CN101775243B - Coating structure, chemical composite used for preparing same and preparation method thereof - Google Patents
Coating structure, chemical composite used for preparing same and preparation method thereof Download PDFInfo
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- CN101775243B CN101775243B CN200910002505A CN200910002505A CN101775243B CN 101775243 B CN101775243 B CN 101775243B CN 200910002505 A CN200910002505 A CN 200910002505A CN 200910002505 A CN200910002505 A CN 200910002505A CN 101775243 B CN101775243 B CN 101775243B
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Abstract
The invention provides a coating structure, a chemical composite used for preparing same and a preparation method thereof. The coating structure of the invention comprises a resin layer solidified by ultraviolet light and a fluoride monomolecular layer, wherein the organosilicon groups of organosilicon molecules contained in the resin layer extend from the surface of the resin layer, wax fine powder and nanometer dioxide particles are exposed from the surface of the resin layer to form a peak-valley microstructure; and chemical bonds are formed between the fluorinated molecules of the fluoride monomolecular layer and the surface of the resin layer to expose fluorine-containing groups. When the coating structure is formed, resin layer which can be solidified by ultraviolet light is partially solidified, then the fluorinated molecules are activated to bond with the surface of the resin layer and the resin layer is completely solidified.
Description
Technical field
The present invention relates to a kind of coating structure, be used to form this coating structure chemical compsn, and form the method for this coating structure, particularly relate to a kind of have antifouling, abrasion performance, and the high coating structure of hardness, be used to form this coating structure chemical compsn, and form the method for this coating structure.
Background technology
Known when the preparation high-gloss coating; Can select to use ultraviolet curing transparent coating (being commonly referred to as the UV polishes); This is because UV polishes solids component is high, cross-linking density is strong; The coating porosity that obtains low, have certain anti-soil effect basically, can wipe out pollutent with a little sanitising agent mostly.But along with the technology accumulation, simple UV polishes can't satisfy the demands.Someone begins to add a spot of low surface energy auxiliary agent, for example, and silicane, fluorochemical analog assistant; When coating was dry, auxiliary agent can spontaneously float over coatingsurface made coating have the anti-soil effect of short-term, but still can't reach the ideal effect of long-acting anti-soil; This is because examples of such additives is micromolecular compound; Long-time run off easily, or the low surface energy group can receive biomolecules and induces and can't extend to coatingsurface, make the forfeiture of anti-soil effect.
Except the pollution resistance that promotes UV polishes coating itself, also can carry out some processing simultaneously in an enterprising step of coating, for example, use the polished tile waxing, use vehicle glass drying detergent treatment etc.But above-mentioned processing has the common shortcoming, can't keep anti-soil usefulness for a long time exactly, and can influence the gloss and the hardness of original coating.This is because do not have chemical bonded refractory between they and the coated article, and only relies on faint physical force to keep.
In addition; What the novel patent of TaiWan, China proposed a kind of plastics material for M319150 number fluoridizes the protective membrane structure; As shown in Figure 1; It is the layer 2 of coating one deck modification on plastic basis material 1, and the layer 2 of modification is mainly the inorganic thin film that contains nanometer grade silica or siloxanes, fluoridizes resist 3 in layer 2 surface coated of modification again.With the layer of modification 2 as plastic basis material 1 with fluoridize the interface between the resist 3, coat on the plastic basis material 1 but make with fluoridizing resist 3 close and firm, make the surface energy reduction of the plastic basis material 1 after the coating, with the antifouling effect of reinforcement protective membrane structure.But such protective membrane structure is not because the cause of many porosities of silica membrane has the outward appearance of high glossiness.
Therefore, still need a kind of novel coating structure and method for making thereof with high glossiness, long-acting and anti-fouling, abrasion performance character.
Summary of the invention
An object of the present invention is to provide a kind of coating structure, be used to form this coating structure chemical compsn, and form the method for this coating structure; This coating structure has high glossiness and abrasion performance character simultaneously; And can reach good and long lasting anti-soil, anti-fingerprint function, to solve prior art problems.
Coating structure according to the present invention comprise be formed at substrate surface to be coated through the resin layer of ultraviolet light polymerization and be formed at the fluorochemical unimolecular layer on this resin layer.Resin layer further comprises organosilicon molecule, wax class fine powder and nano-oxide particles.The organosilicon radical of organosilicon molecule extends out from the surface of resin layer, and wax class fine powder and nano-oxide particles expose from the surface of resin layer and form the mountain peak-mountain valley structure of microcosmic.The fluorinated molecule of fluorochemical unimolecular layer and the surface of resin layer form chemical bonded refractory to expose fluoro-containing group.
