CN108957616A - A kind of manufacturing method of dye-type polaroid - Google Patents
A kind of manufacturing method of dye-type polaroid Download PDFInfo
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- CN108957616A CN108957616A CN201811057874.5A CN201811057874A CN108957616A CN 108957616 A CN108957616 A CN 108957616A CN 201811057874 A CN201811057874 A CN 201811057874A CN 108957616 A CN108957616 A CN 108957616A
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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
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
Abstract
A kind of manufacturing method of dye-type polaroid provided by the invention, using under the premise of not changing existing dye-type polaroid manufacturing process substantially, method by the way that specific amides compound is added, it is uneven to solve dyeing in the prior art, the big technical problem of optical index deviation, the uniformity that dye distribution can be significantly improved in fact, improves the technical effect of the quality of product.
Description
Technical field
The present invention relates to polaroid fields, in particular to a kind of manufacturing method of dye-type polaroid.
Background technique
It is well known that liquid crystal display is straight with its light matter and thin body, low-work voltage, passive display, radiationless harm, plane
Angle is shown, image stabilization does not flash, the advantages that being easily achieved large-area displays and micro- energy consumption, and the mainstream for becoming the information age is aobvious
Show product and Primary Component.And the one integral as liquid crystal display --- polarisation, i.e. polarizing film, are also faced with and further mention
The problem of rising performance quality；In polaroid, dichroic substance is the key that polarizing efficiency.Dichroic substance is made of iodine
Polaroid, referred to as iodine polarizing piece, dichroic substance is using polaroid, referred to as dyestuff system polaroid made of dyestuff；Due to
Iodine is unstable to heat, steam, strong illumination etc., therefore, in the presence of a harsh environment, such as high temperature, low temperature, high humility, strong illumination
Deng iodine polarizing piece performance is far away from dyestuff system polaroid.Therefore, exploitation dye-type polaroid meets market urgent need
Effective ways.
JP2006-226398 discloses the dye-type of preparation and the use dry method extension method preparation of a kind of dichroic dye
The application of polaroid；KR2005-0070697 discloses a kind of preparation of dichroic dye and using the preparation of wet process extension method
Application of the dye-type polaroid in OLED device.
Illustrate current dyestuff system polaroid manufacturing technology below.
First to the polyvinyl alcohol resin film, hereinafter referred to as PVA film, implement swelling process, after being swollen process
It is dyeing process, dichroic dye is not particularly limited, as long as dyeing to PVA film, can enumerate azo system, green onion quinone
The dichroic dye of system, quinophthalone system etc., such as: C.I. directly Huang 12, C.I. directly Huang 28, C.I. directly Huang 4, C.I. are direct
Orange 26, C.I. direct orange 39, C.I. direct orange 107, C.I. directly red 2, C.I. directly red 31, C.I. directly red 79, C.I. are straight
Connect red 81, C.I. directly red 247, C.I. directly indigo plant 237, C.I. directly indigo plant 273, C.I. directly indigo plant 274, C.I. direct green 80,
C.I. direct green 59 and Japanese Unexamined Patent Publication 2001-33627, Japanese Unexamined Patent Publication 2002-296417, Japanese Unexamined Patent Publication 2003-21538,
WO2004/092282, Japanese Unexamined Patent Publication 2001-0564112, Japanese Unexamined Patent Publication 2001-027708, Japanese Unexamined Patent Publication 11-218611, day
The organic dyestuff etc. recorded in this Japanese Laid-Open Patent Publication 11-218610 and Japanese Unexamined Patent Application 60-156759 bulletin.These organic dyestuff remove
In the form of free acid except use, it is also used as alkali metal salt, such as Na salt, K salt, Li salt, ammonium salt or amine etc.
The form of salt uses.
In actual operation, the one or more of above-mentioned dyestuff be can choose, to reach final products to tone and polarisation
The requirement of performance.
