Dimension and the surface chemistry bonding action of resin.
(3) initial contact angle of the carbon fiber after being handled using the surface conditioning agent reduces 17%-20%, stable state contact
Angle reduces 18%-21%, effectively accelerates wet-out rate of the cyanate ester resin in carbon fiber surface, improves wetting capacity,
Reduce the groove of carbon fiber surface, while reduce the degree of roughness and specific surface area of carbon fiber surface, actually preparing
Cheng Zhong, is conducive to resin and is more fully contacted with carbon fiber surface, and then improves interface cohesion effect.
(4) interface mechanical characteristic of carbon mono-filaments is remarkably improved after being handled using the surface conditioning agent.
(5) this surface conditioning agent can increase the interlaminar shear strength of fibre reinforced cyanate resin base composite material.
(6) surface conditioning agent need to can only be made with being added to after distilled water mixed diluting in carbon fiber device for sizing
With process is convenient, nontoxic and pollution-free.
Brief description of the drawings
Fig. 1 is the surface treatment of carbon fibers agent that the present invention is used for cyanate ester resin matrix and preparation method thereof embodiment 1
The surface infrared spectrum analysis of carbon fiber (MCF) after carbon fiber (CF) and the surface conditioning agent processing of surface conditioning agent before processing
Figure；
Fig. 2 is the surface treatment of carbon fibers agent that the present invention is used for cyanate ester resin matrix and preparation method thereof embodiment 1
X-ray photoelectron spectroscopy (XPS) analysis chart on CF surfaces；
Fig. 3 is the surface treatment of carbon fibers agent that the present invention is used for cyanate ester resin matrix and preparation method thereof embodiment 1
X-ray photoelectron spectroscopy (XPS) analysis chart on MCF surfaces；
Fig. 4 is the surface treatment of carbon fibers agent that the present invention is used for cyanate ester resin matrix and preparation method thereof embodiment 1
The carbon fiber surface contact angle variation diagram of CF and MCF；
Fig. 5 is the surface treatment of carbon fibers agent that the present invention is used for cyanate ester resin matrix and preparation method thereof embodiment 1
The photoelastic style figure of single wire fracture of CF；
Fig. 6 is the surface treatment of carbon fibers agent that the present invention is used for cyanate ester resin matrix and preparation method thereof embodiment 1
The photoelastic style figure of single wire fracture of MCF；
Embodiment
The specific embodiment of the present invention is given below.Specific embodiment is only used for that the present invention is further described, unlimited
The application scope of the claims processed.
The present invention provides a kind of surface treatment of carbon fibers agent (abbreviation surface conditioning agent) for cyanate ester resin matrix,
It is characterized in that the surface conditioning agent is by polyester polyol, isophorone diisocyanate (IPDI), dibutyl tin laurate
(DBTDL), stannous octoate (T9), dimethylformamide (DMF) solution of 2,2- dihydromethyl propionic acids (DMPA), epoxy resin,
Triethylamine (TEA), diethylenetriamine (DETA) and acetone composition；The specifically polyester polyol of 20-40 parts by weight, 5-12 weight
Stannous octoate, the mass fraction of 10-50 parts by weight of DBTDL, 0.05-0.1 parts by weight of IPDI, 0.1-0.3 parts by weight of part
DMF solution, the epoxy resin of 3-11 parts by weight, the triethylamine of 5-10 parts by weight, the DETA of 2-6 parts by weight for 3% DMPA
With the acetone of 10-20 parts by weight, each component quality sum is 100%；
The polyester polyol be phthalic acid, phthalate anhydride, phthalic acid ester, adipic acid, halo phthalic acid with
Ethylene glycol, propane diols, pentaerythrite, butanediol, 1,3 butanediols, 1,4- butanediols, diglycol, trimethylolpropane
The polyester polyol that middle one or more are polymerized, the molecular weight ranges of polyester polyol are preferably 1000-5000.
