CN116299808A - Durable high-retroreflection reflecting material - Google Patents
Durable high-retroreflection reflecting material Download PDFInfo
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- CN116299808A CN116299808A CN202310325546.3A CN202310325546A CN116299808A CN 116299808 A CN116299808 A CN 116299808A CN 202310325546 A CN202310325546 A CN 202310325546A CN 116299808 A CN116299808 A CN 116299808A
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 230000001070 adhesive effect Effects 0.000 claims abstract description 109
- 239000000853 adhesive Substances 0.000 claims abstract description 108
- 239000010410 layer Substances 0.000 claims abstract description 108
- 239000012790 adhesive layer Substances 0.000 claims abstract description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 claims abstract description 45
- 239000004332 silver Substances 0.000 claims abstract description 45
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 39
- 239000011324 bead Substances 0.000 claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000007747 plating Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims description 56
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000004814 polyurethane Substances 0.000 claims description 24
- 229920002635 polyurethane Polymers 0.000 claims description 24
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 14
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 20
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 description 21
- 239000002994 raw material Substances 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 9
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 150000003573 thiols Chemical class 0.000 description 6
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- -1 glycol ester Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 3
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000009430 construction management Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/12—Reflex reflectors
- G02B5/126—Reflex reflectors including curved refracting surface
- G02B5/128—Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a durable high-retroreflection reflecting material, and belongs to the technical field of reflecting materials. In order to solve the problem of poor adhesion, the durable high-retroreflection reflecting material comprises a substrate layer, a silver coating and a glass bead layer, wherein an adhesive layer I is arranged between the substrate layer and the silver coating, an adhesive layer II is arranged between the glass bead layer and the silver coating, the glass beads of the glass bead layer are inlaid on the adhesive layer II, and the adhesive layer I and the adhesive layer II are respectively formed by adopting an adhesive containing epoxy trimethoxy silane coupling agent independently; the first bonding layer is bonded with the silver plating layer through a third bonding layer; and the bonding layer II is bonded with the bonding layer IV between the silver plating layers, and the bonding layer III and the bonding layer IV are respectively and independently formed by adopting an adhesive containing a sulfhydryl silane coupling agent. The light reflecting material has the advantages of good durability and high retroreflectivity.
Description
Technical Field
The invention relates to a durable high-retroreflection reflecting material, and belongs to the technical field of reflecting materials.
Background
The reflective material is used for generating strong reflective effect under the irradiation of a light source, has the purposes of marking, warning and the like, also provides safety guarantee for travelers at night, is widely applied to the fields of life-saving clothes, traffic police clothes, reflective cloth or reflective hot stickers and the like, and is also added on working clothes for personnel safety in the operations of highway construction management, fire protection, maritime work, transportation and the like, and the application field of the reflective material is continuously expanded along with the maturation of the production process and the technology of the reflective material.
The reflective component of the reflective material generally adopts metals such as aluminum, silver and the like as a reflective layer, and the aluminum has active properties and is easy to be corroded by acid and alkali to blacken, so that the reflective performance is lost, and silver metal is also adopted as the reflective layer in order to avoid the corrosion phenomenon. The prior reflective material comprises the steps of planting bead glass beads in a carrier film, coating a glue layer on the surface, forming a metal reflective layer such as a silver metal reflective layer on the surface of the glue layer, bonding a substrate layer to form a corresponding reflective material, and further covering a hot melt adhesive layer and a fabric layer on the surface of the metal reflective layer to obtain a corresponding reflective hot-paste or reflective cloth product. However, the adhesive force between the adhesive and the metal layer used in the existing reflective material is poor, the phenomenon of falling off due to poor adhesion is easy to occur, and the durability is poor, and the aging is easy to occur in the use process, so that the performance of the product such as the retroreflection coefficient is reduced, and the reflective performance is reduced.
Disclosure of Invention
The invention aims at the defects in the prior art, provides a durable high-retroreflection reflecting material, and solves the problem of improving the interlayer bonding adhesive force performance.
