WO2015079969A1 - 偏光子及びそれを含む偏光板 - Google Patents
偏光子及びそれを含む偏光板 Download PDFInfo
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- WO2015079969A1 WO2015079969A1 PCT/JP2014/080445 JP2014080445W WO2015079969A1 WO 2015079969 A1 WO2015079969 A1 WO 2015079969A1 JP 2014080445 W JP2014080445 W JP 2014080445W WO 2015079969 A1 WO2015079969 A1 WO 2015079969A1
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- polarizer
- film
- absorbance
- polarizing plate
- resin
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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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
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
Definitions
- the present invention relates to a polarizer and a polarizing plate including the same.
- the polarizing plate has been widely used in display devices such as liquid crystal display devices, particularly in recent years for various mobile devices such as smartphones and slate PCs. With the development of mobile devices, there is an increasing demand for thinner and lighter polarizing plates, and on the other hand, excellent heat resistance is also required.
- Examples of conventional methods for suppressing discoloration or decolorization of a polarizer include, for example, a method of containing a sulfate ion in a polarizer [Japanese Patent Application Laid-Open No. 2009-193047 (Patent Document 1)]; A method of adding a film dipping treatment to an aqueous solution adjusted to a pH range of [JP 2009-282137 (Patent Document 2) and JP 2008-070571 (Patent Document 3)]; A method of providing a protective layer [Japanese Patent Laid-Open No.
- Patent Document 4 a method of adjusting the ratio of iodine content and potassium content in a polarizer [Japanese Patent Laid-Open No. 2007-114581 (Patent Document) 5)]; I 3 adsorbed in the polarizer - the method [Patent 2004-341503 (Patent Document 6 to improve the alignment of)]; a method of incorporating zinc ions polarizer [Tokuoyake 60-033245 (Patent Document 7), Kokoku 02-034001 (Patent Document 8), and JP 2000-035512 (Patent Document 9)], and the like.
- An object of the present invention is to provide a polarizing plate that is less prone to reddening under a heat resistance test even when the thickness of the polarizer is small, and a polarizer that is suitably applied to obtain such a polarizing plate. There is.
- the present invention provides the following polarizer and polarizing plate.
- a polarizer having a thickness of 10 ⁇ m or less is included,
- the ratio A 700 / A 450 between the absorbance A 450 of absorbance A 700 and wavelength 450nm at a wavelength of 700nm is 0.85 or more, the polarizer.
- the thickness is 10 ⁇ m or less, A polarizer having an absolute value of a difference between the absorbance A 700 at a wavelength of 700 nm and the absorbance A 450 at a wavelength of 450 nm of 0.11 or less when heat-treated at 100 ° C. for 30 minutes.
- a polarizing plate comprising the polarizer according to [4].
- the polarizer and polarizing plate of the present invention it is possible to suppress red discoloration under a heat resistance test and maintain a neutral display even though the thickness of the polarizer is as small as 10 ⁇ m or less.
- FIG. 1 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate according to the present invention.
- the polarizing plate of this invention is the polarizer 5 of thickness 10 micrometers or less, and the 1st protective film 10 laminated
- stacked through the 2nd adhesive bond layer 25 on the other surface can be provided.
- the polarizing plate 1 may further have another optical functional layer, an adhesive layer, or the like laminated on the first protective film 10 and / or the second protective film 20.
- the polarizing plate of the present invention includes a polarizer 5 having a thickness of 10 ⁇ m or less and a first protective film laminated on one surface of the polarizing plate 5 with a first adhesive layer 15 as in the polarizing plate 2 shown in FIG. 10 may be a polarizing plate with a single-side protective film.
- the polarizing plate 2 may further include another optical functional layer, an adhesive layer, or the like laminated on the first protective film 10 and / or the polarizer 5.
- the polarizing plate of the present invention includes a polarizer having a thickness of 10 ⁇ m or less, and absorbs A 700 at a wavelength of 700 nm (hereinafter simply referred to as “absorbance A 700 ”).
- the ratio A 700 / A 450 of the absorbance A 450 at a wavelength of 450 nm (hereinafter also simply referred to as “absorbance A 450 ”) is 0.85 or more.
- the thickness of the polarizer 5 is as small as 10 ⁇ m or less, the amount of moisture entering and exiting the polarizer 5 is significantly higher than that of a conventional polarizer having a relatively large thickness (about 35 ⁇ m).
- a heat resistance test usually 500 to 750 hours at 80 to 85 ° C.
- the present inventor has analyzed the cause of reddening of a thin film polarizer having a thickness of 10 ⁇ m or less, and the thin film polarizer absorbs light on the shorter wavelength side (blue region) than a conventional polarizer having a thickness (about 35 ⁇ m).
