CN1421500A - Coating material for reflecting film and its production process - Google Patents
Coating material for reflecting film and its production process Download PDFInfo
- Publication number
- CN1421500A CN1421500A CN 01132354 CN01132354A CN1421500A CN 1421500 A CN1421500 A CN 1421500A CN 01132354 CN01132354 CN 01132354 CN 01132354 A CN01132354 A CN 01132354A CN 1421500 A CN1421500 A CN 1421500A
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- reflecting film
- coating material
- nano silicon
- reactive thinner
- agent
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Abstract
The coating material for regressive reflecting film consists of acrylic polyurethane prepolymer, nano silica, silane coupling agent, light initiator, leveling agent, polymerization inhibitor and active acrylate diluent. The production process of the coating material includes preparation of nano silica dispersing liquid; preparation of paint; and filtering and packing. The paint has excellent light permeability, water resistance, resistance to soiling and weather resistance. It is painted to the surface of regressive reflecting film and ultraviolet light cured to form the surface film.
Description
Technical field: the present invention relates to a kind of coated material that is used to improve the reflecting film performance, refer in particular to a kind of nano silicon that contains, can be by coated material ultraviolet light polymerization, that be used for the reflecting film surface.
Background technology:
Reflecting film is because of having regression specular reflection characteristic, and most of luminous energy that can will shine on the film reflects to light source direction, therefore is widely used in making road and traffic mark board, license plate, place name sign and billboard etc.Reflecting film is made up of transparent surface layer, glass microballon, focus layer, reflecting layer and backing layer successively.Because reflecting film mostly is outdoor application, need stand wind for a long time, drench with rain, Exposure to Sunlight and dust smeary pollute and corrode, environment for use is very abominable, therefore to tapetum lucidum, especially it is that the specification of quality of its surface material is very high, not only require light transmission good, and require to have good weather resisteant, resistance to soiling and weather resistance.
In the prior art, the surface material of this tapetum lucidum mainly uses polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), urethane (PU) or polycarbonate (PC) etc.The transparency of these materials and manufacturability all can, but still having weak point aspect other physical and chemical performances.Resistance to marring and anti-dissolubility as polymethylmethacrylate (PMMA) are relatively poor, and the resistance to soiling of urethane (PU) is not enough, even adopt heat-curable urethane, performances such as its anti-soil still can't meet the demands, and adopt polyvinyl chloride (PVC) resin, and then weather resisteant is not good enough.
Summary of the invention:
The objective of the invention is to propose a kind of coated that is used as in the coated material on reflecting film surface; because this coating contains the nanometer titanium dioxide silicon materials; adopt ultraviolet light polymerization; has good water tolerance; solvent resistance, resistance to soiling and weather resisteant, coated is outside the reflecting film surface layer; can be used as new protective layer, thereby can overcome the various defectives that prior art exists effectively.
A kind of coating material for reflecting film of the present invention, its composition comprise vinylformic acid polyester-urethane prepolymer, acrylate reactive thinner, nano silicon, silane coupling agent, light trigger, flow agent and stopper; Its consisting of by weight:
Vinylformic acid polyester-urethane prepolymer 20-50%,
Nano silicon 1-30%,
Silane coupling agent 1-5%,
Light trigger 1-8%,
Flow agent 0.1-0.8%,
Stopper 0.01-0.1%
All the other are the acrylate reactive thinner.
Wherein:
Described vinylformic acid polyester-urethane prepolymer, synthetic by polyester polyol, aliphatic isocyanates and Propylene glycol monoacrylate or Hydroxyethyl acrylate, be rich in toughness and can yellowing.
Described nano silicon is that the white carbon black of 10-40nm is through surface treatment with grind decentralized system and get by initial size.Also available commercially available nano silicon directly is scattered in the coating.Nano silicon is dispersed in the coating, can significantly improves the performance of coating.