Solution containing dichroic dye can contain the conducts such as sodium chloride, sodium sulphate, anhydrous sodium sulfate, sodium tripolyphosphate
PVA film can be impregnated in containing dichroic dye by dyeing assistant as the method for mixing dichroic dye by above-mentioned
Solution in carry out, but dichroic dye can also be added in the stage for carrying out processing and forming to PVA film and make to realize
Its purpose for containing dichroic dye.
After dyeing process, cleaning process is carried out, the dyestuff that the surface of PVA film will be attached in dyeing process carries out clearly
It washes, is transferred in the liquid followed by processing with preventing or reducing dyestuff；After cleaning process, carry out containing PVA film
The process of crosslinking agent and/or resistance to hydrated agent；It is allowed to after the process containing crosslinking agent and/or resistance to hydrated agent, carries out stretching process；
It after stretching process, needs to be cleaned again, to remove the analysis in film surface crosslinking agent that may be present and/or resistance to hydrated agent
Out or impurity etc., after cleaning process, the drying process of film is carried out.
After completing drying process, PVA film is commonly referred to as " plain film ", in its single or double setting transparent protective layer to obtain
Polarizing film has been arrived, in order to which transparent protective layer to be bonded with plain film, has needed adhesive.It is not particularly limited as adhesive, preferably
Polyethenol series adhesive.As polyethenol series adhesive, it can be cited for example that Japan synthesizes Chemical Co., Ltd.
Gohseno1NH-26, GOHSEFIMER Z-200 etc., but it is not limited to the above example.It can be added in adhesive known
Crosslinking agent and/or resistance to hydrated agent.It can be cited for example that ISOBAM#18, ISOBAM#04 of Kuraray Co. Ltd. system,
The DENACOL EX-521 () of ISOBAM104, ISOBAM110, Nagasechemtex society, three well gas chemistry societies
Tetrad-C etc..In addition, as the adhesive other than polyvinyl alcohol resin, polyurethane series, acrylic acid series, epoxy can be used
The known adhesives such as system.After being bonded transparent protective layer using adhesive, it is dried or is heat-treated with temperature appropriate, thus
Obtain polaroid.
By the further investigation of present inventor, there is the uneven deficiency of dyeing in the product of above scheme in performance.It is straight
The polaroid that shows as seen has local color difference, optical index, such as singleton transmittance, degree of polarization, and it is biggish that there is also deviations
Problem.
Summary of the invention
The present invention provides a kind of manufacturing method of dye-type polaroid, using not changing existing dye-type polaroid substantially
Under the premise of manufacturing process, by the method for the specific amides compound of addition, dyeing in the prior art is solved unevenly, light
Learn the big technical problem of indicator deviation.
The manufacturing method for this dye-type polaroid that the present invention provides to solve above-mentioned technical problem, including to PVA
Film successively carries out process, the stretching that swelling process, dyeing process, cleaning process, PVA film contain crosslinking agent and/or resistance to hydrated agent
Cleaning process, drying process, in the single or double of plain film transparent protective layer, the swelling process or/and described is arranged in process
Amides compound is added when carrying out in dyeing process, and the amides compound includes R1、R2、R3Alkyl, the R of=H, C1-61、R2、
R3Alkyl, the R of=H, C1-41、R2、R3Alkyl, the R of=H, C1-21、R2、R3、R4Alkyl, the R of=H, C1-41、R2、R3、R4=H,
The alkyl of C1-2, for the preferred R of structure 11、R2、R3The alkyl of=H, C1-6, more preferably R1、R2、R3The alkyl of=H, C1-4, it is more excellent
Select R1、R2、R3The alkyl of=H, C1-2；For the preferred R of structural formula 21、R2、R3、R4The alkyl of=H, C1-4, more preferable R1、R2、R3、
R4The alkyl of=H, C1-2.
The amount that the amides compound is added is 0.1-50 weight %.
The amides compound is using formamide, acetamide, propionamide, butyramide, N.N- dimethylformamide, urine
One of element, N.N- methylurea, N.N- Methylethyl urea.
