CN102050834B - Reactive silica compound and optical protective film with same - Google Patents
Reactive silica compound and optical protective film with same Download PDFInfo
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- CN102050834B CN102050834B CN 200910209396 CN200910209396A CN102050834B CN 102050834 B CN102050834 B CN 102050834B CN 200910209396 CN200910209396 CN 200910209396 CN 200910209396 A CN200910209396 A CN 200910209396A CN 102050834 B CN102050834 B CN 102050834B
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Abstract
The invention discloses a reactive silica compound with a molecular formula shown in the formula (I) described in the specification of the invention, wherein each R is an independent reactive functional group shown in the formula (II) or the formula (III) which is described in the specification of the invention, wherein R1, RS and R3 comprise H or CH3 independently, n1 is approximate to an integer between 1 and 6, and n2 is approximate to an integer between 0 and 4. The invention also discloses an optical protective film which comprises the reactive silica compound and cellulose triacetate.
Description
[technical field]
The present invention relates to a kind of response type silicon dioxide compound and optical protection layer; and be particularly related to a kind of optical protection layer that comprises this response type silicon dioxide compound, wherein the response type silicon dioxide compound can lower the phase differential and the penetration that increases protective membrane of optical protection layer.
[background technology]
The nanometer grade silica material is used in works as transparent stopping composition in the macromolecular material, to increase surface hardness, physical strength and the thermotolerance of macromolecular material, it is widely used in the surface treatment of coating material, coating, film and automobile.
At present, the nanometer grade silica material also is used on the blooming, but can cause mist degree (haze) to increase when consumption increases.
A.Tagaya, H.Ohkita, M.Mukaoh, R.Sakaguchi, Y.Koike, Science, 301,812, (2003) disclosure macromolecular material mixes the inorganic salts crystalline compounds and can reduce R
0Value, but can't reduce R
ThValue.
Disclose among US Patent No. 6828006 and the US 6844033, the addition of nanometer grade silica material is not higher than 0.3% in the cellulosetri-acetate blooming, because when being higher than 0.3%, the penetration of blooming can descend, and mist degree can significantly raise, and can't reach the application requiring of optical grade.
Need at present a kind of new optical protection layer badly, it has low phase differential and low haze.Therefore in the present invention, provide the optical protection layer that contains the reaction type nm grade silicon dioxide, have low phase differential and low haze.And the surface modification of reaction type nm grade silicon dioxide material can increase the consistency with macromolecular material, and then improves the penetration of material, reduces mist degree, can reach the application requiring of optical grade.
The response type silicon dioxide compound can solve the birefringence effect (out-of-plane) of high-order polarisation protective membrane, reduces light leak and the color drift at wide-angle visual angle, and reduces the contrast of bright attitude/dark attitude.It can be applicable to the optical fields such as plastic cement solar concentrating lens in addition.
[summary of the invention]
The invention provides a kind of response type silicon dioxide compound, wherein the molecular formula of this response type silicon dioxide compound is suc as formula shown in (I):
Wherein each R is reactive functional groups independently, suc as formula (II) or (III):
Formula (II)
And R wherein
1, R
2With R
3Comprise independently H or CH
3, n
1Integer and n for about 1-6
2Integer for about 0-4.
The present invention also provides a kind of optical protection layer, and it comprises: above-mentioned response type silicon dioxide compound; And cellulosetri-acetate.
For above and other purpose of the present invention, feature and advantage can more be become apparent, hereinafter especially exemplified by preferred embodiment, and by reference to the accompanying drawings, be described in detail below:
[description of drawings]
Fig. 1 a and Fig. 1 b show the detailed formation mechanism of response type silicon dioxide compound.
Fig. 2 shows that the response type silicon dioxide compound imports the synoptic diagram of macromolecular material.
Fig. 3 a shows the content of the response type silicon dioxide compound that embodiment A is synthetic and the R of optical protection layer
ThThe graph of a relation of value.