Invention also provides a kind of (letter of preparation method of the surface treatment of carbon fibers agent for cyanate ester resin matrix
Title method), it is characterised in that this method comprises the following steps：
1) IPDI and polyester polyol are added in reaction kettle, and adds DBTDL and stannous octoate as catalyst, in nitrogen
Be warming up under gas shielded 85-90 DEG C reaction 2-2.5 it is small when；
2) 50-55 DEG C is cooled to, the DMF solution for the DMPA that mass fraction is 3% is added and is warming up to 80-85 DEG C of reaction
When 1-1.5 is small, epoxy resin is then added, the prefabricated of surface conditioning agent is made when reaction 5-6 is small at a temperature of 80-85 DEG C
Body；
3) precast body is cooled to 20-30 DEG C, adding acetone reduces viscosity, after dropwise addition triethylamine is neutralized, is stirred for
Reaction 30-40 minutes；
4) add distilled water to be disperseed, DETA, 20-25 points of chain extension is added dropwise after waiting uniform and stable lotion to be formed
Clock, vacuum distillation remove acetone, and filtering, that is, obtain the surface conditioning agent.
Embodiment 1
(1) polyadipate-Isosorbide-5-Nitrae butanediol ester that 10g IPDI and 28g relative molecular weight are 3000 is weighed to add and be equipped with back
In the four-hole boiling flask for flowing condenser pipe, blender and thermometer, and 0.2g DBTDL and 0.08g T9 are added as catalyst, in nitrogen
Be warming up under gas shielded 85 DEG C reaction 2 it is small when；
(2) 55 DEG C are cooled to, adds the DMF solution 50g for the DMPA that concentration is 3%, and it is small to be warming up to 85 DEG C of reactions 1
When, 8g epoxy resin is then added, the precast body of surface conditioning agent is made when insulation reaction 5 is small at a temperature of 85 DEG C；
(3) precast body is cooled to 30 DEG C, adding acetone 18g reduces viscosity, and TEA8g is added dropwise and is neutralized, and is stirred for anti-
Answer 30 minutes；
(4) add distilled water to be disperseed, DET 5g are added dropwise dropwise after waiting uniform and stable lotion to be formed, chain extension 20 divides
Clock, vacuum distillation remove acetone, and filtering, that is, obtain surface conditioning agent.
Embodiment 2
(1) poly terephthalic acid-butanediol ester that 5g IPDI and 25g relative molecular weight are 3000 is weighed to add and be equipped with back
In the four-hole boiling flask for flowing condenser pipe, blender and thermometer, and 0.1g DBTDL and 0.05g T9 are added as catalyst, in nitrogen
Be warming up under gas shielded 85 DEG C reaction 2.5 it is small when；
(2) 55 DEG C are cooled to, adds the DMF solution 15g for the DMPA that concentration is 3%, and it is small to be warming up to 80 DEG C of reactions 1.5
When, 4g epoxy resin is then added, the precast body of surface conditioning agent is made when insulation reaction 6 is small at a temperature of 80 DEG C；
(3) precast body is cooled to 30 DEG C, adding acetone 10g reduces viscosity, and TEA5g is added dropwise and is neutralized, and is stirred for anti-
Answer 40 minutes；
(4) add distilled water to be disperseed, DET 3g are added dropwise dropwise after waiting uniform and stable lotion to be formed, chain extension 20 divides
Clock, vacuum distillation remove acetone, and filtering, that is, obtain surface conditioning agent.