The chemical compsn that is used to form coating according to the present invention comprises the uv-curable resin of 100 weight parts; 0.01 organosilicon molecule to 5 weight parts; 0.1 wax class fine powder with low surface energy to 5 weight parts; And the nano-oxide particles of 0.5 to 5 weight part.
Comprise according to the method for formation coating of the present invention the wax class fine powder that comprises uv-curable resin, organosilicon molecule, have low surface energy, and the mixture of nano-oxide particles are provided; Mixture is coated on the surface of substrate to be coated, forms coat; Coat is heated and is left standstill, make the organosilicon molecule, have low surface energy wax class fine powder, and nano-oxide particles migrate to the coat surface; Partly solidified to the coat irradiating ultraviolet light to carry out; Partly solidified coat is applied one deck fluorochemical unimolecular layer; The coat that applies the fluorochemical unimolecular layer is heated with activating fluorinated thing; And to the coat irradiating ultraviolet light of heat-activated with completely solidified.
Compared with prior art; The present invention utilizes the lotus leaf biomimetic features of coatingsurface antifouling; And utilize the chemical bonded refractory power of fluorochemical molecule and its lower floor's coating; The low surface energy group firmly is fixed in outside surface, makes the gained coating have the long-acting and anti-fouling effect, and have high glossiness and abrasion performance character simultaneously.
Description of drawings
Fig. 1 shows the diagrammatic cross-section of known coating structure.
Fig. 2 shows the diagrammatic cross-section according to coating structure of the present invention.
Fig. 3 shows the enlarged diagram of Fig. 2.
Fig. 4 shows the synoptic diagram antifouling according to the lotus leaf biomimetic features of coating structure of the present invention.
Fig. 5 shows the synoptic diagram of fluorinated molecule and resin layer surface chemical bonded refractory among the present invention.
The primary clustering nomenclature
The layer of 1 plastic basis material, 2 modifications
3 fluoridize resist 10 substrates to be coated
12 resin layers, 14 fluorochemical unimolecular layers
16 organosilicon molecule 1s, 8 wax class fine powders
20 nano-oxide particles, 22 fluorinated molecules
24 pollutents
Embodiment
As shown in Figure 2, coating structure of the present invention is formed on the surface of substrate 10 to be coated.Coating structure according to the present invention comprises through the resin layer 12 of ultraviolet light polymerization and fluorochemical unimolecular layer 14.More specifically, with reference to enlarged diagram shown in Figure 3, of the present invention have organosilicon molecule 16, wax class fine powder 18, an and nano-oxide particles 20 in the resin layer 12 of ultraviolet light polymerization.The organosilicon radical of organosilicon molecule 16 extends out from the surface of resin layer 12.Wax class fine powder 18 exposes from the surface of resin layer 12 with nano-oxide particles 20 and forms the mountain peak-mountain valley structure of microcosmic.The fluorinated molecule 22 of fluorochemical unimolecular layer 14 forms chemical bonded refractory with resin layer 12 surfaces, to expose fluoro-containing group.Be noted that each figure only is schematically, do not represent actual dimension scale relation.
The method for making of coating structure of the present invention is described below.At first be provided for forming the batching of coating, that is, chemical compsn, it comprises uv-curable resin, organosilicon molecule, has the wax class fine powder of low surface energy, reaches nano-oxide particles.Employed amount for example can be: the uv-curable resin of 100 weight parts; 0.01 to 5 weight parts, the organosilicon molecule of 0.01 to 2 weight part more preferably; 0.1 to 5 weight parts, the wax class fine powder with low surface energy of 0.1 to 2 weight part more preferably; And 0.5 to 5 weight part, the nano-oxide particles of 0.75 to 4 weight part more preferably.
Wherein, uv-curable resin (the UV polishes that promptly is commonly called as) can include but not limited to acrylic acid or the like, PU class, polyester etc.Preferably, the hardness of the resin layer that forms behind the uv-curable resin solidification is more than the H level, and glass transition temp Tg value is high; And coating compactness is good; So that just have certain anti-soil effect, after scribbling with the oil pen, can remove with a little sanitising agent through the resin layer of ultraviolet light polymerization itself.
The organosilicon molecule is the small molecules organosilicon with organosilicon radical, for example can be silicane, type siloxane or polyethers/ester modified (modified) silicoorganic compound class.