The invention aims at realizing the technical scheme that the durable high-retroreflection reflecting material comprises a substrate layer, a silver coating and a glass bead layer, wherein a bonding layer I is arranged between the substrate layer and the silver coating, a bonding layer II is arranged between the glass bead layer and the silver coating, and the glass beads of the glass bead layer are inlaid on the bonding layer II; the first bonding layer is bonded with the silver plating layer through a third bonding layer; and the bonding layer II is bonded with the bonding layer IV between the silver plating layers, and the bonding layer III and the bonding layer IV are respectively and independently formed by adopting an adhesive containing a sulfhydryl silane coupling agent.
According to the invention, the adhesive containing the epoxy trimethoxy silane coupling agent and the adhesive containing the mercapto silane coupling agent are adopted to act together, so that the double-layer adhesive property of the glass bead and the silver coating is realized by the adhesive layer, the integral bonding force between layers is improved, and the phenomenon that the adhesive layer is easy to fall off from the glass bead or the silver coating is effectively prevented. Specifically, the bonding layer I and the bonding layer III between the bonding layer II and the silver coating are formed by adopting an adhesive containing a sulfhydryl silane coupling agent respectively and independently, the added sulfhydryl silane coupling agent can have good bonding performance on silver metal, the sulfhydryl silane coupling agent can form a bonding structure layer on the surface of silver metal through the action of chemical adsorption, so that the bonding force between the bonding layer I and the silver coating is effectively improved, but the bonding property between the sulfhydryl silane coupling agent and the glass beads is poor, so that the bonding layer II is bonded under the glass beads firstly, the bonding layer II adopts the adhesive containing the epoxy trimethoxy silane coupling agent to have good bonding adhesive force on the glass beads, the effect of improving the bonding force on the whole is realized, the adhesive containing the epoxy trimethoxy silane coupling agent and the adhesive containing the sulfhydryl silane coupling agent also have good durability, the bonding adhesive force is better ensured, the phenomenon of not easily falling off is avoided, and the light reflecting material also has the advantage of high retroreflection coefficient.
In the durable high retroreflective material described above, preferably, the mercaptosilane coupling agent is selected from one or a mixture of several of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane. Compared with the existing physical bonding mode, the bonding force between the sulfur in the mercapto group in the mercapto silane coupling agent and the metallic silver can be better improved, so that the phenomenon of easy falling is effectively avoided; and the addition of the sulfhydryl silane coupling agent can better ensure the integral retroreflection coefficient of the reflecting material, and has the advantage of good optical performance. As a still further preferred, the mercaptosilane coupling agent is a mixture of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane, and the mass ratio of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane is 1:0.3 to 0.5:0.4 to 0.6.
In the durable high retroreflective material described above, preferably, the adhesive containing an epoxy trimethoxysilane coupling agent comprises the following components in parts by weight:
polyurethane adhesive: 30-40; curing agent I: 5 to 10; epoxy trimethoxysilane coupling agent: 0.5 to 1.0. The method is equivalent to the effect that the adopted polyurethane adhesive is taken as a main raw material to better ensure the light reflecting performance and the bonding force by adding the epoxy trimethoxy silane coupling agent into the polyurethane adhesive. The polyurethane adhesive used in the light-reflecting material may be a polyurethane adhesive, such as an adhesive containing a urethane group (-NHCOO-) or an isocyanate group (-NCO) in the molecular chain.
In the durable high retroreflective material, preferably, the adhesive containing the mercaptosilane coupling agent is mainly prepared from the following raw materials in parts by weight:
polyurethane adhesive: 30-40; and (2) a curing agent II: 5 to 10; mercaptosilane coupling agent: 0.5 to 1.0. The polyurethane adhesive is used as the main raw material, so that the light reflecting performance and the adhesive binding force can be better ensured. The polyurethane adhesive is adopted as the main raw material, so that the reflection performance and the bonding force can be better ensured; also, the polyurethane adhesive used in the light-reflecting material may be used as the polyurethane adhesive, for example, an adhesive having a urethane group (-NHCOO-) or an isocyanate group (-NCO) in the molecular chain.