The swelling process is by impregnating PVA film in 20 ~ 50 DEG C of solution 30 seconds ~ 10 minutes, and the solution is
Pure water or aqueous solution comprising mixtures one or more of in lower alcohol, hydrochloride, sulfate, carbonate remove in the solution
For ingredient additive amount outside pure water within the scope of 0.1-20%, the lower alcohol includes ethyl alcohol, glycerine.
The dyeing process is impregnated in PVA film in the solution containing dichroic dye or by the solution coating in PVA
On film.Solution temperature in the dyeing process is 15 DEG C ~ 60 DEG C, the model that the time being impregnated in solution is 30 seconds ~ 20 minutes
It encloses.
The utility model has the advantages that the present invention before not changing existing dye-type polaroid manufacturing process substantially possessed by of the invention
It puts, by the way that specific amides compound is added, the uniformity of dye distribution can be significantly improved, improve the quality of product.
Dye-type polaroid of the present invention can be used for the display fields such as LCD, 3D, OLED, such as Vehicular display device, projector, work
Industry control instrument, outdoor use display etc., are also applied for the manufacture of sunglasses.
Detailed description of the invention
Fig. 1 is the manufacturing method flow chart of dye-type polaroid in background technique.
Fig. 2 is the manufacturing method flow chart of dye-type polaroid of the present invention.
Fig. 3 is PVA molecular-crystalline structure of the present invention and amorphous region structural schematic diagram.
Fig. 4 is PVA schematic arrangement.
Fig. 5 is PVA intermolecular hydrogen bonding schematic diagram.
Fig. 6 amides compound destroys PVA intermolecular hydrogen bonding schematic diagram.
Fig. 7 is amides compound structural schematic diagram of the present invention.
Fig. 8 is the selection schematic diagram of sample test point of the present invention.
Fig. 9 is the result schematic diagram of embodiment of the present invention.
Figure 10 is the result schematic diagram of comparative example of the present invention.
Specific embodiment
In conjunction with above-mentioned Detailed description of the invention specific embodiments of the present invention.
As shown in Figure 2, the present invention provides a kind of manufacturing method of dye-type polaroid, including successively carries out to PVA film swollen
Profit process, dyeing process, cleaning process, PVA film contain the process of crosslinking agent and/or resistance to hydrated agent, stretching process, scavenger
Transparent protective layer is arranged in the single or double of plain film in sequence, drying process, the swelling process or/and the dyeing process into
Amides compound is added when row, the amides compound includes R1、R2、R3Alkyl, the R of=H, C1-61、R2、R3=H, C1-4
Alkyl, R1、R2、R3Alkyl, the R of=H, C1-21、R2、R3、R4Alkyl, the R of=H, C1-41、R2、R3、R4The alkyl of=H, C1-2,
For the preferred R of structural formula 11、R2、R3The alkyl of=H, C1-6, more preferably R1、R2、R3The alkyl of=H, C1-4, more preferable R1、R2、R3
The alkyl of=H, C1-2；R preferred for structural formula1、R2、R3、R4The alkyl of=H, C1-4, more preferably R1、R2、R3、R4=H, C1-2
Alkyl.
The amount that the amides compound is added is 0.1-50 weight %.
The amides compound is using formamide, acetamide, propionamide, butyramide, N.N- dimethylformamide, urine
One of element, N.N- methylurea, N.N- Methylethyl urea.
Added amides compound is summarized as follows in the effect of dye-type polaroid manufacturing process:
1. the dyestuff that the amides compound is added is flowed with dye liquor close to PVA film interface;
2. the dyestuff that the amides compound is added passes through diffusion boundary layer to PVA film diffusion into the surface；
3. the dyestuff of the amides compound is added by PVA film adsorption, and hydrogen bond, Van der Waals force are formed with PVA molecule
Or Coulomb force and combine;
4. the dyestuff of the amides compound is added to diffusion inside PVA film and in conjunction with PVA molecule, to anchor at PVA
Inside film.