White carbon black claims colloid silica again, can be divided into two kinds of the vapor phase process and the precipitator method, because its initial size is little, the surfactivity height is assembled the offspring for several microns easily.So need to disperse, can make the dispersion liquid that particle diameter is the nanometer grade silica of 10-50nm through surface treatment and grinding.The surface treatment agent of white carbon black adopts silane coupling agent, can select as vinyltrimethoxy silane vinyltriethoxysilane, methacryloxypropyl trimethoxy silane or aminopropyl triethoxysilane for use.Methoxy or ethoxy in the silane coupled agent molecule be easy to colloid silica in hydroxyl reaction, help the dispersion of silicon-dioxide, and the vinyl in its molecule is crosslinked with other components in ultraviolet light polymerization reaction.The grinding dispersion treatment of described white carbon black is carried out in reactive thinner, and the nanometer grade silica dispersion liquid after the dispersion can be directly used in the coating of the present invention.
Described reactive thinner can adopt the acrylate reactive thinner, as the Macrogol 200 diacrylate, and ethoxylation neopentylglycol diacrylate, the Viscoat 295 of ethoxylation; The Triethylene glycol diacrylate, tripropylene glycol dipropyl enol ester, neopentylglycol diacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410 also can adopt wherein two kinds or multiple mixing use.These reactive thinners have less viscosity and bigger polarity, help the dispersion of silicon-dioxide.
Described light trigger is dimethyl hydroxyl methyl phenyl ketone or 1-hydroxy-cyclohexyl methyl phenyl ketone.
Described flow agent is the Soxylat A 25-7 radical siloxane.
Described stopper is a p-methyl phenol.
The production technique of coating material for reflecting film of the present invention is:
Step 1 is mixed white carbon black, organosilane connection agent and esters of acrylic acid reactive thinner by proportioning after, in ball mill or sand mill or high speed dispersor, disperse, up to obtaining the silica dispersions that particle diameter is 10-50nm, jitter time is relevant with dispersion efficiency, generally need 1-30 hour, and control with transmission electron microscopy observation.
The nano silicon dispersion liquid that step 2 makes with vinylformic acid polyurethane(s) performed polymer, by step 1 or directly adopt commercially available nano silicon, esters of acrylic acid reactive thinner, light trigger, flow agent and stopper to mix by proportioning after put into mixing tank, be heated to about 70 ℃, mix.
Step 3 is filtered the back packing with 300 mesh sieves.
The invention has the advantages that:
1. employing ultraviolet light polymerization, the non-volatility solvent, pollution-free, production efficiency is very high.
2. high boiling reactive thinner and vinylformic acid polyester-urethane prepolymer all are cross-linked into thermoset coating rapidly in light-initiated free radical reaction, this coating is insoluble, do not dissolve, and have good thermotolerance and solvent resistance;
3. aliphatics vinylformic acid polyurethane is under sun exposure, and not yellowing has good weather resisteant;
4. be dispersed in the nanometer grade silica particle in the coating, under the effect of organo silane coupling agent, combine by chemical action, form inorganic-organic composite material, make coating have better scratch resistance, water tolerance and weather resisteant with organic coating;
5. nano silicon is undamped substantially to visible light, with thickness is that the coating of the present invention of 5-10 μ m is coated on the PVC basement membrane that thickness is 20-50 μ m, the transmittance that at wavelength is the visible region of 400-700nm is more than 96% of basement membrane of coating, but UV-light there are scattering and shielding effect, therefore add the brightness that nano silicon can not influence tapetum lucidum, but can improve its ageing resistance;
6. coating of the present invention has good adhesive with the reflecting film that with PVC, PMMA, PU and PC is surface material.
Embodiment:
Now the invention will be further described in conjunction with two embodiment.
Embodiment 1
Step 1 by weight, in 28 parts of precipitated silicas, add 45 parts of 22 parts of thinner Macrogol 200 diacrylates and tri (propylene glycol) diacrylates, and after 5 parts of mixing of silane coupling agent vinyl triethoxyl silane, put into sand mill and grind dispersion 6 hours, make the nano silicon dispersion liquid, and detect the particle diameter of control silicon dioxide granule below 50nm with transmission electron microscope.
Step 2 is got 35 parts of vinylformic acid polyurethane(s) performed polymers, 45 parts of the nano silicon dispersion liquids that makes by step 1,10 parts of 4 parts of thinner Rocryl 410s and Viscoat 295s, 5.5 parts of light trigger dimethyl hydroxyl methyl phenyl ketones, 0.4 part of flow agent Soxylat A 25-7 radical siloxane, 0.1 part of stopper p methoxy phenol is inserted in the mixing tank, be heated to 70 ℃, mix.