As a further preferred aspect, the first and second curing agents are each independently selected from one or both of an epoxy resin curing agent and an aromatic polyisocyanate based on toluene diisocyanate having an NCO content of 10% to 15%.
In the durable high retroreflective sheeting, the adhesive containing a mercaptosilane coupling agent preferably contains 0.2 to 0.4 parts by weight of a mercaptan. The curing effect of the adhesive can be better promoted by adding a small amount of mercaptan, and meanwhile, the adopted mercaptan also contains sulfur atoms, so that the binding force with the metal silver coating can be better realized, and the binding effect is further realized. Preferably, the thiol is one or more of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate). In the best scheme, the thiol adopts a mixture of trimethylolpropane tri (3-mercaptopropionate) and di (3-mercaptopropionic acid) glycol ester, and the mass ratio of the trimethylolpropane tri (3-mercaptopropionic acid) to the di (3-mercaptopropionic acid) glycol ester is 1:0.3 to 0.4.
In the durable high retroreflective material, the adhesive containing an epoxy trimethoxysilane coupling agent preferably contains 5.0 to 8.0 parts by weight of an acrylate adhesive. Because the glass beads are partially exposed on the surface, the bonding force between the glass beads and the bonding force between the glass beads can be better improved by adding a small amount of acrylate adhesive into the adhesive containing the epoxy trimethoxy silane coupling agent, so that the bonding effect between the glass beads and the bonding force between the glass beads is improved, the falling phenomenon is not easy to occur, the interlayer bonding effect is better, and the effect of high retroreflection coefficient is achieved as a whole. The acrylic ester is one or more selected from n-butyl acrylate, n-octyl acrylate and hydroxyethyl acrylate.
In the durable high retroreflective sheeting described above, the retroreflective sheeting is preferably selected from retroreflective sheeting or retroreflective stickers. The reflecting material can be used in different modes according to different environments and places of practical use.
In summary, compared with the prior art, the invention has the following advantages:
1. the invention can form a bonding structure layer on the surface of silver metal through the chemical adsorption action by utilizing the added sulfhydryl silane coupling agent, so that the bonding force between the silver metal and the sulfhydryl silane coupling agent is effectively improved, the bonding agent containing epoxy trimethoxy silane coupling agent and the bonding agent containing sulfhydryl silane coupling agent are adopted, the durability is good, and the reflective material has the advantage of high retroreflection coefficient.
2. By making the adhesive containing the sulfhydryl silane coupling agent contain mercaptan, the bonding force between the bonding layer and silver metal of the metal silver plating layer can be better improved, and the bonding performance can be better improved.
Drawings
Fig. 1 is a schematic structural view of a reflective material of the present invention.
In the figure, 1, a substrate layer; 2. an adhesive layer I; 3. silver plating; 4. an adhesive layer II; 5. a glass bead layer; 6. an adhesive layer III; 7. and a bonding layer IV.
Detailed Description
The technical scheme of the present invention will be further specifically described by means of specific examples and drawings, but the present invention is not limited to these examples.
Example 1
The durable high-retroreflection reflecting material comprises a substrate layer 1, a silver coating layer 3 and a glass bead layer 5, wherein an adhesive layer I2 is arranged between the substrate layer 1 and the silver coating layer 3, an adhesive layer II 4 is arranged between the silver coating layer 3 and the glass bead layer 5, the glass beads of the glass bead layer 5 are inlaid on the adhesive layer II 4, the inlaid depth is equal to the common depth, and more importantly, the adhesive layer I2 and the adhesive layer II 4 are respectively independently formed by adopting an adhesive containing epoxy trimethoxysilane coupling agent; the first bonding layer 2 is bonded with the silver plating layer 3 through the third bonding layer 6; and the second adhesive layer 4 is adhered to the silver plating layer 3 through the fourth adhesive layer 7, and the third adhesive layer 6 and the fourth adhesive layer 7 are respectively and independently formed by adopting an adhesive containing a sulfhydryl silane coupling agent. The reflective material can be processed into a reflective film, a reflective hot patch and the like according to actual needs, and can be further formed by reflective cloth or a product such as a fabric. The third adhesive layer 6 and the fourth adhesive layer 7 are preferably coated on both sides of the silver plating layer 3 by coating or knife coating, that is, the contact surface of the silver plating layer 3 is coated with the adhesive 6 and the adhesive layer 7 formed by the corresponding adhesive containing the mercaptosilane coupling agent. The formed bonding layer is thinner, and the effect of improving the bonding force can be realized.