Embodiment 3
(1) weigh poly- added to adipic acid-propylene glycol ester that 8g IPDI and 30g relative molecular weight are 4000 and reflux is housed
In the four-hole boiling flask of condenser pipe, blender and thermometer, and 0.15g DBTDL and 0.06g T9 are added as catalyst, in nitrogen
Be warming up under gas shielded 85 DEG C reaction 2 it is small when；
(2) 55 DEG C are cooled to, adds the DMF solution 40g for the DMPA that concentration is 3%, and it is small to be warming up to 80 DEG C of reactions 1
When, 6g epoxy resin is then added, the precast body of surface conditioning agent is made when insulation reaction 5 is small under 80 degree celsius temperatures；
(3) precast body is cooled to 30 DEG C, adding acetone 15g reduces viscosity, and TEA7g is added dropwise and is neutralized, and is stirred for anti-
Answer 30 minutes；
(4) add distilled water to be disperseed, DET 4g are added dropwise dropwise after waiting uniform and stable lotion to be formed, chain extension 20 divides
Clock, vacuum distillation remove acetone, and filtering, that is, obtain surface conditioning agent.
With surface conditioning agent obtained above to being tested after carbon fiber processing.
With infrared tester in 4000-400cm-1In the range of to the carbon fiber (CF) of surface conditioning agent before processing and surface
Carbon fiber (MCF) surface after inorganic agent processing is scanned, and observes the change of its surface functional group, wherein embodiment 1 is red
External spectrum test chart is as shown in Figure 1, the infrared spectrogram for the CF that compares, and the infrared spectrogram of MCF is in wavelength 2280cm-1With
3350cm-1Place have also appeared characteristic group (- NCO- asymmetric stretching vibration peaks and the-NH- stretching vibrations of polyurethane (PU)
Peak).
Element composition and the oxygen-containing change in surface with XPS testers test carbon fiber surface, test result such as Fig. 2 institutes of CF
Show, preparing MCF with 1 method of embodiment, the results are shown in Figure 3, then standard is done with C1s (B.E=285.0eV), by organic
The chemical potential in-migration of difference C1s determines the functional group of carbon fiber surface, the comparing result such as institute of table 1 of each embodiment in compound
Show, the results showed that there occurs obvious change, the content of active function groups by the ratio between carbon fiber surface O and C element after surface treatment
It increased, embodiment 1 adds 12.27%, and embodiment 2 adds 8.56%, and embodiment 3 adds 10.33%.
The C1s swarmings analytical table (%) of 1 surface conditioning agent of table carbon fiber surface before and after the processing
It is fine to the carbon before and after starching with intravenous infusion contact angle/interfacial tension measuring instrument using liquid cyanate resin as Fluid Contacting
Dimension surface contact angle measures, and the test result of the MCF of CF and the preparation of 1 method of embodiment is as shown in Figure 4, the results showed that processing
(MCF) has reduced compared with the initial contact angle and Steady-state contact angles of before processing (CF) afterwards, and the results are shown in Table 2.
2 surface conditioning agent of table before and after the processing carbon fiber surface contact angle reduce situation
| Initial contact angle | Steady-state contact angles | |
| CF | 85° | 51° |
| Embodiment 1MCF | 68.5° | 40.5° |
| Embodiment 2MCF | 69.9° | 41.6° |
| Embodiment 3MCF | 69° | 40.8° |
Using polarizing fiber tensilometer, rate of extension 0.0005mm/s, in polarized light microscopy Microscopic observation drawing process, obtains
To the photoelastic style figure of single wire fracture of cyanate ester resin base carbon fiber composite material.The tensile diagram of CF is as shown in figure 5, embodiment 1
MCF as shown in fig. 6, can be seen that two kinds of carbon fiber complex systems all generate interfacial detachment phenomenon by picture, but MCF's is disconnected
Point quantity increase, interface performance make moderate progress.Monofilament tensile strength, monofilament interface shear strength and fibre under the critical length of MCF
The dimension beam interlaminar shear strength CF that compares has a certain upgrade, table 3 specific as follows.
The mechanical property of 3 surface conditioning agent of table material before and after the processing
The present invention does not address part and is suitable for the prior art.
