CN104220531B - Contain the high molecular optical thin film resin combination of trapezoidal silsesquioxane - Google Patents
Contain the high molecular optical thin film resin combination of trapezoidal silsesquioxane Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
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- C08J5/18—Manufacture of films or sheets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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Abstract
The present invention relates to one kind containing the high molecular optical thin film resin combination of trapezoidal silsesquioxane; especially because containing silsesquioxane macromolecule with the high-compatibility of cellulosic resin, with trapezium structure is shown; thus heat resistance, ultraviolet light blocking effect, plasticization effect etc. are excellent; therefore, it effectively is used in the optical thin film of manufacture protective film for polarizing plate, compensation film etc..
Description
Technical field
The present invention relates to one kind containing terraced (ladder) shape silsesquioxane (silsesquioxane) high molecular optics
Film resin combination is more particularly related to a kind of resin combination and the optically thin of the resin combination is utilized
Film and optical instrument, the resin combination contain show it is with the high-compatibility of cellulose (cellulose) resinoid, have
The silsesquioxane macromolecule of trapezium structure, thus heat-resistant quality, ultraviolet light blocking effect, water resistance, plasticization effect etc. are excellent,
So as to effectively be used in the optical thin film of manufacture protective film for polarizing plate, compensation film etc..
Background technology
In general, cellulose family film is due to excellent transparency, and the anisotropy that can be easy to make refractive index is small
Film be therefore widely used on the optical applications of protective film for polarizing plate etc..In particular, not only greatly improving pair of display
Than degree (C/R), and by the technological development of phase difference adjusting etc., as expensive compensation film (Compensation
Film level of application) is also higher.
However, just needing complicated technology essential factor to give several functions, and need the various of film making process
Change, but these directly result in the rise of price, thus is actually pointed out as the stumbling-block of multiple suitable application areas.As representativeness
Example, advanced-cellulose family compensation film be " the wide visual field (Wide view：WV, Japanese fuji film Co., Ltd.) " although property
Can be preeminent, but its complex process, and price is very expensive, thus be difficult to be suitable for the general displays such as laptop, for
Substitute should " wide visual field " and utilize the simply general cellulose family protective film of polyvinyl alcohol (PVA) layer of protection polarizing film
In the case of, occur it could not be expected that the problem of improving the clarity etc of display.
The performance improvement for being broadly divided into two fields and carrying out cellulose family film as described above is increasing in advance first
After the molecular unit operation for moulding agent, optics additive etc., implemented by the subsequent techniques condition such as stretching, bond by adjusting
Desired physical characteristic.In particular, the adjusting of the optical physics characteristic operated by molecular unit is the above-mentioned fiber of research
The core technology element of all enterprises of the performance improvement of plain class film, and necessity of the additive in these stages can be suitable for
Condition is as follows：
1. with cellulosic resin excellent in compatibility and must not have muddy (hazy) phenomenon.
2. must not have disengaging and reactivity under high temperature and alkaline condition.
3. the reduction of the fundamental characteristics such as the transparency of cellulosic resin, hardness, optical isotropy should be made to minimize.
However, organic-monomer the adding ingredient utilized at present in numerous areas cannot fully meet item as described above
Part, thus the limitation of performance improvement is well imagined.
Therefore, in order to overcome the limitation of this performance, gold is utilized in South Korea patent application the 10-2009-0043088th
Belong to class Nanodispersion to improve physical property, by novel amino benzene in South Korea patent application the 10-2009-0132560th
And thiazole is used as adding ingredient to improve the phase difference of film.However, although having paid these a series of effort, compatibility
Limitation and the peeling of molecular unit adding ingredient only locally having improvement, and not yet overcome completely.
Invention content
Technical problem
It is as described above in order to solve the problems, such as, it is an object of the present invention to provide a kind of optical thin film resin combination,
It contains the silsesquioxane macromolecule excellent, with trapezium structure with the compatibility of cellulosic resin, thus heat resistance,
Ultraviolet light blocking effect, water resistance and plasticization effect etc. are excellent.
Moreover, it is an object of the present invention to provide one kind obtained by above-mentioned resin combination, to not only maintain fiber
The excellent translucency of plain class film and improve the optical thin film of physical characteristic and the optical instrument comprising the optical thin film.