Fig. 3 b shows the content of the response type silicon dioxide compound that Embodiment B is synthetic and the R of optical protection layer
ThThe graph of a relation of value.
[main description of reference numerals]
101～tetraethoxysilane (tetraethoxy silane, TEOS);
103～water;
105～silicon-dioxide inorganic sol (sol gel);
107～contain the silane of reactive functional groups;
109～response type silicon dioxide compound;
201～polymer;
203～response type silicon dioxide compound;
205～crosslinked.
[embodiment]
The optical protection layer that the invention provides a kind of response type silicon dioxide compound and comprise this response type silicon dioxide compound.Optical protection layer comprises this response type silicon dioxide compound and cellulosetri-acetate.The molecular formula of response type silicon dioxide compound is suc as formula shown in (I):
Wherein each R can be reactive functional groups independently, suc as formula (II) or (III):
And R wherein
1, R
2With R
3Can comprise independently H or CH
3, n
1Can be integer and the n of about 1-6
2Can be the integer of about 0-4.In one embodiment, optical protection layer comprises that content is this response type silicon dioxide compound of 5-50wt%, and content is the cellulosetri-acetate of 50-95wt%.And have phase differential attenuating and the penetration increase of protective membrane or the effect that mist degree lowers that makes optical protection layer in the response type silicon dioxide compound of this content range.
In above-mentioned response type silicon dioxide compound, the content of reactive functional groups can be about 0.1-95wt%.And response type silicon dioxide compound system is formed by silicon-dioxide and the silane reaction that contains above-mentioned reactive functional groups.The detailed reaction of response type silicon dioxide compound forms mechanism shown in Fig. 1 a and Fig. 1 b.Referring to Fig. 1 a, at first tetraethoxysilane 101 is added water 103 and be hydrolyzed reaction (hydrolysis) and condensation reaction (condensation) and form silicon-dioxide inorganic sol 105, and only react shown in the first half of Fig. 1 b.Afterwards silicon-dioxide inorganic sol 103 and the silane 107 that contains above-mentioned reactive functional groups are reacted, and produce response type silicon dioxide compound 109 of the present invention, shown in Fig. 1 b.Silicon-dioxide is about 10-600 minute with the reaction times that contains the silane reaction of above-mentioned reactive functional groups again, and temperature of reaction is about 10-100 ℃, is about 40 ℃ in one embodiment.The silane that contains above-mentioned reactive functional groups can include but not limited to 3-(methacryloxypropyl) propyl trimethoxy silicane (3-(trimethoxysilyl)-propyl methacrylate) or 3-(epoxy the third oxygen) propyl trimethoxy silicane (3-glycidoxypropyl trimethoxysilane) etc., or its composition.The particle size range of response type silicon dioxide compound is about 0.1-100nm.
And in above-mentioned cellulosetri-acetate, the content of acetoxy group is about 34-44wt%.
Above-mentioned optical protection layer also can comprise softening agent (plasticizer).The content of softening agent can be about 4-20wt%.Softening agent can include but not limited to triphenylphosphate (triphenyl phosphate), 2-xenyl diphenyl phosphate (2-biphenylyl diphenyl phosphate) or ethyl phthalate(DEP) ethyl hexanol acid esters (ethyl phthalyl ethyl glycolate) etc.
Because importing polymer 201 (for example cellulosetri-acetate), response type silicon dioxide compound 203 can upset polymer in the arrangement of membrane plane (in plane); and when film forming, can produce the crosslinked 205 also fixedly arrangements (referring to Fig. 2) of polymer 203 after upsetting; therefore optical protection layer of the present invention has lower phase difference value R than traditional optical protection layer
0With R
ThR
0=(n
x-n
y) * d, n
x, n
yBe the main refractive index value on the blooming plane, d is the thickness of blooming, and the wavelength region of test is 400-700nm.R
Th=((n
x+ n
y)/2-n
z) * d, n
zBe the main refractive index value on the blooming film thickness direction, d is the thickness of blooming, and the wavelength region of test is 400-700nm.The R of above-mentioned optical protection layer
0Value is about 0-3nm, R
ThValue is about 0-100nm.The mist degree of optical protection layer is about 0.1-2.0.The thickness of optical protection layer is about 1-500 μ m.