The swelling process is by impregnating PVA film in 20 ~ 50 DEG C of solution 30 seconds ~ 10 minutes, and the solution is
Pure water or aqueous solution comprising mixtures one or more of in lower alcohol, hydrochloride, sulfate, carbonate remove in the solution
For ingredient additive amount outside pure water within the scope of 0.1-20%, the lower alcohol includes ethyl alcohol, glycerine.
The dyeing process is impregnated in PVA film in the solution containing dichroic dye or by the solution coating in PVA
On film.Solution temperature in the dyeing process is 15 DEG C ~ 60 DEG C, the model that the time being impregnated in solution is 30 seconds ~ 20 minutes
It encloses.
As shown in Figure 1, dyestuff can be divided into four ranks to PVA film progress dyeing course in dyeing in existing technology
Section:
1. dye molecule is flowed with dye liquor close to the PVA film interface;
2. dyestuff passes through diffusion boundary layer to the PVA film diffusion into the surface；
3. dyestuff is formed hydrogen bond, Van der Waals force or Coulomb force with the PVA molecule and is combined by the PVA film adsorption;
4. dyestuff is to diffusion inside the PVA film and in conjunction with the PVA molecule, to anchor inside the PVA film.
Therefore, only guaranteed dye molecule is distributed evenly in the PVA film surface and inside, is likely to acquisition optics and refers to
Mark, the especially uniform polaroid of form and aspect index.
It, can be by promoting the effective concentration of shown dyestuff, improving dye liquor circulating effect, reduction institute in the 1st and the 2nd stage
The charge row for stating dye molecule and the PVA film surface tears the methods of power open and obtains good result；Due to molecular gap and space
The reason of steric hindrance, the amorphous domain of the PVA to the adsorption capacity of the dye molecule be significantly larger than the PVA crystallization or
Orientation area, and the dye molecule enters the probability significantly larger than crystallization or orientation of the PVA intramolecular amorphous domain
Region.Therefore, in the 3rd and the 4th stage, the dye molecule to be made to be evenly distributed, the work in addition to depending on the dye molecule
Property, dyeing it is uniform and stable outer, the uniformity of the PVA film surface and internal property is also vital.And this portion
Point, be in conventional art without reference to.
PVAC polyvinylalcohol molecular structure is simple, and regularity is good, structural formula such as Fig. 4:
Therefore, there is a large amount of hydrogen bond in molecule interchain and intramolecular, as shown in Figure 5:
Crystallization easy to form or orientation texture, the PVA film of alcoholysis degree >=99%, even if being impregnated for a long time in room temperature water, these knots
Structure will not completely disappear, as shown in Figure 3.Main cause is exactly that the intermolecular HYDROGEN BOND INTENSITY of PVA is greater than hydrone and PVA points
The HYDROGEN BOND INTENSITY that son is formed.Therefore, in background technique swelling PVA method, can not completely eliminate crystallization in PVA molecule or
Orientation texture, this is resulted in subsequent dyeing course, the inhomogeneities that dye molecule is distributed in PVA.Its final result is exactly
Cause inhomogeneities of the polaroid there are optical index.
Present inventor's research work shows partial amides class compound, and the hydrogen bond formed with PVA molecule is better than PVA points
Hydrogen bond between son, it is intermolecular that such compound enters PVA, preferentially will form hydrogen bond with PVA molecule and replace the intermolecular hydrogen of PVA
Key, as shown in Figure 6:
Destroy PVA molecular crystalline or orientation texture, make PVA it is intermolecular crystallization or orientation area become loosely, closer to
Amorphous domain, to allow dye molecule evenly into PVA molecule interchain.
Further research shows such amides compound, also will form Hydrogenbond with dye molecule, therefore,
Such amides compound is added in dyeing section, PVA intramolecule can be entered together with dye molecule, imitated to dyeing is improved
Fruit is advantageous.
The manufacturing method of this dye-type polaroid provided by the invention, using the amides chemical combination of structure as shown in Figure 7
Object destroys crystallization or orientation texture in PVA molecule.