Solve Problem Technical Solution
In order to achieve the above object, the present invention provides a kind of optical thin film resin combination, the optical thin film resin
Composition is it is characterized in that, contain：
1) the trapezoidal silsesquioxane macromolecule that weight average molecular weight is 1,000 to 1,000,000；And 2) cellulose family
Resin.
Moreover, the present invention provides a kind of optical thin film by obtained by optical thin film resin combination and comprising the optics
The optical instrument of film.
Invention effect
Optical thin film resin group according to the present invention containing trapezoidal silsesquioxane macromolecule and cellulosic resin
Object is closed, even if containing being also showed that and the trapezoidal silsesquioxane of the high-compatibility of cellulosic resin height without other chemical reaction
Molecule, thus heat resistance, ultraviolet light blocking effect, water resistance and plasticization effect etc. are excellent, therefore, effectively are used in making
It makes and not only maintains the excellent translucency of cellulose family film but also improve the protective film for polarizing plate of physical characteristic, compensation film
Deng cellulose family optical thin film.
Description of the drawings
Fig. 1 is to compare the cellulose solution of synthesis example 1 and according to an embodiment of the invention 1 to 5 mixing with transmissivity
The result of the compatibility of resin combination (content of the celluosic resin in cellulose solution is 10 weight %).
Fig. 2 is compared with the increased compatibility with celluosic resin of the high molecular phenyl of silsesquioxane with transmissivity
Result.
Fig. 3 is using FT-IR spectrometers (Fourier Transform Infrared Spectrometer) for cellulose-silicon according to the present invention times
Half oxygen alkane mixed film determines the result of IR.
Fig. 4 is determined according to the present invention using TGA (thermal gravimetric analyzer, thermogravimetric analyzer)
Cellulose-silsesquioxane mixed film thermolytic mechanism result.
Fig. 5 be using DSC (differential scanning calorimeter) determine cellulose according to the present invention-silsesquioxane mix it is thin
The result of the thermal stability of film.
Specific implementation mode
The optical thin film resin combination of the present invention, which is characterized in that contain：1) weight average molecular weight is 1,000 to 1,
000,000 trapezoidal silsesquioxane macromolecule；And 2) cellulosic resin.
Illustrate each ingredient below.
1) silsesquioxane macromolecule
Silsesquioxane macromolecule as used in the present invention is terraced (ladder) shape silsesquioxane
(silsesquioxane) macromolecule, weight average molecular weight 1,000 to 1,000,000, preferably 10,000 to 100,000.
The above-mentioned trapezoidal silsesquioxane macromolecule preferably structure with following chemical formula 1：
[chemical formula 1]
In above-mentioned chemical formula 1,
R1To R4It is each independently hydrogen, with C1To C20The ring-type or Noncyclic aliphatic organo-functional group of connection, alkyl,
Alkyl halide, aryl, amino, (methyl) acrylic, vinyl, epoxy group or mercapto, at this point, R1To R4It can be by mutually the same
Or mutually different organo-functional group is replaced,
R5To R8It is each independently selected from by C1-5Alkyl, C3-10Naphthenic base, C6-12Aryl, alcohol, alkoxy and
In the group that combination thereof is formed,
N is 1 to 100,000.
Among the above, above-mentioned alcohol or alkoxy are preferably-OCR' or-CR'=N-OH, and R' is C at this time1-6Alkyl.
Being used in the above-mentioned trapezoidal silsesquioxane macromolecule of the present invention can utilize well known method to prepare, or may be used also
To use the silsesquioxane macromolecule of market sale, the silsesquioxane macromolecule of above-mentioned chemical formula 1 preferably to introduce
The trifunctional one type of silane of machine functional group, by making the compound hydrolyzable of following chemical formula 2 be carried out continuously polymerisation later
And it can be made：
[chemical formula 2]
R9 4-m-Qp-Si-(OR10)m
In above-mentioned chemical formula 2,
R9It is hydrogen, with C1To C20The ring-type or Noncyclic aliphatic organo-functional group, alkyl, alkyl halide, aryl, ammonia of connection
Base, (methyl) acrylic, vinyl, epoxy group or mercapto；
R10Selected from by C1-5Alkyl, C3-10Naphthenic base, C6-12Aryl, alcohol, alkoxy and combination thereof institute
In the group of composition,
Q is C1-6Alkylidene or C1-6Alkylene oxide (alkyleneoxy) base,
M is 0 to 4 integer,
P is 0 or 1 integer.