In a more preferred embodiment, the mercaptosilane coupling agent is one or more selected from the group consisting of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane. The adhesive used in the third adhesive layer 6 and the fourth adhesive layer 7 may be the same or different in component ratio, preferably the same adhesive, and the mercaptosilane coupling agent in the adhesive containing the mercaptosilane coupling agent in the third adhesive layer 6 and the fourth adhesive layer 7 is preferably a mixture of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane, and the mass ratio of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane is 1:0.3 to 0.5:0.4 to 0.6, and the preferable mass ratio is 1:0.4:0.5. the bonding effect between the metal silver and the surface of the metal silver can be better ensured.
In a further embodiment, in practical use, the adhesive containing the epoxy trimethoxysilane coupling agent preferably comprises the following components in parts by weight:
polyurethane adhesive: 30-40; curing agent I: 5 to 10; epoxy trimethoxysilane coupling agent: 0.5 to 1.0.
The adhesive containing the mercapto silane coupling agent is mainly prepared from the following raw materials in parts by weight:
polyurethane adhesive: 30-40; and (2) a curing agent II: 5 to 10; mercaptosilane coupling agent: 0.5 to 1.0. More preferably, the first and second curing agents are independently selected from one or two of epoxy resin curing agents and aromatic polyisocyanates based on toluene diisocyanate with NCO content of 10% -15%.
The adhesive containing the mercaptosilane coupling agent further contains 0.2 to 0.4 parts by weight of mercaptan. The adopted mercaptan also contains sulfur atoms, so that the binding force with the metal silver of the metal silver plating layer can be better realized, and the binding effect is further improved. One or more of pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate) and pentaerythritol tetrakis (mercaptoacetate) may be used. Preferably, the thiol is a mixture of trimethylolpropane tri (3-mercaptopropionate) and ethylene glycol di (3-mercaptopropionate) in a mass ratio of 1:0.3 to 0.4.
The performance test of the reflective material provided by the invention shows that the reflective material has the advantage of high bonding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard, the bonding durability is high, the advantage of high bonding adhesive force is realized, and the reflective material has the effect of high retroreflection coefficient.
Example 2
The durable high-retroreflection reflecting material comprises a substrate layer 1, a silver coating layer 3 and a glass bead layer 5, wherein an adhesive layer I2 is arranged between the substrate layer 1 and the silver coating layer 3, an adhesive layer II 4 is arranged between the silver coating layer 3 and the glass bead layer 5, the glass beads of the glass bead layer 5 are inlaid on the adhesive layer II 4, and the adhesive layer I2 and the adhesive layer II 4 are formed by adopting an adhesive containing epoxy trimethoxysilane coupling agent; the first bonding layer 2 is bonded with the silver plating layer 3 through the third bonding layer 6; and the second bonding layer 4 is bonded with the silver plating layer 3 through the fourth bonding layer 7, and the third bonding layer 6 and the fourth bonding layer 7 are formed by adopting an adhesive containing a sulfhydryl silane coupling agent.
Wherein the first bonding layer 2 and the second bonding layer 4 are both adhesives containing epoxy trimethoxy silane coupling agents, and the adhesives containing epoxy trimethoxy silane coupling agents are prepared from the following raw materials in parts by weight:
polyurethane adhesive: 40, a step of performing a; curing agent I: 10; epoxy trimethoxysilane coupling agent: 1.0. the curing agent is epoxy resin curing agent.