Claims (5)
1. a kind of surface treatment of carbon fibers agent for cyanate ester resin matrix, it is characterised in that the surface conditioning agent is more by polyester
First alcohol, IPDI, DBTDL, stannous octoate, the DMF solution of DMPA, epoxy resin, triethylamine, DETA and acetone composition.
2. the surface treatment of carbon fibers agent according to claim 1 for cyanate ester resin matrix, it is characterised in that the table
Surface treatment agent is by the polyester polyol of 20-40 parts by weight, DBTDL, 0.05- of IPDI, 0.1-0.3 parts by weight of 5-12 parts by weight
DMF solution, the epoxy of 3-11 parts by weight of the stannous octoate of 0.1 parts by weight, the DMPA that the mass fraction of 10-50 parts by weight is 3%
Resin, the triethylamine of 5-10 parts by weight, 2-6 parts by weight DET and 10-20 parts by weight acetone composition, each component quality sum
For 100%.
3. the surface treatment of carbon fibers agent according to claim 1 for cyanate ester resin matrix, it is characterised in that described
Polyester polyol is phthalic acid, phthalate anhydride, phthalic acid ester, adipic acid, halo phthalic acid and ethylene glycol, the third two
It is one or more of in alcohol, pentaerythrite, butanediol, 1,3 butanediols, 1,4- butanediols, diglycol, trimethylolpropane
The polyester polyol being polymerized.
4. the surface treatment of carbon fibers agent according to claim 1 for cyanate ester resin matrix, it is characterised in that polyester
The molecular weight ranges of polyalcohol are 1000-5000.
5. the preparation method of a kind of surface treatment of carbon fibers agent for cyanate ester resin matrix, it is characterised in that this method includes
Following steps：
1）IPDI and polyester polyol are added in reaction kettle, and add DBTDL and stannous octoate, is warming up under nitrogen protection
When 85-90 DEG C of reaction 2-2.5 is small；
2）50-55 DEG C is cooled to, the DMF solution for the DMPA that mass fraction is 3% is added and is warming up to 80-85 DEG C of reaction 1-1.5
Hour, epoxy resin is then added, the precast body of surface conditioning agent is made when reaction 5-6 is small at a temperature of 80-85 DEG C；
3）Precast body is cooled to 20-30 DEG C, adds acetone, after addition triethylamine is neutralized, is stirred for 30-40 points of reaction
Clock；
4）Add distilled water to be disperseed, DETA, chain extension 20-25 minutes, vacuum distillation are added after forming uniform and stable lotion
Acetone is removed, filtering, that is, obtain the surface conditioning agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711220379.7A CN108004780B (en) | 2017-11-29 | 2017-11-29 | Carbon fiber surface treating agent for cyanate ester resin matrix and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711220379.7A CN108004780B (en) | 2017-11-29 | 2017-11-29 | Carbon fiber surface treating agent for cyanate ester resin matrix and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5584476A (en) * | 1978-12-21 | 1980-06-25 | Toray Industries | Sizing agent for carbon fiber |
| CN104119831A (en) * | 2014-07-29 | 2014-10-29 | 上海揽胜绿色材料科技有限公司 | Waterborne polyurethane adhesive applied to RFID (radio frequency identification devices) antenna lamination and preparation method thereof |
| CN104508022A (en) * | 2012-07-25 | 2015-04-08 | 东丽株式会社 | Prepreg and carbon-fiber-reinforced composite material |
-
2017
- 2017-11-29 CN CN201711220379.7A patent/CN108004780B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5584476A (en) * | 1978-12-21 | 1980-06-25 | Toray Industries | Sizing agent for carbon fiber |
| CN104508022A (en) * | 2012-07-25 | 2015-04-08 | 东丽株式会社 | Prepreg and carbon-fiber-reinforced composite material |
| CN104119831A (en) * | 2014-07-29 | 2014-10-29 | 上海揽胜绿色材料科技有限公司 | Waterborne polyurethane adhesive applied to RFID (radio frequency identification devices) antenna lamination and preparation method thereof |
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