Among the above, above-mentioned alcohol or alkoxy are preferably-OCR' or-CR'=N-OH, and R' is C at this time1-6Alkyl.
Moreover, in above-mentioned chemical formula 2, R9Or R10It can be the aromatic series organo-functional group as phenyl, but make
For the R of the side chain in the trapezoidal silsesquioxane macromolecule of the present invention1To R4When the content of middle aromatic series organo-functional group is excessive,
There are the tendencies of decrease in transmission, therefore, in side chain R1To R4Total 100% in the content of phenyl be adjusted to rub less than 80
Your % is advisable.This is because the excessive increase of aromatic series organo-functional group is possible to generate pole between cellulose family film
The event of sex differernce.
When preparing the above-mentioned trapezoidal silsesquioxane macromolecule of the present invention, reaction condition can be according to usual in this field institute
Recorded method executes in the method used such as Korean Patent Publication No. 10-2010-0131904.
Moreover, the above-mentioned high molecular degree of polymerization of silsesquioxane is adjustable as 1 to 99.9%, with regard to silsesquioxane macromolecule
For the content of-OH of end, diversely can arbitrarily be adjusted according to the change in polarity of the mixed cellulosic resin used and
It is applicable in, it can in the case where the content of-OH of silsesquioxane macromolecule end is 0.01 to 50% preferably in terminal groups
The resin combination of keeping excellent in stability is made.
Moreover, the various ultraviolet absorbers being usually known are introduced when preparing the compound of above-mentioned chemical formula 1
To R1To R8In the case of, for being stopped the additive of characteristic ultraviolet when also acting as manufacture optical thin film.As specific
An example, the compound that can be used as ultraviolet absorber include：2- (the chloro- 2H- benzotriazole -2- bases of 5-) -6- (1,1- dimethyl second
Base) -4- methyl-phenols (2- (5-chloro-2H-benzotriazole-2-yl) -6 (1,1-dimethylethyl) -4-
Methyl-phenol), octyl -3- [3- tertiary butyl-4-hydroxies -5- (the chloro- 2H- benzotriazole -2- bases of 5-) phenyl] propionic ester
(Octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]
The ultraviolet absorber containing halogen such as propionate)；And bis- tertiary fourths of 2- (2H- benzotriazole -2- bases) -4,6-
Base phenol (2- (2H-benzotriazol-2-yl) -4,6-ditertylphenol), 2- (2H- benzotriazole -2- bases) -4,6-
Bis- (1- methyl-1s-phenethyl) phenol (2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-
Phenylethyl) phenol), -4 (1,1,3,3- tetramethyl butyl) phenol (2- (2H- of 2- (2H- benzotriazole -2- bases)
Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), 2- (2H- benzotriazole -2- bases) -
6- (1- methyl-1s-phenethyl) -4- (1,1,3,3- tetramethyl butyl) phenol (2- (2H-benzotriazol-2-yl) -6- (1-
Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [4- [(2- hydroxyl -3- (2'-
Ethyl) hexyl) oxygen] -2- hydroxyphenyls] bis- (2,4- 3,5-dimethylphenyl) -1,3,5-triazines (2- [the 4- [(2-Hydroxy-3- of -4,6-
(2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] 4,6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine), 2- [4- [(2- hydroxyl -3- dodecyls oxygen propyl group) oxygen] -2- hydroxyphenyls] bis- (2, the 4- dimethyl benzenes of -4,6-
Base) -1,3,5-triazines (2- [4- [(2-Hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] 4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine) etc. be free of halogen ultraviolet absorber.
2) cellulosic resin
The optical thin film resin combination of the present invention contains cellulosic resin.It, can as above-mentioned cellulosic resin
With preferably by acylated cellulose (cellulose acylate), cellulosic triacetate (cellulose triacetate), vinegar
Sour cellulose butyrate (cellulose acetate butyrate), cellulose acetate propionate (cellulose acetate
) etc. propionate acylated celluloses (cellulose acylate) resinoid individually or mixes two or more and uses, best
Cellulosic triacetate can be used.In this case, especially good with the high molecular compatibility of trapezoidal silsesquioxane, thus
The optics such as transmissivity, heat resistance and water resistance, physical characteristic can be met simultaneously.