The adhesive containing the sulfhydryl silane coupling agent adopted by the third adhesive layer 6 and the fourth adhesive layer 7 comprises the following raw materials in parts by weight:
polyurethane adhesive: 40, a step of performing a; and (2) a curing agent II: 10; mercaptosilane coupling agent: 0.5 to 1.0 percent, wherein the curing agent II is epoxy resin curing agent, and the mercapto silane coupling agent is 3-mercapto methyl dimethoxy silane. The performance test of the reflective material of the invention shows that the reflective material has the advantage of high binding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard, and the reflective material has the effect of high retroreflectivity, and the retroreflectivity is 0.2/-4 and reaches 750 cd.lx at an observation angle of 0.2 DEG and an incidence angle of-4 DEG -1 ·m -2 The above.
Example 3
Referring to fig. 1, the durable high retroreflective material of this embodiment is substantially the same as that of embodiment 2, except that the first adhesive layer 2 and the second adhesive layer 4 are both adhesives containing epoxy trimethoxysilane coupling agent, wherein the adhesives containing epoxy trimethoxysilane coupling agent are prepared from the following raw materials in parts by weight:
polyurethane adhesive: 30; curing agent I: 5, a step of; epoxy trimethoxysilane coupling agent: 0.5. the curing agent is epoxy resin curing agent.
Wherein the adhesive containing the sulfhydryl silane coupling agent adopted by the third adhesive layer 6 and the fourth adhesive layer 7 comprises the following raw materials in parts by weight:
polyurethane adhesive: 30; and (2) a curing agent II: 5.0; mercaptosilane coupling agent: 0.8, the curing agent II is epoxy resin curing agent, and the mercapto silane coupling agent is 3-mercapto propyl trimethoxy silane. The performance test of the reflective material of the invention shows that the reflective material has the advantage of high binding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard, the durability is high, the adhesion between layers is high, and the reflective material has the advantages ofThe effect of high retroreflection coefficient is that the retroreflection coefficient of 0.2/-4 reaches 752 cd.lx at the observation angle of 0.2 degrees and the incident angle of-4 degrees -1 ·m -2 The above.
Example 4
The durable high-retroreflection reflecting material comprises a substrate layer 1, a silver coating layer 3 and a glass bead layer 5, wherein an adhesive layer I2 is arranged between the substrate layer 1 and the silver coating layer 3, an adhesive layer II 4 is arranged between the silver coating layer 3 and the glass bead layer 5, the glass beads of the glass bead layer 5 are inlaid on the adhesive layer II 4, and the adhesive layer I2 and the adhesive layer II 4 are formed by adopting an adhesive containing epoxy trimethoxysilane coupling agent; the first bonding layer 2 is bonded with the silver plating layer 3 through the third bonding layer 6; and the second bonding layer 4 is bonded with the silver plating layer 3 through the fourth bonding layer 7, and the third bonding layer 6 and the fourth bonding layer 7 are formed by adopting an adhesive containing a sulfhydryl silane coupling agent.
Wherein the first bonding layer 2 and the second bonding layer 4 are both adhesives containing epoxy trimethoxy silane coupling agents, and the adhesives containing epoxy trimethoxy silane coupling agents are prepared from the following raw materials in parts by weight:
polyurethane adhesive: 35; curing agent I: 6, preparing a base material; epoxy trimethoxysilane coupling agent: 0.8. the curing agent is epoxy resin curing agent.
The adhesive containing the sulfhydryl silane coupling agent adopted by the third adhesive layer 6 and the fourth adhesive layer 7 comprises the following raw materials in parts by weight:
polyurethane adhesive: 40, a step of performing a; and (2) a curing agent II: 10; mercaptosilane coupling agent: 0.5, the curing agent II is an epoxy resin curing agent, the mercapto silane coupling agent adopts a mixture of 3-mercapto methyl dimethoxy silane, 3-mercapto propyl triethoxy silane and 3-mercapto propyl trimethoxy silane, and the mass ratio of the 3-mercapto methyl dimethoxy silane, 3-mercapto propyl triethoxy silane and 3-mercapto propyl trimethoxy silane is 1:0.3:0.4. the performance tests of the reflective material of the invention show that the reflective material has the advantage of high binding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard, and the adhesion of the product obtained in the adhesive force advantage example 3The force is improved by more than 15 percent on the basis of the embodiment, and the effect of high retroreflectivity is achieved, and the retroreflectivity is 0.2/-4 and reaches 789 cd.lx at the observation angle of 0.2 DEG, the incident angle of-4 DEG -1 ·m -2 The above.