Wax class fine powder is preferably the wax class powder of low surface energy, for example the thin wax powder, Vilaterm, polymeric amide or Vestolen PP 7052 (PP) fine powder that blend together of polytetrafluoroethylene (PTFE), tetrafluoroethylene and Vilaterm (PTFE/PE).Wax class fine powder particle diameter is preferably 10 microns to 50 microns.It is baked to softening temperature, slight fusing, thus make it may be interspersed in coatingsurface.Because be low molecule, institute also can anti-fingerprint so that coating is touched smooth sense.
Nano-oxide particles is then preferably selected the oxidate nano sized particles of high slippery, anti scuffing, for example, and aluminium sesquioxide, silicon-dioxide, zinc oxide (ZnO) or cerium dioxide (CeO
2) particle, it further increases the hydrophobic/oleophobic property of coating.The particle diameter of nano-oxide particles is preferably 10 nanometer to 100 nanometers.
Above-mentioned chemical compsn is mixed the formation mixture, and mechanical system capable of using mixes.For example stirred 5 minutes with stirrer low speed (200 to 400rpm) earlier.If LV for example below 2,000 centipoises (cps), was then disperseed 5 to 10 minutes with 5000 to 9000rpm with clarifixator.If medium-high viscosity, for example 2, more than the 000cps, then disperseed 10 to 15 minutes with 500 to 1000rpm with stirrer.
This mixture is coated on the surface of substrate to be coated, forms coat.The thickness of coat can confirm as required that for example 5 to 50 μ m are preferably 5 to 25 μ m.The mode that applies can be for example printing or spraying.After the application, paint film should be bright smooth.
Then, coat is heated and leave standstill.The purpose of heating and leaving standstill be make the organosilicon molecule, have low surface energy wax class fine powder, and nano-oxide particles migrate to the coat surface; Simultaneously solvent (if containing the words of solvent) is removed from coat; And promote the coat levelling; Therefore height and the length of time to temperature does not have special restriction, as long as can reach this purpose.For example, toasted 30 to 180 minutes down at 60 to 80 ℃ with hot-blast formula or infrared rays (IR) mode.This baking also can make coat dry.
Then, partly solidified to carry out to the coat irradiating ultraviolet light, this fashion is not all solidified, and uses in subsequent step to stay some functional groups.For example, if illumination needs 100 to 1000mJ/cm
2During with completely solidified, only with for example 80 to 90% the shining and get final product of the required illumination of completely solidified, (for example hydroxyl (OH)) is so that combine with the fluorochemical unimolecular layer to reserve 10% to 20% functional group.
Then, partly solidified coat is applied one deck fluorochemical unimolecular layer.The mode application of for example immersion plating (dip-coating), spraying, printing.For example; The coat of partly solidified processing is immersed in the fluoride aqueous solution with dip-coating (dip-coating) mode; At this moment, the substrate of coat below also can be immersed together, stops then for example 10 to 30 seconds; Fluorochemical is adsorbed on the ultraviolet curable coating surface, again with 50 to 2000mm/min the speed that draws high slowly with test piece pull-up in soup.The temperature that preferably controls environment simultaneously is 25 ± 1 ℃, and relative humidity is 50 ± 5%.Fluoride aqueous solution is mainly by fluorinated molecule and solvent composition, and fluorinated molecule for example can be that number-average molecular weight (Mn) is the PFPE more than 1000, and solvent can be organic solvent.For example can use the formed fluoride aqueous solution of EGC-1720 product of Minnesota Mining and Manufacturing Company, it can comprise content at the PFPE below 10%, additive (for example catalyzer, adhesion promoter etc.) and the organic solvent more than 90% below 5%.
In addition, the fluorinated silane that has a following formula also can be used as fluorinated molecule of the present invention:
R
f-[-R
1-SiY
3-xR
2 x]
y，
Wherein, R
fBe unit price or divalence multi-fluoro polyether base, R
1Be-C (O) NHR ', R ' is an alkylidene group, R
2Be C
1-C
4Alkyl, Y are halogen, C
1-C
4Alkoxyl group or C
1-C
4Acyloxy, x are 2 or 1, and y is 1 or 2.R
fFor example can be-CF
2O (CF
2O)
m(C
2F
4O)
pCF
2-,-C
3F
7O (CF (CF
3) CF
2O)
p(CF) (CF
3)-,-CF
3O (C
2F
4O)
pCF
2-,-CF (CF
3) O (CF (CF
3) CF
2O)
p(CF
3)-,-CF
2O (C
2F
4O)
pCF
2-,-(CF
2)
3O (C
4F
8O)
p(CF
2)
3-, wherein the MV of m is 0 to 50, and the MV of p is 0 to 50, and m and p can not be zero simultaneously in same group.