[embodiment]
1. the response type silicon dioxide compound is synthetic
Embodiment A
20wt%SiO with 50ml
2Dispersion liquid is (at CH
2Cl
2In, median size is that 30 ± 6nm) (the commodity nano sol of Changchun petro-chemical corporation) mix with 3-(methacryloxypropyl) propyl trimethoxy silicane of 15ml, reaction is 4 hours under 40 ℃ of temperature, then be down to room temperature and continue to stir after 48 hours, obtain containing the SiO of methacrylic ester (methacrylate) reactive functional groups
2(median size is 10 ± 5nm) to dispersion liquid.
Embodiment B
20wt%SiO with 50ml
2Dispersion liquid is (at CH
2Cl
2In, median size is that 30 ± 6nm) (the commodity nano sol of Changchun petro-chemical corporation) mix with 3-(epoxy the third oxygen) propyl trimethoxy silicane of 15ml, reaction is 4 hours under 40 ℃ of temperature, then be down to room temperature and continue to stir after 48 hours, obtain containing the SiO of glycidoxypropyl (glycidoxyl) reactive functional groups
2(median size is 17 ± 5nm) to dispersion liquid.
Embodiment C
20wt%SiO with 50ml
2Dispersion liquid is (at CH
2Cl
2In, median size is that 30 ± 6nm) (the commodity nano sol of Changchun petro-chemical corporation) mix with 3-(methacryloxypropyl) propyl trimethoxy silicane of 10ml, reaction is 4 hours under 40 ℃ of temperature, 3-(epoxy the third oxygen) propyl trimethoxy silicane that then adds again 5ml mixes, reaction is 4 hours under 40 ℃ of temperature, then be down to room temperature and continue to stir after 48 hours, obtain containing the SiO of methacrylic ester (methacrylate) and glycidoxypropyl reactive functional groups
2(median size is 15 ± 6nm) to dispersion liquid.
2. the assay of reactive functional groups in the response type silicon dioxide compound
First with the SiO that contains reactive functional groups of embodiment A-C gained
2Dispersion liquid is placed in 105 ℃ the hot-air oven dry 3 hours, then with dried SiO
2Put in loft drier, rising again to room temperature 6 hours.SiO after afterwards drying being risen again
2Sample places thermogravimeter (ThermogravimetricAnalyzer, TGA), under nitrogen atmosphere, the rising temperature produces weight loss to causing reactive functional groups cracking in the sample, the record sample can be judged SiO with the variation of the weight of temperature or time
2The ratio of the reactive functional groups composition of material.The result is as shown in table 1.
Table 1, the content of reactive functional groups in the response type silicon dioxide compound
| TGA thermo-cracking temperature and composition % | Embodiment A | Embodiment B | Embodiment C |
| 25～100℃(％) | 0.33 | 0.21 | 0.29 |
| 100～400℃(％) | 31.25 | 32.15 | 31.80 |
| 400～600℃(％) | 68.42 | 67.64 | 67.91 |
| Cracking temperature ℃ | 286.30 | 292.05 | 290.70 |
| The ratio of reactive functional groups composition (%) | 31.35 | 32.21 | 31.89 |
3. the formation of low phase differential optical protection layer
(1) adds the synthetic response type silicon dioxide compound of embodiment A
Embodiment A-1
The preparation of cellulosetri-acetate dope (TAC dope):
In the 500ml serum bottle, add 35.54g cellulosetri-acetate, 3.95g triphenylphosphate and 224.64g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 10.5g that adds again the synthetic response type silicon dioxide compound of embodiment A, at room temperature continuous rolling is 24 hours, then the membrane filtration with 15 μ m polypropylene (polypropylene, PP) materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The transparent cellulosetri-acetate dope that above-mentioned preparation is finished; pour in the mould; the clearance control of mould and glass substrate is at 700 μ m; be coated with linear velocity 2.5cm/sec; after being painted with wet film put into hot-air oven with 100 ℃ of dryings 8 hours, again optical protection layer is peeled off from glass substrate, be placed in the climatic chamber with RH50; 25 ℃ of balances of temperature 8 hours, the average film thickness that obtains are 71 ± 2 μ m.