Example 5
Referring to fig. 1, the durable high retroreflective material of this embodiment is substantially the same as that of embodiment 4 except that the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent used for the third and fourth adhesive layers 6 and 7, and the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent comprising the following raw materials in parts by weight:
polyurethane adhesive: 40, a step of performing a; and (2) a curing agent II: 10; mercaptosilane coupling agent: 1.0, wherein the curing agent II is an epoxy resin curing agent, the mercapto silane coupling agent adopts a mixture of 3-mercapto methyl dimethoxy silane, 3-mercapto propyl triethoxy silane and 3-mercapto propyl trimethoxy silane, and the mass ratio of the 3-mercapto methyl dimethoxy silane, the 3-mercapto propyl triethoxy silane and the 3-mercapto propyl trimethoxy silane is 1:0.5:0.6. the performance tests of the reflective material of the invention show that the reflective material has the advantage of high bonding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard and has the effect of high retroreflection coefficient, the adhesive force of the product obtained in the adhesive force advantage example 3 is improved by more than 15 percent on the basis of the adhesive force in the example 3 and has the effect of high retroreflection coefficient, and the retroreflection coefficient of 0.2/-4 reaches 788 cd-lx at an observation angle of 0.2 degrees and an incidence angle of-4 degrees -1 ·m -2 The above.
Example 6
Referring to fig. 1, the durable high retroreflective material of this embodiment is substantially the same as that of embodiment 4 except that the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent used for the third and fourth adhesive layers 6 and 7, and the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent comprising the following raw materials in parts by weight:
polyurethane adhesive: 40, a step of performing a; and (2) a curing agent II: 10; mercaptosilane coupling agent: 1.0, thiol: 0.2, wherein the curing agent is epoxy resin curing agent and mercapto siliconThe alkane coupling agent adopts 3-mercapto methyl dimethoxy silane, and the mercaptan adopts trimethylolpropane tri (3-mercapto propionate). The performance test of the reflective material of the invention shows that the reflective material has the advantage of high binding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard, the adhesive force of the product obtained in the adhesive force advantage example 3 is improved by more than 30 percent on the basis of the adhesive force of the product example 3, the reflective material has the effect of high retroreflectivity, and the retroreflectivity of 0.2/-4 reaches 791 cd-lx at an observation angle of 0.2 DEG and an incidence angle of-4 DEG -1 ·m -2 The above.
Example 7
Referring to fig. 1, the durable high retroreflective material of this embodiment is substantially the same as that of embodiment 4 except that the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent used for the third and fourth adhesive layers 6 and 7, and the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent comprising the following raw materials in parts by weight:
polyurethane adhesive: 37, respectively; and (2) a curing agent II: 8, 8; mercaptosilane coupling agent: 0.8, thiol: and 0.4, wherein the curing agent II is an epoxy resin curing agent, the mercapto silane coupling agent is 3-mercapto methyl dimethoxy silane, and the mercaptan is glycol bis (3-mercapto propionic acid) ester. The performance test of the reflective material provided by the invention shows that the reflective material has the advantage of high binding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard, and the reflective material has the effect of high retroreflection coefficient. Adhesive force advantages the adhesive force of the product obtained in example 3 is improved by more than 30% on the basis of example 3, and has the effect of high retroreflectivity, and the retroreflectivity of 0.2/-4 reaches 798 cd.lx at an observation angle of 0.2 DEG, an incident angle of-4 DEG -1 ·m -2 The above.