- the band is not easily degraded, but the absorption band on the long wavelength side (red region) is found to be a factor of red discoloration because the thin film polarizer is more susceptible to degradation.
- it has been found that it is extremely effective to set the absorbance ratio A 700 / A 450 to 0.85 or more in order to prevent light in the red region from preferentially leaking from the polarizer by a heat test. Is.
- absorbance A 700 and “absorbance A 450 ” of the polarizing plate (and polarizer) are the absorbance at the base of the absorption band on the long wavelength side (red region) and the absorption band on the short wavelength side (blue region), respectively. Absorbance at the base of.
- the absorption bands on the long wavelength side and the short wavelength side of the polarizing plate before the heat resistance test are very large, so the UV-visible spectrophotometer often saturates and the intensity cannot be grasped.
- the absorption band intensities on the side and the short wavelength side are sufficiently correlated with “absorbance A 700 ” and “absorbance A 450 ”, respectively.
- the intensities of the absorption bands on the long wavelength side and the short wavelength side are respectively “absorbance A 700 ”.
- “absorbance A 450 ” and “absorbance A 700 ” and “absorbance A 450 ” in the polarizing plate as an alternative evaluation physical property of such absorption band intensity, and the ratio A 700 / A 450 is set to 0 It has been found that it is extremely advantageous to suppress reddening to be .85 or more, and the polarizing plate according to this embodiment has been achieved.
- the absorbance ratio A 700 / A 450 of the polarizing plate is preferably 0.87 or more, more preferably 0.90 or more, from the viewpoint of more effectively suppressing reddening.
- the absorbance ratio A 700 / A 450 is usually 2.0 or less, and preferably 1.5 or less from the viewpoint of keeping the initial black display near neutral.
- the absorbance A 700 and absorbance A 450 of the polarizing plate can be in the range of 0.1 to 0.6 and 0.1 to 0.6, respectively. than to realize increased to absorbance ratio a 700 / a 450 0.85 or higher than normal 700, who realized the absorbance ratio a 700 / a 450 0.85 over the absorbance a 450 to be lower than normal Therefore, the absorbance A 450 is preferably 0.42 or less, and more preferably 0.41 or less.
- the polarizing plate according to this embodiment has an absorbance A 700 and an absorbance A when heat-treated at 100 ° C. for 30 minutes according to a second embodiment described later, from the viewpoint of effectively suppressing reddening under a heat resistance test.
- a polarizing plate including a polarizer 5 having an absolute difference from 450 of 0.11 or less is preferable.
- the absorbance A 700 and absorbance A 450 of the polarizing plate can be measured using an absorptiometer such as an ultraviolet-visible spectrophotometer. Natural light is used as the incident light.
- the absorbance value obtained may vary depending on the orientation when the sample is set on the absorptiometer.
- some absorptiometers measure the incident light due to the influence of mirrors and optical elements between the light source and the sample, and some polarization separation elements such as prisms are included. Sometimes care is needed.
- the polarizing plate is measured at a certain angle (meaning a certain direction around the optical axis), and then measured again at a direction rotated by 90 degrees.
- the polarizing plate of the present invention has a thickness of 10 ⁇ m or less, and the absolute value of the difference between the absorbance A 700 and the absorbance A 450 when heat-treated at 100 ° C. for 30 minutes is 0.11 or less.
- a polarizer 5 is included.
- the polarizing plate of the present invention including a polarizer exhibiting such light absorption characteristics is also capable of maintaining a neutral display even if it is subjected to a heat test, even though the thickness of the polarizer 5 is as small as 10 ⁇ m or less. It has excellent heat resistance.
- Such high heat resistance (difficulty of red discoloration) lasts for a long time even when the polarizing plate is applied to a display device such as a liquid crystal display device and put into actual use.
- the test for heat treatment at 100 ° C. for 30 minutes is also referred to as “100 ° C. test”.
- the absorbance characteristic of the polarizer 5 here (the absolute value of the difference between the absorbance A 700 and the absorbance A 450 is 0.11 or less) is different from the absorbance ratio A 700 / A 450 described above, and a protective film is pasted. In other words, it indicates the absorbance characteristics of a polarizer as a polarizing plate as a raw material of the polarizing plate.
- the red color change of the polarizing plate is caused by the difference between the ease of deterioration of the long wavelength side absorption band and the ease of deterioration of the short wavelength side absorption band under the heat resistance test. It has been found that the absorption band intensity on the short wavelength side can be evaluated by the absorbance A 700 and the absorbance A 450 of the polarizer, respectively. Furthermore, when the 100 ° C. test is performed, the absolute value of the difference between these absorbances is 0.11 or less. It is found that a polarizing plate that does not easily turn red even when subjected to a heat resistance test (usually 500 to 750 hours at 80 to 85 ° C.) is obtained. Has been reached.