As shown in fig. 7, being directed to structure 1, it is contemplated that the activity and its dissolubility of compound, preferably R1、R2、R3=H, C1-6's
Alkyl, more preferably R1、R2、R3The alkyl of=H, C1-4, more preferable R1、R2、R3The alkyl of=H, C1-2；The compound that can be enumerated is first
Amide, acetamide, propionamide, butyramide, N.N- dimethylformamide etc., preferably N.N- dimethylformamide DMF；
For structure 2, it is contemplated that the activity and its dissolubility of compound, preferably alkyl, more preferably R1, R2, R3, R4=H, C1-4
Alkyl, more preferable R1, R2, R3, R4=H, C1-2 alkyl；The compound that can be enumerated is urea, N.N- methylurea, N.N- methyl second
Base urea etc., preferably urea.
The amides compound can in polaroid manufacturing process the swelling process, in the dyeing process it is any
One section of addition, can also be added simultaneously in two sections of processes；The amount of the amides compound, addition is 0.1-50 weight %, if low
In 0.1 weight %, then effect is unobvious, if be higher than 50%, on the one hand, uniformity effects are no longer promoted, and increase solution prepare and
Difficult management, on the other hand, due to the presence of salt effect, some dyes can be precipitated from solution, reduce dyeing effect.Meanwhile
By the solubility limit of partial amides class compound, solution is prepared difficult；It is preferred that 1-30 weight %, more preferable 2-15 weight %；On
The amides compound for stating two kinds of structures, can be used alone, and can also be used in mixed way, other techniques require can along to
Toward technology.
Hereinafter, will the present invention is described in detail with example.The example, is not intended to limit the scope of the invention, in skill
In scope known to art, equivalent transformation is carried out to description of the invention and claim content, belongs to model of the invention
In enclosing.
Embodiment 1, by with a thickness of 75 μm of polyvinyl alcohol resin film PVA film, swelling 2 divides in 30 DEG C of deionized water
Clock, in the dichroic dye of the C.I. containing 0.08 weight % directly red 81, the DMF amides compound of 4 weight %, N, N- diformazan
Base formamide, the Na of 0.5 weight %2SO4In mixed aqueous solution, middle immersion 1 minute at 40 DEG C, to adsorb dichroic substance, then
It is cleaned by 30 seconds pure water, then is soaked in 50 DEG C, the boric acid containing 4 weight %, the Na of 0.5 weight %2SO4In mixed aqueous solution,
Simultaneously extend to 5.5 times of former film, is then cleaned at room temperature with deionized water, and heated-air drying 10 is divided at 55 DEG C
The plain film with polarization function is made in clock.Using PVA system glue by this plain film two sides stick after saponification process with a thickness of
80 μm of three cellulose acetate membrane, that is, TAC film, it is 10 minutes dry through 75 DEG C, obtain polarizer samples；By sample along drawing
The sample that axis direction cuts into 20cm × 20cm is stretched, according to test point as shown in Figure 8, according to national standard GB/T 25275-2010
Defined method measures the transmitance and degree of polarization and a, b value of each point with spectrophotometer U7100, referring to CIE1964
Regulation, judge dyeing uniformity by comparing the standard deviation of data.Standard deviation is smaller, and uniformity is better；Data are such as
Shown in Fig. 9, data explanation: Ts is transmitance；Py is degree of polarization, 400-700nm visible light wave range average value；A, b is CIE1964
Tone index；STD is standard deviation.