Example 8
Referring to fig. 1, the durable high retroreflective material of this embodiment is substantially the same as that of embodiment 4 except that the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent used for the third and fourth adhesive layers 6 and 7, and the adhesive containing mercaptosilane coupling agent is replaced with the adhesive containing mercaptosilane coupling agent comprising the following raw materials in parts by weight:
polyurethane adhesive: 34; and (2) a curing agent II: 6, preparing a base material; mercaptosilane coupling agent: 0.5, thiol: 0.4, wherein the curing agent II is an epoxy resin curing agent, the mercapto silane coupling agent is 3-mercapto methyl dimethoxy silane, the mercaptan is a mixture of trimethylolpropane tri (3-mercapto propionate) and di (3-mercapto propionic acid) glycol ester, and the mass ratio of the two is 1:0.4. the performance test of the reflective material of the invention shows that the reflective material has the advantage of high binding fastness, the washing result of the product completely meets the DIN EN ISO20471 standard, the adhesive force of the product obtained in the adhesive force advantage example 3 is improved by more than 30 percent on the basis of the adhesive force of the product example 3, the reflective material has the effect of high retroreflectivity, and the retroreflectivity of 0.2/-4 reaches 802 cd-lx at an observation angle of 0.2 DEG and an incidence angle of-4 DEG -1 ·m -2 The above.
The specific embodiments described herein are offered by way of illustration only. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (8)
1. The durable high-retroreflection reflective material comprises a substrate layer (1), a silver coating layer (3) and a glass bead layer (5), wherein an adhesive layer I (2) is arranged between the substrate layer (1) and the silver coating layer (3), an adhesive layer II (4) is arranged between the glass bead layer (5) and the silver coating layer (3), and the glass beads of the glass bead layer (5) are inlaid on the adhesive layer II (4), and the durable high-retroreflection reflective material is characterized in that the adhesive layer I (2) and the adhesive layer II (4) are respectively independently formed by adopting an adhesive containing an epoxy trimethoxy silane coupling agent; the first bonding layer (2) is bonded with the silver plating layer (3) through a third bonding layer (6); the second adhesive layer (4) is adhered to the silver plating layer (3) through the fourth adhesive layer (7), and the third adhesive layer (6) and the fourth adhesive layer (7) are respectively and independently formed by adopting an adhesive containing a mercaptosilane coupling agent.
2. The durable high retroreflecting retroreflective material of claim 1 wherein the mercaptosilane coupling agent is selected from the group consisting of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.
3. The durable high retroreflective material of claim 2 wherein the mercaptosilane coupling agent is a mixture of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane and the mass ratio of 3-mercaptomethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane is 1:0.3 to 0.5:0.4 to 0.6.
4. The durable high retroreflective material of claim 2 wherein the epoxy trimethoxysilane coupling agent-containing adhesive comprises the following components in parts by weight:
polyurethane adhesive: 30-40; curing agent I: 5 to 10; epoxy trimethoxy coupling agent: 0.5 to 1.0.
5. The durable high retroreflective sheeting of claim 4 wherein the mercaptosilane coupling agent-containing adhesive is prepared from the following materials in parts by weight:
polyurethane adhesive: 30-40; and (2) a curing agent II: 5 to 10; mercaptosilane coupling agent: 0.5 to 1.0.
6. The durable high retroreflective sheeting of claim 5 wherein the first and second curing agents are each independently selected from one or both of an epoxy curing agent and an aromatic polyisocyanate based on toluene diisocyanate having an NCO content of 10% to 15%.
7. The durable high retroreflective sheeting of claims 1, 2, 3 or 4 wherein the epoxy trimethoxy coupling agent-containing adhesive comprises 5.0 to 8.0 parts by weight acrylate adhesive.
8. The durable high retroreflecting retroreflective material of claim 1 or 2 or 3 or 4, wherein the retroreflective material is selected from retroreflective sheeting and retroreflective stickers.
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| CN115785866A (en) * | 2022-11-30 | 2023-03-14 | 广州回天新材料有限公司 | Epoxy adhesive and preparation method and application thereof |
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| CN1260049A (en) * | 1997-08-01 | 2000-07-12 | 美国3M公司 | Retroreflective article having a binder layer contg. an epoxy resin an a silicone cross-linked polymer |
| JP2013074170A (en) * | 2011-09-28 | 2013-04-22 | Dainippon Printing Co Ltd | Easily adhesive layer composition, and easily adhesive rear surface protective sheet |
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