Step 3 is filtered the back barrelling with 300 mesh sieves,
With the coating that makes as stated above; with roller coating or curtain coating coated on the surface layer of Polyurethane surface layer reflecting film; the thickness of coating is 10-20 μ m; ultraviolet source with 80-120W/cm2 carries out the 1-20 curing in second again, can make the topped reflecting film that coating material of the present invention is arranged as new protective layer.
Embodiment 2
Step 1 is got 24 parts of thermal silicas, add 45 parts of 26 parts of thinner Macrogol 200 diacrylates and tri (propylene glycol) diacrylates, 5 parts of silane coupling agent methacryloxypropyl trimethoxy silane, be placed on after the mixing to grind in the sand mill and disperseed 8 hours, detect with transmission electron microscope, the particle diameter of silicon dioxide granule is controlled at less than 50nm, makes the nano silicon dispersion liquid.
Step 2 is got 32 parts of vinylformic acid polyurethane(s) performed polymers, 48 parts of the nano silicon dispersion liquids that makes by step 1,10 parts of 4 parts of thinner hydroxyethyl methylacrylates and Viscoat 295s, 5.5 parts of light trigger 1-hydroxy-cyclohexyl methyl phenyl ketones, 0.4 part of flow agent Soxylat A 25-7 radical siloxane, 0.1 part of stopper p methoxy phenol is inserted in the mixing tank, be heated to 70 ℃, mix.
Step 3 is filtered the back barrelling with 300 mesh sieves.
Evidence is done kerosene, turps immersion test and 2min (standard code 1min) toluene, dimethylbenzene, methyl alcohol immersion test through 20min (standard code 10min), and the solvent resistance of coating reaches the requirement of standard code; After 36h (standard code 24h) high temperature test and 100h (standard code 72h) low-temperature test, the resistance to elevated temperatures of coating and resistance to low temperature all reach standard-required; Through the salt-fog test in 8 cycles (5 cycles of standard code), corrosion resistance of coating reaches standard-required.This shows that the physical and chemical performance of coating of the present invention is very stable.
Claims (10)
1. coating material for reflecting film, its composition comprises vinylformic acid polyester-urethane prepolymer, acrylate reactive thinner, nano silicon, silane coupling agent, light trigger, flow agent and stopper; Its consisting of by weight:
Vinylformic acid polyester-urethane prepolymer 20-50%,
Nano silicon 1-30%,
Silane coupling agent 1-5%, light trigger 1-8%,
Flow agent 0.1-0.8%,
Stopper 0.01-0.1%
All the other are the acrylate reactive thinner.
2. according to the described coating material for reflecting film of claim 1, it is characterized in that described vinylformic acid polyester-urethane prepolymer, synthetic by polyester polyol, aliphatic isocyanates and Propylene glycol monoacrylate or Hydroxyethyl acrylate.
3. according to the described coating material for reflecting film of claim 1, it is characterized in that described nano silicon, is that the white carbon black of 10-40nm gets through surface treatment and grinding decentralized system by initial size.
4. according to the described coating material for reflecting film of claim 1, it is characterized in that described nano silicon directly is scattered in the coating with commercially available nano silicon.
5. according to the described coating material for reflecting film of claim 3, it is characterized in that the surface treatment agent of described white carbon black adopts silane coupling agent, it grinds dispersion treatment and carries out in reactive thinner.
6. according to the described coating material for reflecting film of claim 5, the surface treatment agent silane coupling agent that it is characterized in that described white carbon black, can select for use as vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane or aminopropyl triethoxysilane.
7. according to claim 1 or 5 described coating material for reflecting film, it is characterized in that described reactive thinner can adopt the acrylate reactive thinner, as the Macrogol 200 diacrylate, the ethoxylation neopentylglycol diacrylate, the Viscoat 295 of ethoxylation, the Triethylene glycol diacrylate, tripropylene glycol dipropyl enol ester, neopentylglycol diacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410 also can adopt wherein two kinds or multiple mixing use.
