CN103467779A - Cellulose triacetate membrane - Google Patents
Cellulose triacetate membrane Download PDFInfo
- Publication number
- CN103467779A CN103467779A CN2013104093195A CN201310409319A CN103467779A CN 103467779 A CN103467779 A CN 103467779A CN 2013104093195 A CN2013104093195 A CN 2013104093195A CN 201310409319 A CN201310409319 A CN 201310409319A CN 103467779 A CN103467779 A CN 103467779A
- Authority
- CN
- China
- Prior art keywords
- cellulose triacetate
- plasticizer
- thin film
- membrane
- biphosphonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a cellulose triacetate membrane which is prepared from a solution containing cellulose triacetate, a solvent and a plasticizer by using a solution curtain-casting method. The cellulose triacetate membrane is characterized in that the dosage of the plasticizer is 3-15% of weight of the cellulose triacetate; the plasticizer is prepared from a triphenyl phosphate primary plasticizer and an aryl diphosphate coplasticizer; the weight ratio of aryl diphosphate to triphenyl phosphate is 1/6 to 4/5. By adopting the cellulose triacetate membrane, precipitation of the plasticizer caused by fluctuation of a production process condition in a membrane production process is solved; apparent defects of the membrane caused by precipitation of the plasticizer are avoided; the apparent mass, the optical property and the physical and mechanical properties of the membrane are ensured; meanwhile, the cellulose triacetate membrane accords with the environment-friendly emission requirements.
Description
Technical field
The present invention relates to a kind of cellulose triacetate thin film.
Technical background
The acetyl cellulose of average acetify degree 57.5 ~ 62.5% generally is referred to as cellulose triacetate; its cellulose triacetate film of making (TAC film) is because having excellent optical isotropy; be suitable as the polaroid inner protection film or types of functionality retes such as chromatic color filter, anti-dazzling film, antireflection film, phase retardation film for liquid-crystal display, and its market is in expansion at full speed.
The TAC film generally adopts the solution casting method preparation, being about to cellulose triacetate, softening agent, each analog assistant etc. is dissolved in solvent, form thickness high density cotton glue, then high density cotton glue curtain coating for no reason on support, is formed to film through series of processes such as super-dry, rollings at band shape or cydariform.With other method, as melting casting method, melt extrusion method, compare, the optical isotropy of the film that solution casting method obtains is fabulous, and has splendid optical characteristics and physical and chemical performance, is particularly useful for the application that optics shows.
For optical property and the physicals of improving the TAC film, when preparing, it need to use softening agent.From known documents and materials, can find, in prior art, softening agent commonly used is that phosphoric acid ester is as triphenylphosphate, phenylbenzene xenyl phosphoric acid ester, three hot phosphoric acid ester, tolyl diphenyl phosphoester, three hot phosphoric acid ester, Tributyl phosphate ester, phthalate, these softening agent can be used separately, also can several plasticizer combinations use.
Along with the raising of people's level of understanding and the reinforcement of environment protection; some developed countries have strengthened containing the likely monitoring of harmful material; as phthalic ester can enter human body by approach such as respiratory tract, digestive tube and skins, human body is produced to larger injury.EPA (EPA) is listed 6 kinds of phthalate compounds in the pollutent list of 129 kinds of priority controls in, comprises dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), dioctyl phthalate (DOP) (DOP), butyl benzyl phthalate (BBP) and phthalic acid two (2-ethylhexyl) ester (DEHP).Therefore find new nontoxic, free of contamination softening agent, substitute phthalic ester plasticizer and do not affect the performance index of cellulose triacetate thin film, seem extremely important.
In order to substitute phthalic ester plasticizer, related documents discloses and can be used in combination to improve by triphenyl phosphoric acid lipid and xenyl diphenyl phosphoester the physical and mechanical properties of film, but, fluctuation because of manufacturing condition in the production process of film causes plasticizer extraction, and then it is apparent to affect film, form quality drawback.
Summary of the invention
Technical problem to be solved by this invention is the deficiency existed for prior art, and a kind of cellulose triacetate thin film is provided, and it has splendid apparent, optical characteristics and physical and chemical performance.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of cellulose triacetate thin film, the solution that it will contain cellulose triacetate, solvent and softening agent adopts the solution casting method preparation, the consumption of described softening agent is 3% ~ 15% of cellulose triacetate weight, softening agent is comprised of triphenylphosphate primary plasticizer and aryl biphosphonate co-plasticizer, and the weight ratio between aryl biphosphonate and triphenylphosphate is 1/6 ~ 4/5.
Above-mentioned cellulose triacetate thin film, the weight ratio between described aryl biphosphonate and triphenylphosphate is 1/5 ~ 2/3.
Above-mentioned cellulose triacetate thin film, the weight ratio between described aryl biphosphonate and triphenylphosphate is 1/4 ~ 1/3.
Above-mentioned cellulose triacetate thin film, described aryl biphosphonate is selected from Resorcinol tetraphenyl bisphosphate, dihydroxyphenyl propane two (diphenyl phosphoester), bisphenol S two (hexichol phosphoric acid ester).
Above-mentioned cellulose triacetate thin film, described solvent comprises solvent and solubility promoter, wherein, solvent is selected from one or more in acetone, butanone, methylene dichloride, trichloromethane, ethyl acetate, butylacetate; Solubility promoter is selected from one or more in methyl alcohol, ethanol, butanols.
Compared with prior art, the present invention is by adopting being used in combination of triphenylphosphate primary plasticizer and aryl biphosphonate co-plasticizer, and pass through the control of consumption between usage ratio, softening agent and cellulose triacetate between major-minor softening agent, solved in the film production process plasticizer extraction that fluctuation because of manufacturing condition causes, avoided because of the apparent disadvantage of the plasticizer extraction film caused, guarantee apparent mass, optical property and the physical and mechanical properties of film, met national Environmental policy requirement simultaneously.
Embodiment
The softening agent that the present invention adopts has following performance: (1) has good intermiscibility with cellulose triacetate; (2) plasticizing efficiency is high; (3) stable to thermo-optical; (4) volatility is low; (5) transport property is little; (6) low temperature flexibility is good; (7) good flame resistance; (8) electrical insulating property is good; (9) colourless, tasteless, nontoxic; (10) stain resistance is good; (11) the plastipaste viscosity stability is good; (12) inexpensive.
According to above-mentioned performance requriements, guarantee the performance of film simultaneously, the softening agent in the present invention adopts being used in combination of triphenylphosphate primary plasticizer and aryl biphosphonate co-plasticizer.From chemical structure, the speedup of low-molecular-weight softening agent higher molecular weight is effective.Adopt the triphenylphosphate of small molecules amount as primary plasticizer is good with the cellulose triacetate consistency, flame retardant effect is good; In addition, micromolecular triphenylphosphate is easy to motion, reduced the anti-deformation behavior of cellulose triacetate inside, overcome between macromolecular cellulose triacetate the adhesive power that directly phase mutual friction and Van der Waals force produce, thereby can play the speedup effect; But due to its molecular weight, its volatility is larger, easily separates out in cellulose triacetate thin film, thereby affect, it is apparent.The aryl biphosphonate of macromolecule is because its molecular weight is larger, so anti-extraction, and transport property is little; But in its molecule, aromatic ring structure is more, consumption too much can make plasticization effect reduce, and therefore needs to control its consumption.Therefore, by being used in combination of they, both guaranteed that the optical property of cellulose triacetate thin film, physical and mechanical properties are qualified, can realize again the apparent optimum of film.
In the present invention, the contriver is by a series of different combination experiments with to the test of cellulose triacetate thin film correlated performance, part by weight between aryl biphosphonate and triphenylphosphate is advisable between being controlled at 1/6 ~ 4/5, more the ratio of greater inequality example is 1/5 ~ 2/3, most preferred ratio is 1/4 ~ 1/3, the film performance obtained like this is more excellent, apparent also better.
Being applicable to aryl biphosphonate of the present invention can adopt and be not limited only to following compound: Resorcinol tetraphenyl bisphosphate, dihydroxyphenyl propane two (diphenyl phosphoester), bisphenol S two (hexichol phosphoric acid ester).
In the present invention, the contriver finds after deliberation, and softening agent can adopt the multiple mode that adds, and can directly add in mixed solvent and dissolve in advance; Also can adopt triphenylphosphate to add in advance in mixed solvent, then two aryl biphosphonates be joined and are dissolved with the TAC(cellulose triacetate) solution in; Also can adopt in the solution conveyor tube road and add, adopt static mixer to mix; Also can when dissolving TAC, together with other auxiliary agents, jointly add; Above adition process all should guarantee that triphenylphosphate or simultaneously adds when adding the aryl biphosphonate.The consumption of softening agent is 3% ~ 15% of TAC weight.
In the present invention, the solvent provided can be one or more in acetone, butanone, methylene dichloride, trichloromethane, ethyl acetate, butylacetate, is preferably methylene dichloride, trichloromethane, ethyl acetate, more preferably methylene dichloride, trichloromethane.
In the present invention, for increasing the dissolving of TAC, also used solubility promoter, being applicable to solubility promoter of the present invention can be one or more in methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, is preferably methyl alcohol, ethanol, propyl carbinol, more preferably methyl alcohol, propyl carbinol.
Cellulose triacetate thin film provided by the invention, adopt the solution casting method preparation, the solution that will contain cellulose triacetate, solvent and softening agent through curtain coating, peel off, dry, rolling and obtaining.
Below in conjunction with specific embodiment, the present invention is described in further detail, and its protection domain includes but not limited to specific embodiment.
Embodiment 1.
1.2 portions of triphenylphosphates, 0.3 part of dihydroxyphenyl propane two (diphenyl phosphoester) are joined in the mixed solvent of 70 parts of methylene dichloride, 6 parts of methyl alcohol, stirring and dissolving, add afterwards 14 parts of cellulose triacetates, after dissolving, filter, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Embodiment 2.
1.0 portions of triphenylphosphates, 0.2 part of bisphenol S two (hexichol phosphoric acid ester) are joined in the mixed solvent of 72 parts of methylene dichloride, 8 parts of methyl alcohol, stirring and dissolving, add afterwards 14 parts of cellulose triacetates, after dissolving, filter, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Embodiment 3.
0.3 portion of triphenylphosphate, 0.2 part of Resorcinol tetraphenyl bisphosphate are joined in the mixed solvent of 76 parts of methylene dichloride, 4 parts of methyl alcohol, stirring and dissolving, add afterwards 14 parts of cellulose triacetates, after dissolving, filter, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Embodiment 4.
1.2 portions of triphenylphosphates, 0.4 part of dihydroxyphenyl propane two (diphenyl phosphoester) are joined in 70 parts of acetone, the methanol mixed solvent of 10 parts, stirring and dissolving, add afterwards 14 parts of cellulose triacetates, after dissolving, filter, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Embodiment 5.
0.6 portion of triphenylphosphate, 0.2 part of dihydroxyphenyl propane two (diphenyl phosphoester) are joined in 72 parts of trichloromethanes, the butanols mixed solvent of 9 parts, stirring and dissolving, add afterwards 15 parts of cellulose triacetates, after dissolving, filter, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Embodiment 6.
1.0 portions of triphenylphosphates, 0.8 part of dihydroxyphenyl propane two (diphenyl phosphoester) are joined in the mixed solvent of 70 parts of butylacetates, 7 parts of butanols, stirring and dissolving, add afterwards 15 parts of cellulose triacetates, after dissolving, filter, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Comparative Examples 1.
| Cellulosetri-acetate | 14 parts |
| Methylene dichloride | 70 parts |
| Methyl alcohol | 6 parts |
| Triphenylphosphate | 1.5 part |
1.5 portions of triphenylphosphates are joined in the mixed solvent of 70 parts of methylene dichloride, 6 parts of methyl alcohol, stirring and dissolving, add 14 parts of cellulose triacetates afterwards, after dissolving, filters, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Comparative Examples 2.
| Cellulosetri-acetate | 14 parts |
| Methylene dichloride | 70 parts |
| Methyl alcohol | 6 parts |
| Triphenylphosphate | 1.2 part |
| The xenyl diphenyl phosphoester | 0.3 part |
1.2 portions of triphenylphosphates, 0.3 part of xenyl diphenyl phosphoester are joined in the mixed solvent of 70 parts of methylene dichloride, 6 parts of methyl alcohol, stirring and dissolving, add afterwards 14 parts of cellulose triacetates, after dissolving, filter, through curtain coating, peel off, dry, rolling, obtain cellulose triacetate thin film of the present invention.Record its performance.
Table 1
| ? | Physical and mechanical properties | Film is apparent | Weathering resistance |
| Embodiment 1 | Excellent | Excellent | Excellent |
| Embodiment 2 | Good | Good | Excellent |
| Embodiment 3 | Good | Good | Good |
| Embodiment 4 | Excellent | Generally | Excellent |
| Embodiment 5 | Good | Generally | Excellent |
| Embodiment 6 | Excellent | Generally | Excellent |
| Comparative Examples 1 | Excellent | Generally | Good |
| Comparative Examples 2 | Excellent | Good | Good |
In table 2, the testing method of correlated performance is as follows
1. water capacity
According to HG/T3558-1988, test.
2. apparent, weathering resistance
According to HG/T 4150-2010, test.
3. mist degree
According to GB/T 25273-2010, test.
4. physical and mechanical properties
According to GB/T 12683-2009, test.
6. rate of expansion, shrinking percentage
According to GB/T 15059-1994, test.
7. folding endurance
According to GB/T 9858-2009 built-in testing.
Table 2
Claims (5)
1. a cellulose triacetate thin film, the solution that it will contain cellulose triacetate, solvent and softening agent adopts the solution casting method preparation, it is characterized in that, the consumption of described softening agent is 3% ~ 15% of cellulose triacetate weight, softening agent is comprised of triphenylphosphate primary plasticizer and aryl biphosphonate co-plasticizer, and the weight ratio between aryl biphosphonate and triphenylphosphate is 1/6 ~ 4/5.
2. cellulose triacetate thin film according to claim 1, is characterized in that, the weight ratio between described aryl biphosphonate and triphenylphosphate is 1/5 ~ 2/3.
3. cellulose triacetate thin film according to claim 2, is characterized in that, the weight ratio between described aryl biphosphonate and triphenylphosphate is 1/4 ~ 1/3.
4. cellulose triacetate thin film according to claim 3, is characterized in that, described aryl biphosphonate is selected from Resorcinol tetraphenyl bisphosphate, dihydroxyphenyl propane two (diphenyl phosphoester) or bisphenol S two (hexichol phosphoric acid ester).
5. cellulose triacetate thin film according to claim 4, is characterized in that, described solvent comprises solvent and solubility promoter, and wherein, solvent is selected from one or more in acetone, butanone, methylene dichloride, trichloromethane, ethyl acetate, butylacetate; Solubility promoter is selected from one or more in methyl alcohol, ethanol, butanols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104093195A CN103467779A (en) | 2013-09-10 | 2013-09-10 | Cellulose triacetate membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104093195A CN103467779A (en) | 2013-09-10 | 2013-09-10 | Cellulose triacetate membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103467779A true CN103467779A (en) | 2013-12-25 |
Family
ID=49792834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013104093195A Pending CN103467779A (en) | 2013-09-10 | 2013-09-10 | Cellulose triacetate membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467779A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910424A (en) * | 2015-06-29 | 2015-09-16 | 中国乐凯集团有限公司 | Cellulose triacetate film |
| CN105093381A (en) * | 2015-09-24 | 2015-11-25 | 深圳市华星光电技术有限公司 | Quantum dot polarizer and manufacturing method thereof |
| CN110066424A (en) * | 2018-12-27 | 2019-07-30 | 中国乐凯集团有限公司 | A kind of cellulose triacetate thin film and preparation method thereof |
| CN110128707A (en) * | 2018-12-27 | 2019-08-16 | 中国乐凯集团有限公司 | A kind of cellulose triacetate film |
| CN111073011A (en) * | 2019-12-26 | 2020-04-28 | 中国乐凯集团有限公司 | Double-coating cellulose triacetate film |
| CN112525735A (en) * | 2020-11-17 | 2021-03-19 | 中国航发北京航空材料研究院 | Replica method for detecting fatigue small crack condition |
| CN112795037A (en) * | 2021-01-04 | 2021-05-14 | 湖南科技大学 | Preparation method of enhanced cellulose acetate transparent composite film |
| CN113997335A (en) * | 2021-11-24 | 2022-02-01 | 泉州市环球新材料科技有限公司 | Curtain coating membrane and bead cutter of this curtain coating membrane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120092595A1 (en) * | 2010-10-13 | 2012-04-19 | Fujifilm Corporation | Optical film, polarizing plate and liquid crystal display device |