The present invention optical thin film resin combination in, above-mentioned trapezoidal its content of silsesquioxane macromolecule relative to
The cellulosic resin of 1 parts by weight is 0.1 to less than 20 parts by weight, preferably less than 15 parts by weight, in this case can be same
When meet heat resistance, ultraviolet light blocking effect, water resistance and plasticization effect etc..If the high molecular content of silsesquioxane
Cellulosic resin relative to 1 parts by weight is the situation of 20 parts by weight or more, it is likely that excessively production between two substances
Raw polarity is poor and leads to the reduction of compatibilized degree, and is possible to generate muddy effect.
For the optical thin film resin combination of the present invention, can diversely it be utilized with composition itself, but in order to
It is prepared with the conventional method as the solvent cast of compatibilized, solvent can be utilized, for the type of solvent, as long as
No matter the type that two kinds of mixtures will not be caused to detach then using any can also it is expected identical effect.
At this point, the content of solvent is with the tree other than above-mentioned trapezoidal silsesquioxane macromolecule and cellulosic resin
The surplus of fat includes, used solvent so that above-mentioned trapezoidal silsesquioxane macromolecule and cellulosic resin solid
Components total content, which becomes 1 to 50 weight %, to be advisable, and preferably makes above-mentioned trapezoidal silsesquioxane macromolecule and cellulosic resin
Solid constituent amount to content become 10 to 40 weight %.In the case where the content of solid constituent is fallen within the above range, energy
Enough it is well maintained flatness, the operability etc. of film.
Moreover, the optical thin film resin combination of the present invention, can further contain in usual range increase as needed
The functional additive that modeling agent, ultraviolet isolating agent or optical thin film resin combination can usually contain.
Moreover, the present invention provides a kind of optical thin film by manufactured by above-mentioned optical thin film resin combination and including should
The optical instrument of optical thin film.
Optical thin film according to the present invention can be according at this other than using above-mentioned optical thin film resin combination
Field commonly used approach manufactures, for example, using spray-on process, rolling method, spin-coating method etc. on the basis material appropriate with
0.1 to 5,000 μm thickness coating after 30 to 150 DEG C temperature range carry out heated-air drying and can be made, and use
The excellent resin combinations such as heat resistance, ultraviolet light blocking effect, water resistance and plasticization effect, thus effectively be used in
Manufacture not only maintains the excellent translucency of cellulose family film but also improves the protective film for polarizing plate of physical characteristic, compensation
The cellulose family optical thin film of film etc..
Following for contribute to understand the present invention and prompt preferred embodiment, but following embodiments only illustrate the present invention and
, the scope of the present invention is not limited to following embodiments.
Synthesis example 1：The preparation of cellulose solution
By dichloromethane and methanol with 9：9 parts by weight in the mixed solvents of 1 (weight ratio) mixing instill the three of 1 parts by weight
Acetylcellulose (Sigma-Aldrich, Fluka), and be mixed with after 1 day or more, it is prepared for cellulose solution.
Synthesis example 2：The high molecular preparation of silsesquioxane
It is (pure that 15 weight % distilled water, 4 weight % methanol are mixed in the flask for the drying for having cooling tube and blender
Degree for 99.86%) and 1 weight % tetramethylammonium hydroxides (25% aqueous solution (in water)) and it is previously prepared containing urging
After the mixed reaction solvent of agent, the silane monomer of 80 weight % is added in the mixed reaction solvent being ready for.At this point,
The mixing ratio for the silane monomer being added is trimethoxy-benzene base silane (Dow Corning Corporation, trade name DOWCORNING (R) Z-
6124SILANE) 10 moles of %：γ-methacryloxypropyl trimethoxy silane (Dow Corning Corporation, trade name
DOWCORNING (R) Z-6030SILANE) 90 moles of %.