8. according to the described coating material for reflecting film of claim 1, it is characterized in that described light trigger is dimethyl hydroxyl methyl phenyl ketone or 1-hydroxy-cyclohexyl methyl phenyl ketone.
9. according to the described coating material for reflecting film of claim 1, it is characterized in that described flow agent is the Soxylat A 25-7 radical siloxane, described stopper is a p-methyl phenol.
10. according to the production technique of the described coating material for reflecting film of claim 1:
Step 1 is mixed white carbon black, organosilane connection agent and esters of acrylic acid reactive thinner by proportioning after, in ball mill or sand mill or high speed dispersor, disperse, up to obtaining the silica dispersions that particle diameter is 10-50nm, jitter time is relevant with dispersion efficiency, generally need 1-30 hour, and control with transmission electron microscopy observation.
The nano silicon dispersion liquid that step 2 makes with vinylformic acid polyurethane(s) performed polymer, by step 1 or directly adopt commercially available nano silicon, esters of acrylic acid reactive thinner, light trigger, flow agent and stopper to mix by proportioning after put into mixing tank, be heated to about 70 ℃, mix.
Step 3 is filtered the back packing with 300 mesh sieves.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01132354 CN1421500A (en) | 2001-11-29 | 2001-11-29 | Coating material for reflecting film and its production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01132354 CN1421500A (en) | 2001-11-29 | 2001-11-29 | Coating material for reflecting film and its production process |
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| CN1421500A true CN1421500A (en) | 2003-06-04 |
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| CN 01132354 Pending CN1421500A (en) | 2001-11-29 | 2001-11-29 | Coating material for reflecting film and its production process |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323092C (en) * | 2005-01-20 | 2007-06-27 | 辽宁大学 | Modification method for graft polymerization of acrylic ester of silicane coupled to Nano SiO2 |
| WO2008077722A1 (en) | 2006-12-23 | 2008-07-03 | Evonik Degussa Gmbh | Silica- and dispersant-containing radiation-curable formulations with increased corrosion protection on metal substrates |
| WO2008077673A1 (en) | 2006-12-23 | 2008-07-03 | Evonik Degussa Gmbh | Silica-containing radiation-curable formulations with increased corrosion protection on metal substrates |
| CN101851466A (en) * | 2010-06-02 | 2010-10-06 | 长沙华良涂料有限公司 | Antistatic abrasion-resistant UV coating and preparation method thereof |
| CN101985531A (en) * | 2010-03-17 | 2011-03-16 | 上海宏盾防伪材料有限公司 | Photosensitive coating and preparation method thereof and photosensitive film made by utilizing same |
| CN101486591B (en) * | 2008-01-17 | 2013-01-09 | 金在浩 | Water soluble photo-curable antistatic composition and conductive hard tile flooring material coated with the same |
| CN103214888A (en) * | 2013-03-25 | 2013-07-24 | 佛山佛塑科技集团股份有限公司 | Coating liquid for preparation of weather resistant optical grade hard coating film and corresponding hard coating film |
| CN104277517A (en) * | 2014-10-09 | 2015-01-14 | 南京华格电汽塑业有限公司 | UV (ultraviolet) finish paint back-spraying water as well as preparation method and application thereof |
| CN104293166A (en) * | 2014-10-28 | 2015-01-21 | 成都纳硕科技有限公司 | Ultra-violet curing water-based coating with high mechanical strength |
| WO2016127452A1 (en) * | 2015-02-15 | 2016-08-18 | 广东天安新材料股份有限公司 | Preparation method and application of electron beam curable paint and electron beam curable coating |
| CN109085730A (en) * | 2018-08-18 | 2018-12-25 | 南阳理工学院 | A kind of eye-witness report reflector |
| JP2019081330A (en) * | 2017-10-31 | 2019-05-30 | スリーエム イノベイティブ プロパティズ カンパニー | Graphic film for license plate, and method of manufacturing license plate using the graphic film |