R
0With R
ThMeasure:
With the optical protection layer of gained, put into the AXOMETRIX spectrograph and analyze R
0With R
ThAnalyst coverage be 400-700nm, measured R
0Value is 0.16nm, R
ThValue is 75nm.
Haze measurement:
The optical protection layer of gained is put into haze meter (Haze meter) analyze, analyst coverage is 400-700nm, and measured haze value is 0.85.
Embodiment A-2
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 33.65g cellulosetri-acetate, 3.74g triphenylphosphate and 217.08g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 21g that adds again the synthetic response type silicon dioxide compound of embodiment A, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same embodiment A-1, obtaining average film thickness is 78 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same embodiment A-1, measured R
0Value is 0.17nm, R
ThValue is 71nm.
Haze measurement:
The described method of same embodiment A-1, measured haze value are 1.42.
Embodiment A-3
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 31.76g cellulosetri-acetate, 3.53g triphenylphosphate and 209.52g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 31.50g that adds again the synthetic response type silicon dioxide compound of embodiment A, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same embodiment A-1, obtaining average film thickness is 80 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same embodiment A-1, measured R
0Value is 0.18nm, R
ThValue is 57nm.
Haze measurement:
The described method of same embodiment A-1, measured haze value are 2.0.
Embodiment A-4
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 26.09g cellulosetri-acetate, 2.90g triphenylphosphate and 186.84g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 63g that adds again the synthetic response type silicon dioxide compound of embodiment A, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same embodiment A-1, obtaining average film thickness is 90 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same embodiment A-1, measured R
0Value is 0.17nm, R
ThValue is 25nm.
Haze measurement:
The described method of same embodiment A-1, measured haze value are 0.8.
Embodiment A-5
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 16.47g cellulosetri-acetate, 4.12g triphenylphosphate and 156.60g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 105g that adds again the synthetic response type silicon dioxide compound of embodiment A, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same embodiment A-1, obtaining average film thickness is 100 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same embodiment A-1, measured R
0Value is 0.15nm, R
ThValue is 1nm.
Haze measurement:
The described method of same embodiment A-1, measured haze value are 1.0.
Embodiment A-1 is to response type silicon dioxide compound and cellulosetri-acetate ratio and the R thereof of A-5
0With R
ThBe worth as shown in table 2.
Table 2, embodiment A-1 are to the response type silicon dioxide compound of A-5 and ratio and the R thereof of cellulosetri-acetate
0With R
ThValue
| The response type silicon dioxide compound (%) that embodiment A is synthetic | Cellulosetri-acetate (%) | R 0(nm) | R th(nm) | |
| Embodiment A-1 | 5％ | 95％ | 0.3 below | 75 |
| Embodiment A-2 | 10％ | 90％ | 0.3 below | 71 |
| Embodiment A-3 | 15％ | 85％ | 0.3 below | 57 |
| Embodiment A-4 | 30％ | 70％ | 0.3 below | 25 |
| Embodiment A-5 | 50％ | 50％ | 0.3 below | 1 |
And the content of the response type silicon dioxide compound that embodiment A is synthesized and the R of optical protection layer
ThThe graph of a relation of value is shown in Fig. 3 a.Can learn increase along with the content of the synthetic response type silicon dioxide compound of embodiment A, the R of optical protection layer by Fig. 3 a
ThValue lowers.