-
2013
- 2013-09-10 CN CN2013104093195A patent/CN103467779A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120092595A1 (en) * | 2010-10-13 | 2012-04-19 | Fujifilm Corporation | Optical film, polarizing plate and liquid crystal display device |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910424A (en) * | 2015-06-29 | 2015-09-16 | 中国乐凯集团有限公司 | Cellulose triacetate film |
| CN105093381A (en) * | 2015-09-24 | 2015-11-25 | 深圳市华星光电技术有限公司 | Quantum dot polarizer and manufacturing method thereof |
| CN110066424A (en) * | 2018-12-27 | 2019-07-30 | 中国乐凯集团有限公司 | A kind of cellulose triacetate thin film and preparation method thereof |
| CN110128707A (en) * | 2018-12-27 | 2019-08-16 | 中国乐凯集团有限公司 | A kind of cellulose triacetate film |
| CN111073011A (en) * | 2019-12-26 | 2020-04-28 | 中国乐凯集团有限公司 | Double-coating cellulose triacetate film |
| CN112525735A (en) * | 2020-11-17 | 2021-03-19 | 中国航发北京航空材料研究院 | Replica method for detecting fatigue small crack condition |
| CN112795037A (en) * | 2021-01-04 | 2021-05-14 | 湖南科技大学 | Preparation method of enhanced cellulose acetate transparent composite film |
| CN113997335A (en) * | 2021-11-24 | 2022-02-01 | 泉州市环球新材料科技有限公司 | Curtain coating membrane and bead cutter of this curtain coating membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467779A (en) | Cellulose triacetate membrane | |
| TWI433881B (en) | A cellulose-based resin composition and a cellulose-based resin film | |
| CN101679683B (en) | Cellulose ester film, method for producing cellulose ester film, polarizing plate using the same, and liquid crystal display | |
| JP5067366B2 (en) | Retardation film, polarizing plate and liquid crystal display device | |
| EP2910600B1 (en) | Cellulose ester composition | |
| TWI465515B (en) | A fiber-based resin composition and a fiber-based resin film | |
| CN103518151B (en) | Phase retardation film, polaroid, liquid crystal indicator and compound | |
| CN101160348B (en) | Cellulose ester film, manufacturing method thereof, optical film, polarizing plate and liquid crystal display | |
| CN104040385B (en) | Phase retardation film, the manufacture method of phase retardation film, polaroid and liquid crystal indicator | |
| CN104271656A (en) | Cellulose resin composition | |
| DE112012006554T5 (en) | Highly miscible polymer blends and their use | |
| TW201219464A (en) | Cellulose acylate film and method for manufacturing the same, polarizing plate and liquid crystal display | |
| CN101160349B (en) | Cellulose ester film, process for producing the same, optical film, polarizer, and liquid-crystal display | |
| TW201139461A (en) | Cellulose acylate film, polarizing plate and liquid crystal display | |
| CN105723257B (en) | Retardation enhancer, the cellulose resin compositions and film for having used it | |
| US8142864B2 (en) | Cellulose ester pellets, cellulose ester film, manufacturing method of cellulose ester film, polarizing plate, and liquid crystal display | |
| CN104245851B (en) | Blooming, polaroid and liquid crystal indicator | |
| CN102445726A (en) | Phase difference compensation film and manufacturing method thereof | |
| JP5170076B2 (en) | Ultraviolet absorber, optical film containing the same, method for producing optical film, polarizing plate and liquid crystal display device using the same | |
| CN104910424A (en) | Cellulose triacetate film | |
| US8883272B2 (en) | Cellulose acylate film | |
| JP2011069857A (en) | Optical film and polarizing plate using the same, liquid crystal display device, and retardation developing agent | |
| KR20150077487A (en) | Stretched cellulose ester film, polarizing plate and liquid crystal display using the same | |
| JP4285921B2 (en) | Method for producing cellulose acylate film and cellulose acylate film | |
| KR20140112225A (en) | VA LCD viewing angle compensation optical film using cellulose ester film having acetyl group and butyl group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131225 |