- the present invention also provides a polarizer itself having a thickness of 10 ⁇ m or less and an absolute value of a difference between absorbance A 700 and absorbance A 450 of 0.11 or less when a 100 ° C. test is performed.
- the technology provided in association with the invention according to the present embodiment is that the polarizing plate undergoes red discoloration in a heat resistance test after becoming a polarizing plate (or after it is incorporated into a display device such as a liquid crystal display device).
- a method of predicting and evaluating the degree of the above by a 100 ° C. test of a polarizer before becoming a polarizing plate That is, when the absolute value of the difference between the absorbance A 700 and the absorbance A 450 is 0.11 or less when the polarizer is subjected to a 100 ° C. test, it is subjected to a heat resistance test after becoming a polarizing plate or a display device. It can be evaluated that the reddening of is sufficiently suppressed.
- the absolute value of the difference between the absorbance A 700 and the absorbance A 450 of the polarizer after the 100 ° C. test is preferably 0.09 or less, more preferably 0.06, from the viewpoint of more effectively suppressing reddening. It is as follows.
- the absorbance A 700 and absorbance A 450 of the polarizer after the 100 ° C. test can be in the range of 0.1 to 0.6 and 0.1 to 0.6, respectively.
- the 100 ° C. test can be performed, for example, by putting it in a heating furnace (oven) at 100 ° C. for 30 minutes.
- the absorbance A 700 and the absorbance A 450 after the 100 ° C. test are measured except that a polarizer is used as a sample.
- the polarizer is left for a long time after the 100 ° C test, it will absorb moisture and return to its original color. Therefore, after removal from the heating furnace, it will be in an environment of 23-27 ° C and 50-65% RH. It is necessary to carry out the measurement within 30 minutes in the same environment.
- Polarization characteristics of polarizing plate or polarizer can be mainly expressed by numerical values called single transmittance and degree of polarization, respectively.
- Single transmittance ( ⁇ ) 0.5 ⁇ (Tp ( ⁇ ) + Tc ( ⁇ ))
- Polarization degree ( ⁇ ) 100 ⁇ (Tp ( ⁇ ) ⁇ Tc ( ⁇ )) / (Tp ( ⁇ ) + Tc ( ⁇ ))
- Tp ( ⁇ ) is the transmittance (%) of the polarizing plate or the polarizer measured in the relationship between the linearly polarized light having the incident wavelength ⁇ nm and the parallel Nicol
- Tc ( ⁇ ) is the straight line having the incident wavelength ⁇ nm.
- It is the transmittance
- the single transmittance ( ⁇ ) and the degree of polarization ( ⁇ ) obtained for each wavelength are subjected to sensitivity correction called visibility correction, respectively, and the visibility correction single transmittance (Ty) and the visibility correction polarization, respectively. Called degrees (Py). These Ty and Py values can be easily measured with, for example, an absorptiometer (model number: V7100) manufactured by JASCO Corporation.
- the polarizing plate or the polarizer according to the present invention has a visibility corrected single transmittance (Ty) of 40. It is preferably 0.0% or more, and the visibility correction polarization degree (Py) is preferably 99% or more.
- the polarizer 5 can be obtained by adsorbing and orienting a dichroic dye on a uniaxially stretched polyvinyl alcohol resin layer.
- the thickness of the polarizer 5 is 10 ⁇ m or less, preferably 7 ⁇ m or less. While it is possible to reduce the thickness of the polarizing plates 1 and 2 by setting the thickness of the polarizer 5 to 10 ⁇ m or less, according to the present invention, even when such a thin film polarizer 5 is used, Can be effectively suppressed.
- a saponified polyvinyl acetate resin can be used as the polyvinyl alcohol resin constituting the polyvinyl alcohol resin layer.
- the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
- examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
- a film formed of such a polyvinyl alcohol resin constitutes the polarizer 5.
- the method for forming the polyvinyl alcohol-based resin is not particularly limited, and can be formed by a known method. However, the polyvinyl alcohol-based resin is easy to obtain the polarizer 5 having a desired thickness. It is preferable to form a film by applying the above solution on a substrate film.
- the polarizer 5 needs to be stretched and oriented, and is preferably stretched at a stretch ratio of more than 5 times, more preferably more than 5 times and not more than 17 times.
- the degree of saponification of the polyvinyl alcohol-based resin can be in the range of 80.0 to 100.0 mol%, preferably in the range of 90.0 to 99.5 mol%, more preferably 94.0. It is in the range of ⁇ 99.0 mol%.