(2) add the synthetic response type silicon dioxide compound of Embodiment B
Embodiment B-1
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 33.65g cellulosetri-acetate, 3.74g triphenylphosphate and 217.08g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 21g that adds again the synthetic response type silicon dioxide compound of Embodiment B, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The transparent cellulosetri-acetate dope that above-mentioned preparation is finished; pour in the mould; the clearance control of mould and glass substrate is at 700 μ m; be coated with linear velocity 2.5cm/sec; after being painted with wet film put into hot-air oven with 100 ℃ of dryings 8 hours, again optical protection layer is peeled off from glass substrate, be placed in the climatic chamber with RH50; 25 ℃ of balances of temperature 8 hours, obtaining average film thickness is 93 ± 2 μ m.
R
0With R
ThMeasure:
With the optical protection layer of gained, put into the AXOMETRIX spectrograph and analyze R
0With R
ThAnalyst coverage be 400-700nm, measured R
0Value is 0.13nm, R
ThValue is 52nm.
Haze measurement:
With the optical protection layer of gained, to put into Haze meter and analyze, analyst coverage is 400-700nm, measured haze value is 0.48.
Embodiment B-2
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 29.87g cellulosetri-acetate, 3.32g triphenylphosphate and 201.96g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 42g that adds again the synthetic response type silicon dioxide compound of Embodiment B, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same Embodiment B-1, obtaining average film thickness is 79 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same Embodiment B-1, measured R
0Value is 0.29nm, R
ThValue is 27nm.
Haze measurement:
The described method of same Embodiment B-1, measured haze value are 0.37.
Embodiment B-3
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 26.09g cellulosetri-acetate, 2.90g triphenylphosphate and 186.84g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 63g that adds again the synthetic response type silicon dioxide compound of Embodiment B, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same Embodiment B-1, obtaining average film thickness is 75 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same Embodiment B-1, measured R
0Value is 0.12nm, R
ThValue is 12nm.
Haze measurement:
The described method of same Embodiment B-1, measured haze value are 1.06.
Embodiment B-4
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 22.31g cellulosetri-acetate, 2.48g triphenylphosphate and 171.72g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 84g that adds again the synthetic response type silicon dioxide compound of Embodiment B, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same Embodiment B-1, obtaining average film thickness is 95 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same Embodiment B-1, measured R
0Value is 0.27nm, R
ThValue is 2.5nm.
Haze measurement:
The described method of same Embodiment B-1, measured haze value are 0.23.
Embodiment B-5
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 18.53g cellulosetri-acetate, 2.06g triphenylphosphate and 105g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), the speed rolling serum bottle that then encloses with per minute 15, at room temperature continuous rolling is after 24 hours, dispersion liquid (20wt%) 156.60g that adds again the synthetic response type silicon dioxide compound of Embodiment B, at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The described method of same Embodiment B-1, obtaining average film thickness is 83 ± 2 μ m.
R
0With R
ThMeasure:
The described method of same Embodiment B-1, measured R
0Value is 0.08nm, R
ThValue is 1.9nm.
Haze measurement:
The described method of same Embodiment B-1, measured haze value are 1.12.
Embodiment B-1 is to response type silicon dioxide compound and cellulosetri-acetate ratio and the R thereof of B-5
0With R
ThBe worth as shown in table 3.
Table 3, Embodiment B-1 are to the response type silicon dioxide compound of B-5 and ratio and the R thereof of cellulosetri-acetate
0With R
ThValue
| The response type silicon dioxide compound (%) that Embodiment B is synthetic | Cellulosetri-acetate (%) | R 0(nm) | R th(nm) | |
| Embodiment B-1 | 5％ | 95％ | 0.3 below | 52 |
| Embodiment B-2 | 10％ | 90％ | 0.3 below | 28 |
| Embodiment B-3 | 15％ | 85％ | 0.3 below | 12 |
| Embodiment B-4 | 30％ | 70％ | 0.3 below | 2.5 |
| Embodiment B-5 | 50％ | 50％ | 0.3 below | 1.9 |
And the content of the response type silicon dioxide compound that Embodiment B is synthesized and the R of optical protection layer
ThThe graph of a relation of value is shown in Fig. 3 b.Can be learnt by Fig. 3 b, along with the content increase of the synthetic response type silicon dioxide compound of Embodiment B, the R of optical protection layer
ThValue lowers.
(3) comparative example: add unmodified silicon dioxide compound
Comparative example 1
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 31.76g cellulosetri-acetate, 3.53g triphenylphosphate and 209.52g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), then with the speed rolling serum bottle of per minute 15 circles, at room temperature continuous rolling adds 20wt%SiO after 24 hours again
2Dispersion liquid (CH
2Cl
2In, median size is 30 ± 6nm) (the commodity nano sol of Changchun petro-chemical corporation) 31.50g, and at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
The transparent cellulosetri-acetate dope that above-mentioned preparation is finished; pour in the mould; the clearance control of mould and glass substrate is at 700 μ m; be coated with linear velocity 2.5cm/sec; after being painted with wet film put into hot-air oven with 100 ℃ of dryings 8 hours, again optical protection layer is peeled off from glass substrate, be placed in the climatic chamber with RH50; 25 ℃ of balances of temperature 8 hours, obtaining average film thickness is 80 ± 2 μ m.
Haze measurement:
With the optical protection layer of gained, to put into Haze meter and analyze, analyst coverage is 400-700nm, measured haze value is 7.0.
Comparative example 2
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 26.09g cellulosetri-acetate, 2.90g triphenylphosphate and 186.84g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), then with the speed rolling serum bottle of per minute 15 circles, at room temperature continuous rolling adds 20wt%SiO after 24 hours again
2Dispersion liquid (CH
2Cl
2In, median size is 30 ± 6nm) (the commodity nano sol of Changchun petro-chemical corporation) 63g, and at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
With comparative example 1 described method, obtaining average film thickness is 90 ± 2 μ m.
Haze measurement:
With comparative example 1 described method, measured haze value is 10.
Comparative example 3
The preparation of cellulosetri-acetate dope:
In the 500ml serum bottle, add 16.47g cellulosetri-acetate, 4.12g triphenylphosphate and 156.60g CH
2Cl
2/ MeOH mixing solutions (volume ratio: CH
2Cl
2/ MeOH=95/5), then with the speed rolling serum bottle of per minute 15 circles, at room temperature continuous rolling adds 20wt%SiO after 24 hours again
2Dispersion liquid (CH
2Cl
2In, median size is 30 ± 6nm) (the commodity nanosol of Changchun petro-chemical corporation) 105g, and at room temperature continuous rolling is 24 hours, and then the membrane filtration with 15 μ m polypropylene materials obtains transparent cellulosetri-acetate dope.
The preparation of optical protection layer:
With comparative example 1 described method, obtaining average film thickness is 100 ± 2 μ m.
Haze measurement:
With comparative example 1 described method, measured haze value is 14.
Embodiment A-3 to the mist degree of the optical protection layer of A-5 and comparative example 1-3 relatively is shown in table 4.
Table 4, embodiment A-3 are to the mist degree of the optical protection layer of A-5 and comparative example 1-3
| The content of silicon dioxide compound (%) | The mist degree (the response type silicon dioxide compound that contains embodiment A) that the optical protection layer of embodiment is measured | The mist degree (containing unmodified silicon dioxide compound) that the optical protection layer of comparative example is measured |
| 15％ | (2.0 embodiment A-3) | (7.0 comparative example 1) |
| 30％ | (0.8 embodiment A-4) | 10 (comparative examples 2) |
| 50％ | (1.0 embodiment A-5) | 14 (comparative examples 3) |
Table 4 shows; in the situation of the content of identical silicon dioxide compound; the present invention contains the optical protection layer of response type silicon dioxide compound and compares with the optical protection layer that contains unmodified silicon dioxide compound, and optical protection layer of the present invention has lower mist degree.
Although the present invention discloses as above with a plurality of preferred embodiments, so it is not to limit the present invention, any the technical staff in the technical field of the invention, and without departing from the spirit and scope of the present invention, Ying Kezuo is change and retouching arbitrarily.Therefore, protection scope of the present invention should be as the criterion with the appended claims restricted portion.
Claims (12)
1. response type silicon dioxide compound, the molecular formula of this response type silicon dioxide compound is suc as formula shown in (I):
Wherein each R is reactive functional groups independently, suc as formula (II) or (III):
Formula (III),
And R wherein
1, R
2With R
3Comprise independently H or CH
3, n
1Integer and n for 1-6
2Integer for 0-4.
2. response type silicon dioxide compound as claimed in claim 1, wherein in this response type silicon dioxide compound, the content of this reactive functional groups is 0.1-95wt%.
3. response type silicon dioxide compound as claimed in claim 1, wherein this response type silicon dioxide compound system is formed by silicon-dioxide and the silane reaction that contains this reactive functional groups.
4. response type silicon dioxide compound as claimed in claim 3, wherein this silane that contains this reactive functional groups comprises 3-(methacryloxypropyl) propyl trimethoxy silicane and/or 3-(epoxy the third oxygen) propyl trimethoxy silicane.
5. optical protection layer, it comprises:
Response type silicon dioxide compound as claimed in claim 1, its content are 5-50wt%; And
Cellulosetri-acetate, its content are 50-95wt%.
6. optical protection layer as claimed in claim 5, wherein the particle size range of this response type silicon dioxide compound is 0.1-100nm.
7. optical protection layer as claimed in claim 5, wherein in this cellulosetri-acetate, the content of acetoxy group is 34-44wt%.
8. optical protection layer as claimed in claim 5 also comprises softening agent, and wherein the content of this softening agent is 4-20wt%.
9. optical protection layer as claimed in claim 8, wherein this softening agent comprises triphenylphosphate, 2-xenyl diphenyl phosphate or ethyl phthalate(DEP) ethyl hexanol acid esters.
10. optical protection layer as claimed in claim 5, the wherein R of this optical protection layer
0Value is 0-3nm; The R of this optical protection layer
ThValue is 0-100nm.
11. optical protection layer as claimed in claim 5, wherein the mist degree of this optical protection layer is 0.1-2.0.
12. optical protection layer as claimed in claim 5, wherein the thickness of this optical protection layer is 1-500 μ m.
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| CN 200910209396 CN102050834B (en) | 2009-11-06 | 2009-11-06 | Reactive silica compound and optical protective film with same |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070710A1 (en) * | 2004-12-28 | 2006-07-06 | Jsr Corporation | Antireflective film |
| JP2007272156A (en) * | 2006-03-31 | 2007-10-18 | Mitsui Chemicals Inc | High refractive index cured film |
| JP2007314707A (en) * | 2006-05-29 | 2007-12-06 | Konica Minolta Holdings Inc | Plasma treatment method, antireflection film, polarizing plate, and image display device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070710A1 (en) * | 2004-12-28 | 2006-07-06 | Jsr Corporation | Antireflective film |
| JP2007272156A (en) * | 2006-03-31 | 2007-10-18 | Mitsui Chemicals Inc | High refractive index cured film |
| JP2007314707A (en) * | 2006-05-29 | 2007-12-06 | Konica Minolta Holdings Inc | Plasma treatment method, antireflection film, polarizing plate, and image display device |
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