Hereafter, it blows slowly in nitrogen atmosphere and stops the stirring of reaction solution after stirring 8 hours, and place 24 at normal temperatures
Vacuum filter is carried out to the above-mentioned reaction solution containing sediment after a hour and has detached sediment.With distilled water and methanol
Mixed liquor be cleaned multiple times and filter separated sediment and remove impurity and with methanol finally clean after, at normal temperatures into
It has gone the vacuum drying of 20 hours, 1 parts by weight of thus obtained gains has been instilled with 9：1 (weight ratio) is mixed with dichloro
9 parts by weight of mixed solvent of methane and methanol and be prepared for desirable poly- aliphatic aromatic silsesquioxane high score subtree
Fat.The obtained poly- high molecular weight average molecular weight of aliphatic aromatic silsesquioxane is 40,000.At this point, weight average molecular weight
Be using gel permeation chromatography and measure polystyrene conversion average molecular weight.
Synthesis example 3 to 9：The high molecular preparation of silsesquioxane
In addition in 15 weight % distilled water, 4 weight % methanol (purity 99.86%) and 1 weight % tetramethylphosphonihydroxide hydroxides
Instilled except 80 weight % silane monomers with the molar ratio of such as the following table 1 in ammonium (25% aqueous solution (in water)), with it is upper
It states 2 identical method of synthesis example and is prepared for macromolecule silsesquioxane resin.
Table 1
Embodiment 1 to 5：The mixed solution of cellulose/silsesquioxane resin composition prepares and is utilized solution-cast
The thin film fabrication of method
1 parts by weight of cellulose solution prepared by above-mentioned synthesis example 1 are respectively with 0.2,0.4,0.6,0.8 and 1 weight
Part is mixed with the silsesquioxane macromolecule prepared by above-mentioned synthesis example 2 and is prepared for the resin group prepared for solution-cast
Close object.Prepared above-mentioned composition was made thin on a glass and through heated-air drying with speed casting in 20cm/ seconds
Film.
Embodiment 6 to 12
In addition to by prepared by above-mentioned synthesis example 3 to 9 each 1 parts by weight of silsesquioxane macromolecule in above-mentioned synthesis example
Prepared by 11 parts by weight of cellulose solution mixing and be prepared for except respective resin combination, with 1 phase of above-described embodiment
Same method has manufactured film.
Comparative example 1
By the cellulose solution prepared by above-mentioned synthesis example 1 it is same as Example 1 cast in 20cm/ seconds speed
Film has been made on glass plate and through heated-air drying.
Comparative example 2
In addition to by 20 parts by weight of silsesquioxane macromolecule prepared by synthesis example 2 and fibre prepared by synthesis example 1
Except dimension plain solution 1 parts by weight mixing, resin combination and film have been manufactured in method identical with above-described embodiment 1.
Comparative example 3
Other than using 80 weight % trimethoxy-benzenes base silanes as independent silane monomer, with above-mentioned synthesis example 2
Identical method is prepared for resin, is prepared for resin combination and film later in method identical with embodiment 6 to 12.
Test example 1
It confirmed the silsesquioxane/Cellulose resin composition and comparative example 1 of above-described embodiment 1 to 5 by test
With compatibility, turbidity and the transmissivity of 2 resin combination.Specifically, it in order to carry out compatibility test, is cut with intersecting
Segmentation method has made the unit (cellar area=5mm of the 10X10 utilized when the test of substrate bonding power2), for 100 units
Judge and arrange as follows：Think if the number for the unit for being 5% or more with the differences in turbidity of center cell is less than 10
Compatibility is very excellent；Think excellent if less than 20；Think general if less than 30；Think if more than 50 or more
It is difficult to compatibilized.Moreover, in order to critically measure turbidity, by the marginal portion of manufactured all film samples and central part
Turbidity determine 3 times or more respectively and describe its average value.Also, it is surveyed with method, edge and the central part with such as turbidity
Determine method to measure the optical absorption spectra (spectrum) of visible light and be averaged to the transmissivity of manufactured film, in 400nm
It measures and describes light transmittance.The results are shown in the following table 2 and Fig. 1.
Table 2
| Compatibility | Turbidity (%) | Transmissivity (%) | |
| Comparative example 1 | - | 0.4 | 92.0 |
| Embodiment 1 | ◎ | 0.4 | 92.0 |
| Embodiment 2 | ◎ | 0.6 | 91.5 |
| Embodiment 3 | ◎ | 0.5 | 91.4 |
| Embodiment 4 | ◎ | 0.7 | 91.0 |
| Embodiment 5 | ○ | 0.8 | 88.0 |
| Comparative example 2 | × | 5.1 | 61.0 |
(◎：It is very excellent, zero：It is excellent, △：Generally, ×：It is unable to compatibilized)
As shown in upper table 2 and Fig. 1, the transmissivity in view of the basis material film manufactured by comparative example 1 is 92%, it is known that
Its compatibility of 1 to 5 composition is very excellent according to an embodiment of the invention, moreover, the raising of compatibility makes turbidity be less than
1%, show very excellent muddy effect.
In contrast, it can be seen that from following table, in above-mentioned comparative example 2 in the case of prepared composition, two resins
Between compatibility drastically reduce.Understand that this result proportionally impacts on the transmissison characteristic of manufactured film.
Test example 2
It confirmed that the resin combination prepared by above-described embodiment 6 to 12 is compatible with the resin combination of comparative example 3
Property and transmissivity, the results are shown in the following table 3 and Fig. 2.
Table 3
| Compatibility | Turbidity (%) | Transmissivity (%) | |
| Embodiment 6 | ◎ | 0.8 | 88.0 |
| Embodiment 7 | ◎ | 0.8 | 87.8 |
| Embodiment 8 | ◎ | 0.9 | 87.5 |
| Embodiment 9 | ◎ | 1 | 86.5 |
| Embodiment 10 | ○ | 1.1 | 85.5 |
| Embodiment 11 | ○ | 1.3 | 84.5 |
| Embodiment 12 | ○ | 1.2 | 84.1 |
| Comparative example 3 | × | 5.5 | 67.5 |
As shown in upper table 3 and Fig. 2, it can be seen that if aromatic series is organic in organic side chain functional group in silsesquioxane macromolecule
The content of functional group increases to certain level or more, then turbidity (haze) sharply increases.It therefore, can be true from the point of view of this result
Recognizing the content of the aromatic functional groups utilized to improve physical characteristic must be adjusted in certain level.
Test example 3
FT-IR spectrometers are utilized for the cellulose manufactured by above-described embodiment 1-silsesquioxane mixed film
(the ATR patterns of Perkin-Elmer system Spectrum-GX) determines IR, and the results are shown in Fig. 3.
As shown in figure 3, in optical thin film according to the present invention, in 960 to 1,200cm-1It is bimodal (continuous anti-to there is width
Complex shape) absorption peak, this is in silsesquioxane chain on vertical (- Si-O-Si-R) and horizontal direction (- Si-O-Si-)
The stretching vibration (Stretching Vibration) that siloxanes combines.Moreover, when being mixed with cellulose family solution, from structure
On be also able to confirm that out being clearly present for silsesquioxane, and do not occur haze characteristics.
Test example 4
It confirmed manufactured by above-described embodiment 1 using TGA (thermal gravimetric analyzer) and DSC
The thermal stability of cellulose-silsesquioxane mixed film, result are shown in Fig. 4 and Fig. 5.At this point, in nitrogen atmosphere and
50 to 600 DEG C of temperature range is with the scan speed measurement of 10 DEG C/min TGA.
As shown in Figure 4 and Figure 5, can confirm in cellulose according to the present invention-silsesquioxane mixed film, fiber
Thermal characteristics possessed by element does not reduce, and thermal characteristics is improved with the high molecular addition of silsesquioxane.
Test example 5
In order to observe cellulose-silsesquioxane macromolecule mixed film and the comparative example 1 manufactured by above-described embodiment 1
Cellophane moisture permeability change (unit：g/m2/ day), it is carried out under 25 DEG C, 100% environment using Mocon3/33 types
Test, the results are shown in the following table 4.
As shown in upper table 3 and Fig. 2, it can be seen that if aromatic series is organic in organic side chain functional group in silsesquioxane macromolecule
The content of functional group increases to certain level or more, then turbidity (haze) sharply increases.It therefore, can be true from the point of view of this result
Recognizing the content of the aromatic functional groups utilized to improve physical characteristic must be adjusted in certain level.
Test example 3
FT-IR spectrometers are utilized for the cellulose manufactured by above-described embodiment 1-silsesquioxane mixed film
(the ATR patterns of Perkin-Elmer system Spectrum-GX) determines IR, and the results are shown in Fig. 3.
As shown in figure 3, in optical thin film according to the present invention, in 960 to 1,200cm-1It is bimodal (continuous anti-to there is width
Complex shape) absorption peak, this is in silsesquioxane chain on vertical (- Si-O-Si-R) and horizontal direction (- Si-O-Si-)
The stretching vibration (Stretching Vibration) that siloxanes combines.Moreover, when being mixed with cellulose family solution, from structure
On be also able to confirm that out being clearly present for silsesquioxane, and do not occur haze characteristics.
Test example 4
It confirmed manufactured by above-described embodiment 1 using TGA (thermal gravimetric analyzer) and DSC
The thermal stability of cellulose-silsesquioxane mixed film, result are shown in Fig. 4 and Fig. 5.At this point, in nitrogen atmosphere and
50 to 600 DEG C of temperature range is with the scan speed measurement of 10 DEG C/min TGA.
As shown in Figure 4 and Figure 5, can confirm in cellulose according to the present invention-silsesquioxane mixed film, fiber
Thermal characteristics possessed by element does not reduce, and thermal characteristics is improved with the high molecular addition of silsesquioxane.
Test example 5
In order to observe cellulose-silsesquioxane macromolecule mixed film and the comparative example 1 manufactured by above-described embodiment 1
Cellophane moisture permeability change (unit：g/m2/ day), it is carried out under 25 DEG C, 100% environment using Mocon3/33 types
Test, the results are shown in the following table 4.
Table 4
| The cellophane of comparative example 1 | The mixed film of embodiment 1 | |
| 1 time | 623 | 50 |
| 2 times | 650 | 45 |
| 3 times | 590 | 49 |
| 4 times | 660 | 39 |
| It is average | 631 | 46 |
As shown in upper table 4, containing the trapezoidal high molecular film of silsesquioxane according to the present invention, moisture permeability compares fiber
Plain resin film itself reduces 1/14 or so, to show the moisture permeability being greatly reduced.
Therefore, film can more effectively improve protectant cellulose as light polarizing film made in accordance with the present invention
Class film prevents iodine distillation function.
Industrial utilizability
Optical thin film resin group according to the present invention containing trapezoidal silsesquioxane macromolecule and cellulosic resin
Object is closed, even if containing being also showed that and the trapezoidal silsesquioxane of the high-compatibility of cellulosic resin height without other chemical reaction
Molecule, thus heat resistance, ultraviolet light blocking effect, water resistance and plasticization effect etc. are excellent, therefore, effectively are used in making
It makes and not only maintains the excellent translucency of cellulose family film but also improve the protective film for polarizing plate of physical characteristic, compensation film
Deng cellulose family optical thin film.
Claims (9)
1. a kind of optical thin film resin combination, which is characterized in that contain：
1) the trapezoidal silsesquioxane macromolecule 0.1-10 parts by weight that weight average molecular weight is 1,000 to 1,000,000；And
2) 1 parts by weight of cellulosic resin,
Above-mentioned trapezoidal silsesquioxane macromolecule has the structure of following chemical formula 1：
[chemical formula 1]
In above-mentioned chemical formula 1,
In R1To R4Total 100% in aromatic series organo-functional group content be less than 80%,
Above-mentioned cellulosic resin is selected from by acylated cellulose, cellulosic triacetate, acetylbutyrylcellulose and acetic acid
One or more of the group of cellulose propionate composition,
R1To R4It is each independently hydrogen, with C1To C20The ring-type or Noncyclic aliphatic organo-functional group, alkyl halide, virtue of connection
Base, amino, (methyl) acrylic, epoxy group or mercapto, at this point, R1To R4By mutually the same or mutually different organic official
It can roll into a ball and be replaced,
R5To R8It is each independently selected from C1-5Alkyl, C3-10Naphthenic base, C6-12Aryl, hydrogen, n be 1 to 100,000,
In above-mentioned chemical formula 1, the content of-OH of end is 0.01 to 50% in end group.
2. optical thin film resin combination according to claim 1, which is characterized in that
Above-mentioned chemical formula 1 is prepared by being carried out continuously polymerisation after making the compound hydrolyzable of following chemical formula 2
Silsesquioxane macromolecule：
[chemical formula 2]
R9 4-m-Qp-Si-(OR10)m
In above-mentioned formula,
R9It is hydrogen, with C1To C20The ring-type or Noncyclic aliphatic organo-functional group of connection, alkyl halide, aryl, amino, (methyl)
Acrylic, epoxy group or mercapto；
R10Selected from by C1-5Alkyl, C3-10Naphthenic base, C6-12The group that is formed of aryl, hydrogen and combination thereof in,
Q is C1-6Alkylidene or C1-6Alkylene oxide group,
M is 3 or 4 integer,
P is 0 or 1 integer,
And m+p=4.
3. optical thin film according to claim 1 cellulosic resin composition, which is characterized in that
Above-mentioned cellulosic resin is cellulosic triacetate.
4. optical thin film according to claim 1 cellulosic resin composition, which is characterized in that
Above-mentioned resin combination further contains plasticizer, functional additive or ultraviolet isolating agent.
5. optical thin film resin combination described in claim 1 is coated with laggard by a kind of optical thin film on substrate
Row drying and be made.
6. optical thin film according to claim 5, which is characterized in that
The transmissivity of above-mentioned optical thin film is at least 80%.
7. optical thin film according to claim 5, which is characterized in that
It is 50g/m that the moisture permeability of above-mentioned optical thin film, which changes at 25 DEG C,2/ day or less.
8. optical thin film according to claim 5, which is characterized in that
Above-mentioned optical thin film is the compensation film of display or the protective film of polarizing film.
9. a kind of optics or display device, it includes the optical thin films described in claim 5.
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| KR10-2012-0031146 | 2012-03-27 | ||
| KR20120031146 | 2012-03-27 | ||
| KR1020130023227A KR102004493B1 (en) | 2012-03-27 | 2013-03-05 | Ladder-like silsesquioxane polymer and resin composition for optical film comprising the same |
| KR10-2013-0023227 | 2013-03-05 | ||
| PCT/KR2013/002043 WO2013147443A1 (en) | 2012-03-27 | 2013-03-14 | Resin composition containing ladder-like silsesquioxane polymer for optical film |
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| CN104220531A CN104220531A (en) | 2014-12-17 |
| CN104220531B true CN104220531B (en) | 2018-08-14 |
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| KR102363819B1 (en) * | 2014-02-28 | 2022-02-17 | 주식회사 동진쎄미켐 | Silsesquioxane composite polymer and method for manufacturing thereof |
| WO2015130146A1 (en) * | 2014-02-28 | 2015-09-03 | 주식회사 동진쎄미켐 | Transparent substrate having reinforced surfaces and method for manufacturing same |
| KR102367120B1 (en) * | 2014-02-28 | 2022-02-25 | 주식회사 동진쎄미켐 | A surface enhanced transparent substrate and method for manufacturing thereof |
| KR102325278B1 (en) * | 2014-03-07 | 2021-11-16 | 주식회사 동진쎄미켐 | A thermoplastic resin composion comprising silsesquioxane composite polymer |
| KR101698868B1 (en) * | 2014-11-06 | 2017-01-24 | (주)다솜뜰 | Biodegradable polymer film and its preparation method |
| WO2016122191A1 (en) * | 2015-01-26 | 2016-08-04 | 주식회사 동진쎄미켐 | Coated product, and high-hardness curved surface hard coating method |
| CN110139905B (en) * | 2016-12-30 | 2021-09-28 | 株式会社东进世美肯 | Coating composition and film prepared therefrom |
| US11628998B2 (en) * | 2018-12-13 | 2023-04-18 | Johnson & Johnson Vision Care, Inc. | Ultraviolet light inhibiting contact lens package |
| KR102554549B1 (en) * | 2020-12-11 | 2023-07-12 | 엔씨케이 주식회사 | Low Refractive Composition for OLED Overcoat |
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| Publication number | Publication date |
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| JP2015518502A (en) | 2015-07-02 |
| TWI616487B (en) | 2018-03-01 |
| TW201343791A (en) | 2013-11-01 |
| CN104220531A (en) | 2014-12-17 |
| JP6189413B2 (en) | 2017-08-30 |
| KR102004493B1 (en) | 2019-07-26 |
| KR20130110018A (en) | 2013-10-08 |
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