| CN110760222A (en) * | 2018-07-27 | 2020-02-07 | 深圳光启超材料技术有限公司 | Yellow ink and preparation method and application thereof |
| CN114621614A (en) * | 2021-11-04 | 2022-06-14 | 苏州瀚海新材料有限公司 | Photocureable coating and preparation method thereof |
-
2001
- 2001-11-29 CN CN 01132354 patent/CN1421500A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323092C (en) * | 2005-01-20 | 2007-06-27 | 辽宁大学 | Modification method for graft polymerization of acrylic ester of silicane coupled to Nano SiO2 |
| US8283040B2 (en) | 2006-12-23 | 2012-10-09 | Evonik Degussa Gmbh | Radiation-curable formulations comprising silica and dispersant and featuring enhanced corrosion control on metal substrates |
| WO2008077722A1 (en) | 2006-12-23 | 2008-07-03 | Evonik Degussa Gmbh | Silica- and dispersant-containing radiation-curable formulations with increased corrosion protection on metal substrates |
| WO2008077673A1 (en) | 2006-12-23 | 2008-07-03 | Evonik Degussa Gmbh | Silica-containing radiation-curable formulations with increased corrosion protection on metal substrates |
| CN101240143B (en) * | 2006-12-23 | 2013-03-27 | 赢创德固赛有限责任公司 | Silica- and dispersant-containing radiation-curable formulations with increased corrosion protection on metal substrates |
| CN101486591B (en) * | 2008-01-17 | 2013-01-09 | 金在浩 | Water soluble photo-curable antistatic composition and conductive hard tile flooring material coated with the same |
| CN101985531A (en) * | 2010-03-17 | 2011-03-16 | 上海宏盾防伪材料有限公司 | Photosensitive coating and preparation method thereof and photosensitive film made by utilizing same |
| CN101851466B (en) * | 2010-06-02 | 2012-03-28 | 长沙华良涂料有限公司 | Antistatic abrasion-resistant UV coating and preparation method thereof |
| CN101851466A (en) * | 2010-06-02 | 2010-10-06 | 长沙华良涂料有限公司 | Antistatic abrasion-resistant UV coating and preparation method thereof |
| CN103214888A (en) * | 2013-03-25 | 2013-07-24 | 佛山佛塑科技集团股份有限公司 | Coating liquid for preparation of weather resistant optical grade hard coating film and corresponding hard coating film |
| CN104277517A (en) * | 2014-10-09 | 2015-01-14 | 南京华格电汽塑业有限公司 | UV (ultraviolet) finish paint back-spraying water as well as preparation method and application thereof |
| CN104277517B (en) * | 2014-10-09 | 2016-08-24 | 南京华格电汽塑业有限公司 | A kind of UV finish paint returns water spray and preparation method thereof and purposes |
| CN104293166A (en) * | 2014-10-28 | 2015-01-21 | 成都纳硕科技有限公司 | Ultra-violet curing water-based coating with high mechanical strength |
| WO2016127452A1 (en) * | 2015-02-15 | 2016-08-18 | 广东天安新材料股份有限公司 | Preparation method and application of electron beam curable paint and electron beam curable coating |
| JP2019081330A (en) * | 2017-10-31 | 2019-05-30 | スリーエム イノベイティブ プロパティズ カンパニー | Graphic film for license plate, and method of manufacturing license plate using the graphic film |
| JP7074456B2 (en) | 2017-10-31 | 2022-05-24 | スリーエム イノベイティブ プロパティズ カンパニー | A graphic film for a license plate and a method for manufacturing a license plate using the graphic film. |
| CN110760222A (en) * | 2018-07-27 | 2020-02-07 | 深圳光启超材料技术有限公司 | Yellow ink and preparation method and application thereof |
| CN109085730A (en) * | 2018-08-18 | 2018-12-25 | 南阳理工学院 | A kind of eye-witness report reflector |
| CN114621614A (en) * | 2021-11-04 | 2022-06-14 | 苏州瀚海新材料有限公司 | Photocureable coating and preparation method thereof |
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| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI JIEBANG TRAFFIC SAFE NEW MATERIALS CO., Free format text: FORMER OWNER: SHANGHAI XIANPENG INDUSTRY CO., LTD. Effective date: 20031009 |
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| C41 | Transfer of patent application or patent right or utility model | ||
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Effective date of registration: 20031009 Applicant after: Shanghai Jessubond Traffic Safety New Material Co., Ltd. Applicant before: Shanghai Xianpeng Industry Co., Ltd. |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |