CN101424764B - Method for enhancing inner protection film hydrophilicity of polaroid - Google Patents

Method for enhancing inner protection film hydrophilicity of polaroid Download PDF

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CN101424764B
CN101424764B CN2008101671968A CN200810167196A CN101424764B CN 101424764 B CN101424764 B CN 101424764B CN 2008101671968 A CN2008101671968 A CN 2008101671968A CN 200810167196 A CN200810167196 A CN 200810167196A CN 101424764 B CN101424764 B CN 101424764B
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protection film
inner protection
treatment
polaroid
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CN101424764A (en
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钟伟宏
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SHENZHEN SAPO PHOTOELECTRIC CO Ltd
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Abstract

The invention relates to a method for increasing the hydrophilicity of a protecting film in a polaroid. In the process of alkali treatment of the protecting film, the method adds a quaternary ammoniumsalt cation surface active agent with the following chemical structural formula. In the formula, R1, R2, R3 and R4 are alkyl chains, wherein at least one carbon chain is less than or equal to 2, andat least one carbon chain is between 12 and 20; X is one of F, Cl, Br and I of halogen elements; the addition of the surface active agent is 0.001-1 percent; the concentration of the treatment fluid (alkali solution) is from 2-12 percent; the treatment temperature is from 26-45 DEG C; and the treatment time is from 60-110s. On the premise of guaranteeing the treatment effect of the hydrophilicity,the addition of the surface active agent can reduce the concentration of the alkali solution, reduce the treatment temperature (and/or shorten the treatment time); and simultaneously, the uniformityof the treatment is obviously increased, thus, the production cost is lowered, and the pressure of environmental protection treatment is lightened.

Description

A kind ofly be used to improve polaroid inner protection film hydrophilicity method
Technical field
The invention belongs to a kind of polaroid inner protection film hydrophilicity method that is used to improve.
Background technology
Liquid crystal display (LCD) has utilized the photo of liquid crystal material, have Low-voltage Low-power, display effect good, be easy to carry, advantage such as application is wide, in current flat pannel display field (LCD, PDP, rear-projection) occupy the dominance.
The principle of work of LCD display is the deflection angle that changes liquid crystal molecule by extra electric field, and this change, has only by the rising partially of polaroid, analyzing function just to convert visual information (number, pattern, color etc.) to.Therefore, polaroid is one of vitals indispensable among the LCD.Polaroid accounts for the 8-15% of total cost of production in whole LCD display part.
The production run of film-type polaroid has dry-stretch process and wet method drawing process two big main flows, and its process flow diagram is seen accompanying drawing 1, Fig. 2.
With reference to Fig. 1, for wet method drawing process: PVA (polyvinyl alcohol (PVA), down with) film after washing, swelling; enter dyeing, then enter stretching and fixation, fixation enters drying after finishing; compound with the polaroid inner protection film again, dry once more back forms the former mating plate of polaroid.
With reference to Fig. 2, for dry-stretch process: under hot environment, utilize external force that the PVA film is stretched to required multiple after; enter washing, dyeing, fixation; fixation enters drying after finishing, and is compound with the polaroid inner protection film again, and dry once more back forms the former mating plate of polaroid.
Former mating plate has had basic polarizing properties.In processing subsequently, can on the basis of former mating plate, increase according to user's needs as functional membrane material or coatings such as AG, reflection (half reflection), optical compensations, can prepare the polaroid that satisfies multiple demand.
The wet method drawing process was different with dry-stretch process before PVA film fixation in the polaroid production run, but the technological process after the fixation is just the same.All that PVA film and polaroid inner protection film is compound, form the former mating plate of similar " sandwich " structure, in its purpose is wrapped in the PVA film with inner protection film exactly, thereby improve the reliability (being weatherability) of polaroid greatly.
As the material of polaroid inner protection film, require the transparency good, optical property is even, stable, and dimensional stability is good under heat and external force effect, also will take into account each procedure requirement that polaroid is produced simultaneously.Usually the material that adopts is the carboxylic acid cellulose membrane, as three cellulose acetate membrane, cellulose diacetate film, three cellulose butyrate films etc.
Inner protection film and PVA film are compound in the polaroid production, need to use tackifier, and for not influencing the performance of PVA film, the PVA that employing and PVA film intermiscibility are good is a water soluble adhesive usually.But the common water wettability of inner protection film is relatively poor (because carboxylic acid and cellulosic hydroxyl form esterification products; make cellulose lose water wettability); poor with the intermiscibility of water soluble adhesive, have influence on the bonding fastness of PVA film and inner protection film, thereby make inner protection film lose protective effect the PVA film.
For improving the water wettability of inner protection film, method in common has physical method and chemical method at present.
Physical method: be that inner protection film is adopted corona treatment, its process flow diagram is seen Fig. 3, and inner protection film is through unreeling, and through a pair of high-field electrode zone, be subjected to the bombardment of high energy ion after, rolling is with standby again.Its principle is to make air produce ionization by high-tension electricity, forms high-octane ion, and the surface of bombardment inner protection film is ruptured its surperficial chemical bond, generate and have highly active material (as free radical etc.), thereby the acquisition water wettability.
Adopt the method for corona treatment to have certain practical operation limitation; as the complicacy (needing electric high-voltage generator) of equipment, the danger (high-tension electricity that needs 5-25Kv) of operation and the pollution (producing ionized gases such as ozone simultaneously) of environment; in addition after the corona treatment; the water wettability retention time of inner protection film is lacked (20min-20h; decide on storage environment); therefore, the most chemical treatment methods that adopt of the method for during polaroid is produced at present the inner protection film water wettability being handled.
Chemical method: under alkaline environment; the carboxylate that carboxylic acid and cellulose are formed decomposes (title saponification), and cellulosic hydroxyl separates with carboxylate radical, is exposed to the surface of film again; (process flow diagram is seen Fig. 4 to reach hydrophilic raising; inner protection film enters in the aqueous solution that contains highly basic, under certain temperature, time through unreeling; with alkali generation chemical reaction; remove the alkali of remained on surface then by washing or acid neutralization, after super-dry, rolling is standby).
Its principle is seen accompanying drawing 5.The OH-base (hydroxyl, by alkali in water ionization and get) ester group of the carboxylate that forms of attack carboxylic acid and cellulose, carboxylate radical is replaced by the OH-base, separate with cellulose, be free in the water.Improve greatly with the cellulose water wettability that goes up the OH-base.
The factor that influences saponification mainly contains the concentration of alkali, temperature of reaction and reaction time, and in addition, the aqueous solution of alkali also is a key factor to the infiltration degree (homogeneity) of cellulose surface.
Conventional raising water wettability technology is: alkali adopts NaOH or KOH, and concentration is in 15-25% (weight ratio), and temperature is at 45-75 ℃, and the reaction time is 120-300s.For improving treatment effect, normally improve the concentration of alkali, the temperature that improves reaction or prolongation reaction time.
Improve the concentration of alkali, the concentration of OH-is risen, help saponification and carry out.But the concentration of alkali can not infinitely improve (maximum 50%).The concentration of alkali improves simultaneously, can increase viscosity in aqueous solution, influence its flowability and diffusivity, and solution polarity also increases, must influence infiltration and the diffusion of aqueous slkali at not hydrophilic cellulose esters face, hindered the homogeneity of saponification on the contrary and deeply carried out, thereby be limited by the effect that the concentration that improves alkali is improved saponification.Improve the concentration of alkali simultaneously, increase burden for the liquid waste processing in producing, be unfavorable for environmental protection, increased production cost.
Improve temperature of reaction, help improving the reactivity of OH-, accelerate saponification and carry out.But the adverse effect that the rising temperature is brought also is conspicuous.The mechanical property of cellulose membrane descends under the high temperature, causes bad phenomenon such as disconnected film, scuffing, distortion in the production easily; High temperature can increase the evaporation capacity of aqueous slkali simultaneously, pollutes production environment; In addition, keep higher temperature, can improve the requirement of relevant device, energy consumption increases, and operating cost increases.Therefore, to improve the effect of saponification also be limited by improving temperature of reaction.
The prolongation reaction time helps OH-basal orientation cellulose membrane internal layer to infiltrate, and can obviously improve treatment effect.But in actual production, prolong the reaction time, or prolong the time that cellulose membrane soaks in aqueous slkali, or reduce speed of production.It is enough big that the former requires the alkali treatment groove to have, and requires high to equipment and production site; The latter then is to be cost to sacrifice equipment capacity.This all can bring the increase of production cost.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part; a kind of concentration that can reduce aqueous slkali is provided; reduce treatment temperature (and/or shortening the processing time); the homogeneity of improve handling simultaneously, and can reduce production costs, alleviate environmental protection treatment pressure be used to improve polaroid inner protection film hydrophilicity method.
Technical scheme of the present invention is: a kind ofly be used to improve polaroid inner protection film hydrophilicity method; it is characterized in that adding a kind of quaternary ammonium salts cationic surfactant in inner protection film alkali treatment process, the chemical structural formula of described quaternary ammonium salts cationic surfactant is as follows:
Figure G2008101671968D00051
In the formula: R1, R2, R3 and R4 are alkyl chain, wherein, have at least a carbochain to be less than or equal to 2, have a carbochain at least between 12-20;
X is one of halogen F, Cl, Br, I;
The addition of surfactant is 0.001-1%;
Treating fluid is that the concentration of aqueous slkali is 2-12%;
Treatment temperature is 25-45 ℃;
Processing time is 60-110s.
The present invention is the further investigation that improves inner protection film water wettability technology by to the chemical method of routine, and experiment finally draws repeatedly, adds the method for surfactant in the alkali treatment process, improves treatment effect.The adding of surfactant; can improve the surface infiltration degree (homogeneity and the degree of depth) of aqueous slkali effectively to inner protection film; can also strengthen alkali (especially; finger OH-yl) chemical reactivity; improve its attack ability, just played the effect of catalyzer the ester group of carboxylic acid group and cellulose formation.Therefore, the adding of surfactant can reduce the concentration of aqueous slkali under the prerequisite that guarantees the water wettability treatment effect, reduce treatment temperature (and/or shortening the processing time), and simultaneously treated homogeneity is significantly improved.Also provide possibility simultaneously for the pressure that reduces production costs, alleviates environmental protection treatment.
Describe the specific embodiment of the present invention and effect in detail below in conjunction with embodiment.
Description of drawings
Fig. 1: film-type polaroid wet method drawing process synoptic diagram;
Fig. 2: film-type polaroid dry-stretch process synoptic diagram;
Fig. 3: corona method water wettability processing technological flow synoptic diagram;
Fig. 4: chemical method water wettability processing technological flow synoptic diagram;
Fig. 5: the carboxylate that alkali effect carboxylic acid and cellulose form decomposes (saponification);
Fig. 6: contact angle θ synoptic diagram is detected on film to be measured surface.
Embodiment
Fig. 1 is a film-type polaroid wet method drawing process synoptic diagram: PVA (polyvinyl alcohol (PVA); down together) film 1 is after washing and swelling 2; enter dyeing 3; then enter and stretch and fixation 4; after finishing, fixation enters dry 5; compound with polaroid inner protection film 6 and 7 again, dry once more 8 backs form the former mating plate 9 of polaroid.
Fig. 2 is a film-type polaroid dry-stretch process synoptic diagram: under hot environment; after utilizing external force that PVA film 1 drawn 2 (comprising stretching 2-1 and twice stretching of stretching 2-2) is arrived required multiple; enter washing and swelling 3, dyeing 4, fixation 5; after finishing, fixation enters dry 6; compound with polaroid inner protection film 7 and 8 again, dry once more 9 backs form the former mating plate 10 of polaroid.
Fig. 3 is a corona method water wettability processing technological flow synoptic diagram: inner protection film 1 is through unreeling 2, and through a pair of high-field electrode zone 3, be subjected to the bombardment of high energy ion after, rolling 4 is with standby 5 again.
Fig. 4 is a water wettability processing technological flow synoptic diagram, and inner protection film 1 enters and carries out alkali treatment 2 in the aqueous solution that contains highly basic through unreeling; under certain temperature, time, with alkali generation chemical reaction, then by in washing or the acid and 3 alkali of removing remained on surface; after super-dry 4, rolling 5 is standby.
The principle of hydrophilic treatment is seen accompanying drawing 5.The OH-base (hydroxyl, by alkali in water ionization and get) ester group of the carboxylate that forms of attack carboxylic acid and cellulose, carboxylate radical is replaced by the OH-base, separate with cellulose, be free in the water.Improve greatly with the cellulose water wettability that goes up the OH-base.
Surfactant involved in the present invention is a kind of cationic surfactant, and more specifically statement is a kind of quaternary ammonium salts cationic surfactant.Its chemical structural formula is as follows:
Figure G2008101671968D00071
The core of this surfactant is a quaternary ammonium cation.Quaternary ammonium cation has stronger electron-withdrawing power, is the good catalyzer of saponification.
In the formula: R1, R2, R3 and R4 are alkyl chain, for well, adopt the unsaturated alkyl chain to increase burden to cleaning with saturated alkyl, and be because unsaturated group is easy to variable color, especially serious when high temperature drying;
In R1, R2, R3 and four alkyl of R4, have at least a carbochain to be less than or equal 2, otherwise can not guarantee its fine solubility in water; But have at least the carbochain will be between 12-20 in four alkyl, otherwise can not guarantee the affinity of itself and inner protection film, it is soaked into and penetrating power decline, can not play the effect of catalyzer; Alkyl chain can adopt straight chain, also can adopt side chain, but preferably all adopts straight chained alkyl, can make its wellability, infiltration and the water-soluble optimum balance that reaches like this;
The anionicsite X of surfactant can be one of halogen (F, Cl, Br, I).Be preferably Cl, Br.
The addition of surfactant.Consider that surfactant mainly plays two effects in reaction system: the one, soak into and infiltration, the one, catalysis, so its addition will be controlled between the 0.001-1%, is preferably at 0.001-0.5%, is more preferably at 0.01-0.1%.(be less than 0.001%) very little, can influence the performance of its infiltration and infiltration function, (surpass 1%) too much, its catalysis and infiltration, infiltration function promote not obvious, increase burden for simultaneously the cleaning of road, back, wastewater treatment, increase production cost.
After adding surfactant, the treatment facility that water wettability improves, process route and operation can be prolonged and used conventional method, and technological parameter will be done suitable adjustment.
The concentration for the treatment of fluid (aqueous slkali):
Because the strong catalytic action of surfactant makes the chemical activity of alkali (refering in particular to the OH-yl) improve greatly, and reaction uniformity also has obvious lifting, and treatment effect reduces the sensitivity of alkaline concentration, can select in a big way.Consider the cleaning and the wastewater treatment of back segment, under the prerequisite that guarantees treatment effect, can suitably reduce its concentration.The concentration of aqueous slkali is 2-12% in this patent, is 5-10% preferably, and that best is 5-8%.
Processing time and temperature:
Treatment temperature is bigger to the catalytic action influence of surfactant, and under the prerequisite of same treatment effect, processing time and treatment temperature are the inverse ratio state.Be and reach the same treatment effect, can shorten the processing time, also can reduce treatment temperature by prolonging the processing time by improving treatment temperature.
Treatment temperature generally is controlled at 25-45 ℃ in this patent, is controlled at 30-40 ℃ preferably, and best is controlled at 35-40 ℃.Temperature is too low, needs the cooling refrigeration in the actual production, increases production cost, and the too high reaction of temperature is too violent, wayward treatment effect.
The processing time generally is controlled at 60-110s in this patent, is controlled at 70-100s preferably, the best 90-100s that is controlled at.
The requirement of surfactant is:
1. anti-strong alkali environment (PH 〉=14);
2. good water-solubility (solubleness under working temperature 〉=2%), and aqueous solution is to the equipment non-corrosiveness;
3. there is not chemical reaction with alkali;
4. under working temperature and in the strong alkali environment, do not have bad chemical reaction (refer to that non-volatility and selfdecomposition, autohemagglutination, precipitation separate out, with other substance reaction in the environment or generate insoluble slightly solubility material etc.) takes place;
5. body (or its aqueous solution) color and luster is light or colourless, and is easy to clean;
6. do not produce new environmental issue (or after simple process, can meet the environment protection emission requirement);
7. nontoxic or low toxicity own.
The selected surfactant of the present invention meets above-mentioned requirements fully.
Embodiment:
The material explanation:
The polaroid inner protection film: three cellulose acetate membrane (be called for short the TAC film, down with), German LOFO company produces;
Alkali: NaOH, commercially available, chemical pure;
Surfactant A: DTAC, commercially available, chemical pure;
Surfactant B: cetyl trimethyl ammonium bromide, commercially available, chemical pure;
PVA (polyvinyl alcohol (PVA)) film, Japanese Kuraray company product, VF-P;
Bonding agent: the PVA aqueous solution (PVA-124: Kuraray company product), concentration 5% (weight ratio).
The water wettability effect detection:
Detecting instrument: the SL200A type moves/the static contact angle instrument.
Detection method: under 25 ± 1 ℃/60 ± 5%RH environment, pure water is dropped in film to be measured surface, read contact angle θ (see Fig. 6, D is a film to be measured) in the 10s clock.Each sample is respectively surveyed 5 points, represents treatment effect (24-32 ° is the best) with mean value, with extreme difference value (maximal value and minimum value poor) expression process uniformity (the smaller the better).Reference standard: GB/T18396-2001.ISO1409、T5370-1999。
Transmitance detects:
Detecting instrument: day island proper Tianjin UV-1700 ultraviolet-visible pectrophotometer
Detection method: carry out with reference to GB/T 2410-1980;
Polaroid preparation: adopt the preparation of technological process shown in the accompanying drawing 2.
Adhesive property detects:
Detecting instrument: XLW-intelligent electronic tension tester.
Detection method: under 25 ± 2 ℃/60 ± 5%RH environment, detect the peel strength (180 °) of TAC film and PVA film.Reference standard: GB/T 2791-1995, GB/T 2790-1995.
The treatment process process is carried out with reference to accompanying drawing 4.
Reference examples:
Reference examples technology table is as follows:
Sequence number NaOH(%) Treatment temperature (℃) Processing time (s) Processing procedure
Reference examples 1 25 50 120 No abnormal
Reference examples 2 20 65 120 No abnormal
Reference examples 3 15 75 120 Disconnected film, 1
Reference examples 4 15 65 100 No abnormal
Reference examples 5 10 50 150 No abnormal
Reference examples 6 10 65 240 No abnormal
Annotate: 1. face turns white, the serious distortion distortion.
The reference examples testing result is as follows:
Sequence number Contact angle (°) (mean value/extreme difference) Transmitance (%) (before handling/after handling) Peeling force (g/25mm) Appearance index
Reference examples 1 28/5 92/92 1020 No abnormal
Reference examples 2 24/6 92/92 1050 Slight distortion
Reference examples 3 22/6 92/78 1080 Serious distortion
Reference examples 4 26/6 92/91 880 No abnormal
Reference examples 5 33/5 92/92 650 No abnormal
Reference examples 6 26/5 92/91 1080 Slight distortion
Embodiment:
Embodiment technology table is as follows:
Sequence number Kinds of surfactants/amount (‰) NaOH (%) Treatment temperature (℃) Processing time (s) Processing procedure
Embodiment 1 A/1 8 30 90 No abnormal
Embodiment 2 B/1 8 30 90 No abnormal
Embodiment 3 B/0.5 6 35 90 No abnormal
Embodiment 4 B/0.2 10 35 90 No abnormal
Embodiment 5 A/0.8 6 30 70 No abnormal
Embodiment 6 B/0.8 4 45 90 No abnormal
The embodiment testing result is as follows:
Sequence number Contact angle (°) (mean value/extreme difference) Transmitance (%) (before handling/after handling) Peeling force (g/25mm) Appearance index
Embodiment
1 25/3 92/92 1180 No abnormal
Embodiment
2 24/3 92/92 1250 No abnormal
Embodiment
3 24/3 92/92 1250 No abnormal
Embodiment
4 25/3 92/91 1150 No abnormal
Embodiment
5 26/4 92/92 1050 No abnormal
Embodiment 6 25/5 92/92 1020 No abnormal
Embodiment only is the partial content that the present invention relates to, and the present invention is not limited only to the scope that embodiment embodies.

Claims (14)

1. one kind is used to improve polaroid inner protection film hydrophilicity method, it is characterized in that adding a kind of quaternary ammonium salts cationic surfactant in inner protection film alkali treatment process, and the chemical structural formula of described quaternary ammonium salts cationic surfactant is as follows:
Figure F2008101671968C00011
In the formula: R1, R2, R3 and R4 are alkyl chain, wherein, have at least a carbochain to be less than or equal to 2, have a carbochain at least between 12-20;
X is one of halogen F, Cl, Br, I;
The addition of surfactant is 0.001-1%;
Treating fluid is that the concentration of aqueous slkali is 2-12%;
Treatment temperature is 25-45 ℃;
Processing time is 60-110s.
2. according to claim 1ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that described alkyl chain is a saturated alkyl.
3. according to claim 2ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that described alkyl chain is a straight chained alkyl.
4. describedly be used to improve polaroid inner protection film hydrophilicity method according to claim 1,2 or 3, it is characterized in that X is Cl or Br.
5. according to claim 4ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that described surfactant is a DTAC.
6. according to claim 4ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that described surfactant is a cetyl trimethyl ammonium bromide.
7. according to claim 1 and 2ly be used to improve polaroid inner protection film hydrophilicity method, the addition that it is characterized in that surfactant is 0.001-0.5%.
8. according to claim 7ly be used to improve polaroid inner protection film hydrophilicity method, the addition that it is characterized in that surfactant is 0.01-0.1%.
9. according to claim 1 and 2ly be used to improve polaroid inner protection film hydrophilicity method, the concentration that it is characterized in that aqueous slkali is 5-10%.
10. according to claim 9ly be used to improve polaroid inner protection film hydrophilicity method, the concentration that it is characterized in that aqueous slkali is 5-8%.
11. according to claim 1 and 2ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that treatment temperature is 30-40 ℃.
12. according to claim 11ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that treatment temperature is 35-40 ℃.
13. according to claim 1 and 2ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that the processing time is 70-110s.
14. according to claim 13ly be used to improve polaroid inner protection film hydrophilicity method, it is characterized in that the processing time is 90-100s.
CN2008101671968A 2008-10-08 2008-10-08 Method for enhancing inner protection film hydrophilicity of polaroid Active CN101424764B (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1388402A (en) * 2001-05-28 2003-01-01 日东电工株式会社 Transparent protective film for sheet polarizer and its prodcing teconology
CN1540373A (en) * 2003-04-16 2004-10-27 住友化学工业株式会社 polarizing board and its mfg. method
CN101223463A (en) * 2005-07-21 2008-07-16 柯尼卡美能达精密光学株式会社 Polarizing plate, liquid crystal display device, and process for producing hydrophilic polymer film
CN101226253A (en) * 2007-01-17 2008-07-23 毛利聪 Method for alkalization processing polarization board protective film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1388402A (en) * 2001-05-28 2003-01-01 日东电工株式会社 Transparent protective film for sheet polarizer and its prodcing teconology
CN1540373A (en) * 2003-04-16 2004-10-27 住友化学工业株式会社 polarizing board and its mfg. method
CN101223463A (en) * 2005-07-21 2008-07-16 柯尼卡美能达精密光学株式会社 Polarizing plate, liquid crystal display device, and process for producing hydrophilic polymer film
CN101226253A (en) * 2007-01-17 2008-07-23 毛利聪 Method for alkalization processing polarization board protective film

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