Fluorochemical unimolecular layer thickness in the outmost surface coating is thin, for example is about the thickness of several nanometers to tens nanometer, so that ultra-low surface energy-CF
3Group can be compelled to be fixed on the coat outside surface.Fluorinated molecule also need have functional group's (for example hydroxyl) simultaneously; So that fluorinated molecule can with coat (that is, and ultraviolet curing resin, but it preferably has the functional group of donating bond knot; Hydroxyl for example) coat on surface itself carries out chemical bonded refractory, thereby firmly is fixed in the coat surface.
Then, the coat that applies the fluorochemical unimolecular layer is heated with activating fluorinated thing.For example the coat with above-mentioned dip-coating perfluoro-compound solution heats with activating fluorinated thing.The fluorochemical molecule must be heated to certain temperature with the fluorochemical molecule activation after coating, make it be covered with the coat surface as far as possible and engage with the uv-curable resin key knot on surface.The key knot is just passable as long as Heating temperature scope and time can make the fluorochemical molecule activation.Different according to base material, to the Heating temperature scope and time different choice can be arranged, for example for plastic material, be about 60 to 80 ℃, 30 to 180 minutes; For non-plastic material, be about 120 to 150 ℃, 30 to 45 minutes.
At last, to the coat irradiating ultraviolet light of heat-activated so that uv-curable resin completely solidified.That is, with coat with the UV-irradiation of reserving illumination (for example 10% to 20% illumination) with completely solidified, so can obtain good and long lasting high gloss antifouling surface.
Coating structure of the present invention is fit to be formed in the substrate of plastic material or non-plastic material.Plastic material can be for example PC, PMMA, but is not limited thereto.Non-plastic material can be glass, metal etc., but is not limited thereto.
In the present invention, be matrix with resin layer through ultraviolet light polymerization, add three types additive again: organosilicon, low surface energy wax class fine powder and nano-oxide auxiliary agent, to reach better antifouling and anti-fingerprint effect.The function that this additive of three types is had nothing in common with each other.From microcosmic, as shown in Figure 3, still have trickle uneven and surface pore through resin layer 12 top layers of ultraviolet light polymerization, if after the attract dirt, then be difficult to remove, therefore, the resin layer through ultraviolet light polymerization still can't reach good anti-soil effect merely.Add organosilicon, the organosilicon radical of organosilicon molecule is extended out, from the surface of resin layer to reach anti-fouling effect.When organic silicon group is when Surface Vertical extends out, can get best relatively anti-fouling effect.But organosilicon radical arbitrarily stretches along with factor such as rate of drying, envrionment temperature and humidity sometimes, and the organosilicon small molecules runs off easily simultaneously, therefore, only adds organic silicon additive and can't reach the ideal anti-fouling effect.Therefore, the present invention also further adds wax class fine powder and nano-oxide particles, and wax class fine powder and nano-oxide particles is exposed from the surface of resin layer except adding the organosilicon analog assistant.For example shown in Figure 4; Utilize micron order wax class fine powder 18 as the mountain peak, nano-oxide particles 20 withstands pollutent 24 as the mountain valley; Air abrim between mountain peak and mountain valley; Make pollutent 24 be difficult to invade, as having formed micron-nanometer compound " lotus leaf effect " bionic function, can be effectively not contaminated thing be stained with sticking.
Add above-mentioned three kinds and add the significantly anti-fouling effect of enhancement coating of auxiliary agents, but because auxiliary agent is moved to the process on surface in film process be the result of the spontaneous formation of thermodynamics, make the difficult control of the final condition of surface of coating.In view of this, the present invention further is formed at the UV-cured resin laminar surface with the fluorochemical unimolecular layer.As shown in Figure 5, fluorinated molecule 22 forms chemical bonded refractory with the hydroxyl of the resin that is positioned at the surface of resin layer 12, so that the fluoro-containing group of low surface energy (for example-CF
3) outstanding delaying in the surface.Owing to be chemical bonded refractory, be difficult for breaking away from, therefore can reach more really and long lasting anti-fouling effect.