Embodiment 2, by with a thickness of 75 μm of polyvinyl alcohol resin film PVA film, in 130 DEG C of air atmosphere, by turning
Speed ratio is two rollers of 1:5.5, this PVA film is stretched to 5.5 times of original size, then by cleaning 2 points in 32 DEG C of pure water
Clock, in the dichroic dye of the C.I. containing 0.10 weight % directly red 81, the DMF amides compound of 4 weight %, N, N- diformazan
Base formamide, the Na of 0.5 weight %2SO4In mixed aqueous solution, middle immersion 1.5 minutes at 42 DEG C, to adsorb dichroic substance, so
It is cleaned afterwards by 30 seconds pure water, then is soaked in 50 DEG C, the boric acid containing 4 weight %, the Na of 0.5 weight %2SO4Mixed aqueous solution
In 6 minutes, then cleaned at room temperature with deionized water, and heated-air drying 10 minutes at 55 DEG C, be made have polarization function
Plain film.It is tight state that all processes, which keep PVA film,.Then this plain film is sticked by saponification process using PVA system glue
Afterwards with a thickness of 80 μm of three cellulose acetate membrane, that is, TAC film, it is 10 minutes dry through 75 DEG C, obtain polarizer samples, will
Sample cuts into the sample of 20cm × 20cm along axis direction is stretched, according to test point as shown in Figure 8, according to national standard GB/T
Method as defined in 25275-2010 measures the transmitance and degree of polarization and a, b value of each point, ginseng with spectrophotometer U7100
According to the regulation of CIE1964, dyeing uniformity is judged by comparing the standard deviation of data.Standard deviation is smaller, and uniformity is got over
It is good；Data are as shown in figure 9, data illustrate: Ts is transmitance；Py is degree of polarization, 400-700nm visible light wave range average value；a,b
It is the tone index of CIE1964；STD is standard deviation.
Embodiment 3, by with a thickness of 75 μm of polyvinyl alcohol resin film PVA film, swelling 2 divides in 30 DEG C of deionized water
Clock, in the dichroic dye of the C.I. direct green 80 containing 0.08 weight %, the DMF amides compound of 4 weight %, N, N- diformazan
Base formamide, it is middle at 40 DEG C to impregnate 1 minute in the NaCl mixed aqueous solution of 0.5 weight %, to adsorb dichroic substance, then pass through
The pure water cleaning for spending 30 seconds, then it is soaked in 50 DEG C, the boric acid containing 4 weight %, in the NaCl mixed aqueous solution of 0.5 weight %, together
Shi Jinhang extends to 5.5 times of former film, is then cleaned at room temperature with deionized water, and heated-air drying 10 minutes at 55 DEG C,
The plain film with polarization function is made.Using PVA system glue by this plain film stick after saponification process with a thickness of 80 μm
Three cellulose acetate membrane, that is, TAC film, it is 10 minutes dry through 75 DEG C, obtain polarizer samples；By sample along stretching axis direction
The sample for cutting into 20cm × 20cm, according to test point as shown in Figure 8, the side according to as defined in national standard GB/T 25275-2010
Method measures the transmitance and degree of polarization and a, b value of each point with spectrophotometer U7100, referring to the regulation of CIE1964, leads to
It crosses and compares the standard deviations of data to judge dyeing uniformity.Standard deviation is smaller, and uniformity is better；Data as figure 9, data
Illustrate: Ts is transmitance；Py is degree of polarization, 400-700nm visible light wave range average value；A, b is the tone index of CIE1964；
STD is standard deviation.
Embodiment 4, by with a thickness of 75 μm of polyvinyl alcohol resin film PVA film, swelling 2 divides in 30 DEG C of deionized water
Clock, it is middle at 40 DEG C to impregnate 1 minute in the DMF containing 4 weight % of addition, the sodium tripolyphosphate solution of 0.5 weight %, with absorption
Then dichroic substance cleans by 30 seconds pure water, then is soaked in 50 DEG C, the boric acid containing 4 weight %, and the three of 0.5 weight %
In polyphosphate sodium mixed aqueous solution, while extend to 5.5 times of former film, is then cleaned at room temperature with deionized water, and
The plain film with polarization function is made in heated-air drying 10 minutes at 55 DEG C.This plain film is sticked by soap using PVA system glue
Change that treated with a thickness of 80 μm of three cellulose acetate membrane, that is, TAC film, it is 10 minutes dry through 75 DEG C, obtain polaroid
Sample；The sample that sample is cut into 20cm × 20cm along stretching axis direction, according to test point as shown in Figure 8, according to national standard
Method as defined in GB/T 25275-2010 measures the transmitance and degree of polarization and a, b of each point with spectrophotometer U7100
Value judges dyeing uniformity by comparing the standard deviation of data referring to the regulation of CIE1964.Standard deviation is smaller, uniformly
Property is better；Data are as shown in figure 9, data illustrate: Ts is transmitance；Py is degree of polarization, and 400-700nm visible light wave range is average
Value；A, b is the tone index of CIE1964；STD is standard deviation.
Embodiment 5, by with a thickness of 75 μm of polyvinyl alcohol resin film PVA film, swelling 2 divides in 30 DEG C of deionized water
Clock, in the dichroic dye of the C.I. containing 0.08 weight % directly red 81, the urea amides compound of 4 weight %, N, N- bis-
Methylformamide, the Na of 0.5 weight %2SO4In mixed aqueous solution, middle immersion 1 minute at 40 DEG C, to adsorb dichroic substance, so
It is cleaned afterwards by 30 seconds pure water, then is soaked in 50 DEG C, the boric acid containing 4 weight %, the Na of 0.5 weight %2SO4Mixed aqueous solution
In, while extend to 5.5 times of former film, it is then cleaned at room temperature with deionized water, and the heated-air drying 10 at 55 DEG C
Minute, the plain film with polarization function is made.Using PVA system glue by this plain film stick after saponification process with a thickness of 80
μm three cellulose acetate membrane, that is, TAC film is 10 minutes dry through 75 DEG C, obtains polarizer samples；By sample along tensile axis
Direction cuts into the sample of 20cm × 20cm, according to test point as shown in Figure 8, is provided according to national standard GB/T 25275-2010
Method, the transmitance and degree of polarization and a, b value of each point are measured with spectrophotometer U7100, referring to the rule of CIE1964
It is fixed, dyeing uniformity is judged by comparing the standard deviation of data.Standard deviation is smaller, and uniformity is better；Data such as Fig. 9 institute
Show, data explanation: Ts is transmitance；Py is degree of polarization, 400-700nm visible light wave range average value；A, b is the color of CIE1964
Adjust index；STD is standard deviation.
Embodiment 6, by with a thickness of 75 μm of polyvinyl alcohol resin film PVA film, swelling 2 divides in 30 DEG C of deionized water
Clock, the C.I. containing 0.08 weight % directly red 81 dichroic dye, DMF: urea=1:1 ratio solution of 4 weight %, N,
Dinethylformamide, the Na of 0.5 weight %2SO4It is middle at 40 DEG C to impregnate 1 minute in mixed aqueous solution, to adsorb dichroism object
Then matter cleans by 30 seconds pure water, then is soaked in 50 DEG C, the boric acid containing 4 weight %, the Na of 0.5 weight %2SO4Mixing water
In solution, while extend to 5.5 times of former film, is then cleaned at room temperature with deionized water, and the hot air drying at 55 DEG C
Dry 10 minutes, the plain film with polarization function is made.This plain film is sticked by the thickness after saponification process using PVA system glue
It is 10 minutes dry through 75 DEG C for 80 μm of three cellulose acetate membrane, that is, TAC film, obtain polarizer samples；By sample along drawing
The sample that axis direction cuts into 20cm × 20cm is stretched, according to test point as shown in Figure 8, according to national standard GB/T 25275-2010
Defined method measures the transmitance and degree of polarization and a, b value of each point with spectrophotometer U7100, referring to CIE1964
Regulation, judge dyeing uniformity by comparing the standard deviation of data.Standard deviation is smaller, and uniformity is better；Data are such as
Shown in Fig. 9, data explanation: Ts is transmitance；Py is degree of polarization, 400-700nm visible light wave range average value；A, b is CIE1964
Tone index；STD is standard deviation.
Comparative example 1, in addition to without using amides compound, other operations are same as Example 1.
Comparative example 2, in addition to without using amides compound, other operations are same as Example 2.
Comparative example 3, in addition to making 0.05 weight % of DMF content, other operations are same as Example 1.
Comparative example 4, in addition to making 60 weight % of DMF content, other operations are same as Example 1.
Above-mentioned comparative example performance test data such as Figure 10.
As shown in Figure 9 and Figure 10, from embodiment 1 with comparative example 1, embodiment 2 compared with comparative example 2 as can be seen that no matter
It is that dry method extends or wet process extends, adding the amides compound is apparent to the promotion effect of dyeing uniformity；From
From the point of view of embodiment 3, the amides compound has similar effect to different dyestuffs；From the point of view of embodiment 4, the amides
Compound can also be added and have effect in swelling process；From the point of view of embodiment 5, two kinds of acyls mentioned by the present invention
Aminated compounds has close effect；From the point of view of embodiment 6, two kinds of amides compounds mentioned by the present invention can
To be used in mixed way；From the point of view of comparative example 3, when the amides compound content is too low, effect is deteriorated；From the point of view of comparative example 4,
When the amides compound too high levels, there is precipitation phenomenon in dyestuff, is decreased obviously effect instead, and sample can be seen that bright
Aobvious dyeing is uneven.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Present invention specific implementation is only limited to these instructions, for those of ordinary skill in the art to which the present invention belongs, not
Under the premise of being detached from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the protection of invention
Range.
Claims (5)
1. a kind of manufacturing method of dye-type polaroid, it is characterised in that: this method includes successively carrying out swelling work to PVA film
Sequence, dyeing process, cleaning process, PVA film contain the process of crosslinking agent and/or resistance to hydrated agent, stretching process, cleaning process, dry
Drying process adds when transparent protective layer, the swelling process or/and dyeing process progress is arranged in the single or double of plain film
Enter amides compound, the amides compound includes R1、R2、R3Alkyl, the R of=H, C1-61、R2、R3The alkyl of=H, C1-4,
R1、R2、R3Alkyl, the R of=H, C1-21、R2、R3、R4Alkyl, the R of=H, C1-41、R2、R3、R4The alkyl of=H, C1-2.
2. the manufacturing method of dye-type polaroid according to claim 1, it is characterised in that: the amides compound adds
The amount entered is 0.1-50 weight %.
3. the manufacturing method of dye-type polaroid according to claim 2, it is characterised in that: the amides compound is adopted
With formamide, acetamide, propionamide, butyramide, N.N- dimethylformamide, urea, N.N- methylurea, N.N- Methylethyl urea
One of.
4. the manufacturing method of dye-type polaroid according to claim 1, it is characterised in that: the swelling process is to pass through
PVA film is impregnated 30 seconds ~ 10 minutes in 20 ~ 50 DEG C of solution, the solution is pure water or comprising lower alcohol, hydrochloride, sulphur
The aqueous solution of one or more of mixtures in hydrochlorate, carbonate, the ingredient additive amount in the solution in addition to purified water is in 0.1-20%
In range, the lower alcohol includes ethyl alcohol, glycerine.
5. the manufacturing method of dye-type polaroid according to claim 1, it is characterised in that: the dyeing process be by
PVA film is impregnated in the solution containing dichroic dye or by the solution coating in the solution on PVA film, in the dyeing process
Temperature is 15 DEG C ~ 60 DEG C, the range that the time being impregnated in solution is 30 seconds ~ 20 minutes.
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| CN110764179A (en) * | 2019-09-20 | 2020-02-07 | 深圳市盛波光电科技有限公司 | Method for preparing polaroid without grain defect |
| CN111025684A (en) * | 2019-12-31 | 2020-04-17 | 佛山纬达光电材料股份有限公司 | Manufacturing method of polarized PVA film for sunglasses and polarized PVA film |
| CN112248611A (en) * | 2020-10-12 | 2021-01-22 | 深圳市盛波光电科技有限公司 | Preparation method of polaroid |
| JP7348755B2 (en) | 2019-06-14 | 2023-09-21 | 住友化学株式会社 | Polarizing plate, method for manufacturing the polarizing plate, and image display device using the polarizing plate |
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Application publication date: 20181207 |