Anti-fingerprint effect to according to coating structure of the present invention is estimated.It is generally acknowledged that pollutent is the water oil mixt,, then can think to have anti-fouling effect if coating has hydrophobic and oleophobic effects.Therefore carry out two kinds of evaluations, the one, the water contact angle of mensuration coating, with apparatus measures, contact angle is big more, and then hydrophobicity is strong more; Another is to carry out ink test, scribbles at coatingsurface with the unusual pen of blue alcohols (for example Sambalion board Simbalion), if ink forms discontinuous drop, and available dried cloth wipes, and do not stay vestiges, then thinks qualified.On this binomial was estimated, coating structure of the present invention all obtained good evaluation.
Embodiment
With the PTFE wax powder of the silicone additives of uv-curable resin (viscosity 800cps), the 0.1g of 100 grams (g), 0.3g, and the nano aluminium oxide of 2.0g stirred 5 minutes with 200rpm with stirrer earlier, disperseed 10 minutes with 5000rpm with high-shear homogenizer again.Scattered coating fluid is coated on the PC injection moulding transparent plastic sheet with spraying method.2 crust (bar) are pressed in spray, shower nozzle 1.1mm, intersection spraying twice.The test piece that spraying is good is 60 ℃ of following standing and drying 30 minutes, again with 270mJ/cm
2Illumination carry out ultraviolet light polymerization (with the required illumination 300mJ/cm of completely solidified
290% shine).Test piece after handling is immersed in the fluoride aqueous solution, this fluoride aqueous solution by the raw spirit of the per-fluoro polyether compound of 0.1 weight %, 99.4 weight %, and the catalyzer of 0.5 weight % form, stopped 30 seconds, draw high with the speed of 100mm/min.Temperature is controlled to be 25 ± 1 ℃, and relative humidity is 50 ± 5%.The test piece that to soak with fluoride aqueous solution was 80 ℃ of following heat-activated 30 minutes.Ultraviolet lighting with the illumination (supplying 10% illumination of reservation) of 30mJ/min is incident upon completely solidified again, thereby obtains according to coating structure of the present invention.This coating structure has high glossiness and the surface is smooth, and surface hardness is greater than 2H (pencil hardness meter 750g), and measuring water contact angle is 97.9 °, has hydrophobicity.Scribble with oil pen (Sambalion board SIMBALION) and to carry out anti-soil test, the result finds that black liquid can shrink very soon, has oleophobic properties.Gently wipe away with non-dust cloth simultaneously, can wipe black trace, and it is residual to repeat to embrocate 50 also inkless traces.
The above is merely preferred embodiment of the present invention, and every equalization of having done according to accompanying claims of the present invention changes and modifies, and all should belong to covering scope of the present invention.
Claims (20)
1. coating structure comprises:
Be formed at the resin layer through ultraviolet light polymerization of substrate surface to be coated; This resin layer also comprises organosilicon molecule, wax class fine powder and nano-oxide particles; The organosilicon radical of this organosilicon molecule extends out from the surface of this resin layer, and this wax class fine powder and this nano-oxide particles expose from the surface of this resin layer and form the mountain peak-mountain valley structure of microcosmic; And
Be formed at this fluorochemical unimolecular layer through the resin layer surface of ultraviolet light polymerization, wherein the surface of the fluorinated molecule of this fluorochemical unimolecular layer and this resin layer forms chemical bonded refractory, to expose fluoro-containing group.
2. coating structure as claimed in claim 1, wherein this substrate to be coated comprises plastic material.
3. coating structure as claimed in claim 1, wherein this substrate to be coated comprises non-plastic material.
4. chemical compsn that is used to form coating comprises:
The uv-curable resin of 100 weight parts;
0.01 organosilicon molecule to 5 weight parts;
0.1 wax class fine powder with low surface energy to 5 weight parts; And
0.5 nano-oxide particles to 5 weight parts.
5. chemical compsn as claimed in claim 4, wherein this organosilicon molecule comprises silicane, type siloxane, polyether-modified organosilicon or the organosilicon of polyester modification.
6. chemical compsn as claimed in claim 4, wherein this wax class fine powder comprises tetrafluoroethylene, Vilaterm, polymeric amide or Vestolen PP 7052.
7. chemical compsn as claimed in claim 4, wherein the particle diameter of this wax class fine powder is 10 to 50 microns.
8. chemical compsn as claimed in claim 4, wherein, this nano-oxide particles comprises aluminium sesquioxide, silicon-dioxide, zinc oxide or cerium dioxide.
9. method that forms coating comprises:
Provide and comprise uv-curable resin, organosilicon molecule, have the wax class fine powder of low surface energy and the mixture of nano-oxide particles;
This mixture is coated on the surface of substrate to be coated, thereby forms coat;
This coat is heated and left standstill, make this organosilicon molecule, wax class fine powder and nano-oxide particles migrate to this coat surface with low surface energy;
Partly solidified to this coat irradiating ultraviolet light to carry out;
The coat that this is partly solidified applies the fluorochemical unimolecular layer;
This coat that applies this fluorochemical unimolecular layer is heated with this fluorochemical of activation; And
To this coat irradiating ultraviolet light of heat-activated with completely solidified.
10. method as claimed in claim 9, the thickness of this coat that is wherein formed by this mixture is 5 to 50 microns.
11. method as claimed in claim 10, wherein the required illumination of irradiating ultraviolet light completely solidified is 100 to 1000mJ/cm
2
12. method as claimed in claim 9 is wherein heated this coat and the step that leaves standstill is at 60 to 80 ℃ of these coats of baking 30 to 180 minutes down.
13. method as claimed in claim 9, the UV-light illumination of wherein carrying out using when partly solidified is 80% to 90% of the required UV-light illumination of completely solidified.
14. method as claimed in claim 9, the method that wherein will this partly solidified coat applies this fluorochemical unimolecular layer comprises dip-coating, spraying or printing.
15. the method for formation coating as claimed in claim 14, wherein this dip-coating comprises the coat dip-coating fluoride aqueous solution that this is partly solidified.
16. method as claimed in claim 15, wherein to comprise content be that PFPE and content below 10% is the organic solvent more than 90% to this fluoride aqueous solution.
17. method as claimed in claim 16, step that wherein will this partly solidified this fluoride aqueous solution of coat dip-coating comprises:
Make this partly solidified coat stay in this fluoride aqueous solution 10 to 30 seconds; And
This coat of speed pull-up with 50 to 2000mm/min.
18. method as claimed in claim 17, wherein, the step of this fluoride aqueous solution of coat dip-coating that this is partly solidified is carried out under the relative humidity of 24 to 26 ℃ envrionment temperature and 45% to 55%.
19. method as claimed in claim 9, wherein, this substrate to be coated comprises plastic material, and the step of this heat-activated is carried out under 60 to 80 ℃.
20. method as claimed in claim 9, wherein, this substrate to be coated comprises non-plastic material, and the step of this heat-activated is carried out under 120 to 150 ℃.
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| CN102808148B (en) * | 2011-05-30 | 2016-03-30 | 比亚迪股份有限公司 | A kind of preparation method of touch screen surface anti-fingerprint film |
| JP5045857B1 (en) * | 2012-02-22 | 2012-10-10 | ソニー株式会社 | Antifouling layer, antifouling substrate, display device and input device |
| CN104448680B (en) * | 2014-11-28 | 2018-01-26 | 上海锦湖日丽塑料有限公司 | The high glaze resin combination that a kind of finger mark improves |
| JP6755951B2 (en) * | 2016-07-12 | 2020-09-16 | シャープ株式会社 | Manufacturing method of antifouling film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1553940A (en) * | 2001-09-11 | 2004-12-08 | 3M | Smudge resistant nanocomposite hardcoats and methods for making same |
| CN201089748Y (en) * | 2007-08-02 | 2008-07-23 | 兆震实业股份有限公司 | Plastic rubber fluoridation protective film structure |
| CN201120753Y (en) * | 2007-08-01 | 2008-09-24 | 兆震实业股份有限公司 | Anti-soil protection structure for material |
| CN201158188Y (en) * | 2007-12-04 | 2008-12-03 | 兆震实业股份有限公司 | Improved structure of touch control element |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1553940A (en) * | 2001-09-11 | 2004-12-08 | 3M | Smudge resistant nanocomposite hardcoats and methods for making same |
| CN201120753Y (en) * | 2007-08-01 | 2008-09-24 | 兆震实业股份有限公司 | Anti-soil protection structure for material |
| CN201089748Y (en) * | 2007-08-02 | 2008-07-23 | 兆震实业股份有限公司 | Plastic rubber fluoridation protective film structure |
| CN201158188Y (en) * | 2007-12-04 | 2008-12-03 | 兆震实业股份有限公司 | Improved structure of touch control element |
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