- the degree of saponification is less than 80.0 mol%, the water resistance and heat-and-moisture resistance of the obtained polarizing plates 1 and 2 are lowered.
- a polyvinyl alcohol-based resin having a saponification degree exceeding 99.5 mol% is used, the dyeing speed becomes slow, the productivity decreases, and the polarizer 5 having sufficient polarization performance may not be obtained.
- the degree of saponification is the unit ratio (mol%) of the ratio of acetate groups (acetoxy groups: —OCOCH 3 ) contained in polyvinyl acetate resin, which is a raw material for polyvinyl alcohol resins, to hydroxyl groups by the saponification process.
- the following formula: Saponification degree (mol%) 100 ⁇ (number of hydroxyl groups) ⁇ (number of hydroxyl groups + number of acetate groups) Defined by The saponification degree can be determined according to JIS K 6726 (1994). The higher the degree of saponification, the higher the proportion of hydroxyl groups, and thus the lower the proportion of acetate groups that inhibit crystallization.
- the polyvinyl alcohol resin may be a modified polyvinyl alcohol partially modified.
- polyvinyl alcohol resins modified with olefins such as ethylene and propylene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; alkyl esters of unsaturated carboxylic acids, acrylamide, and the like can be used.
- the proportion of modification is preferably less than 30 mol%, and more preferably less than 10%. When modification exceeding 30 mol% is performed, it becomes difficult to adsorb the dichroic dye, and the polarizer 5 having sufficient polarization performance may not be obtained.
- the average degree of polymerization of the polyvinyl alcohol-based resin is preferably 100 to 10,000, more preferably 1500 to 8000, and further preferably 2000 to 5000.
- the average degree of polymerization of the polyvinyl alcohol resin can also be determined according to JIS K 6726 (1994).
- polyvinyl alcohol resins suitably used in the present invention are trade names, “PVA124” (degree of saponification: 98.0 to 99.0 mol%) manufactured by Kuraray Co., Ltd., “ PVA117 "(degree of saponification: 98.0 to 99.0 mol%),” PVA624 “(degree of saponification: 95.0 to 96.0 mol%),” PVA617 “(degree of saponification: 94.5 to 95) 5 mol%); “AH-26” (degree of saponification: 97.0 to 98.8 mol%) and “AH-22” (degree of saponification: 97.5 to 9) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
- the dichroic dye contained (adsorption orientation) in the polarizer 5 can be iodine or a dichroic organic dye.
- the dichroic organic dye include: Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Includes Sky Blue, Direct First Orange S and First Black.
- a dichroic dye may be used individually by 1 type, and may use 2 or more types together.
- the first protective film 10 and the second protective film 20 are each a thermoplastic resin, for example, a chain polyolefin resin (polypropylene resin, etc.), a cyclic polyolefin resin (norbornene resin).
- Polyolefin resin such as cellulose triacetate and cellulose diacetate; polyester resin such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; polycarbonate resin; (meth) acrylic resin Or a transparent resin film made of a mixture or copolymer thereof.
- the first protective film 10 and the second protective film 20 may be the same type of protective film or different types of protective films.
- the cyclic polyolefin resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin.
- cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and chain olefins such as ethylene and propylene (typically Are random copolymers), graft polymers obtained by modifying them with unsaturated carboxylic acids or derivatives thereof, and hydrides thereof.
- norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferably used.
- cyclic polyolefin resins Various products are commercially available for cyclic polyolefin resins.
- Examples of commercial products of cyclic polyolefin resins are trade names, “Topas” (Topas Advanced Polymers GmbH, available from Polyplastics Co., Ltd.), “Arton” (manufactured by JSR Corporation), Includes “ZEONOR” (manufactured by Nippon Zeon Co., Ltd.), “ZEONEX” (manufactured by Nippon Zeon Co., Ltd.), and “Apel” (manufactured by Mitsui Chemicals, Inc.).
- the cellulose ester resin is an ester of cellulose and a fatty acid.
- Specific examples of the cellulose ester resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate.
- these copolymers and those in which a part of the hydroxyl group is modified with other substituents can also be used.
- cellulose triacetate triacetyl cellulose: TAC
- TAC triacetyl cellulose
- Many products of cellulose triacetate are commercially available, which is advantageous in terms of availability and cost.
- Examples of commercial products of cellulose triacetate are trade names of “Fujitac TD80” (manufactured by Fuji Film Co., Ltd.), “Fujitac TD80UF” (manufactured by Fuji Film Co., Ltd.), and “Fujitac TD80UZ” (Fuji Film Co., Ltd.). )), “Fujitac TD40UZ” (manufactured by Fujifilm), “KC8UX2M” (manufactured by Konica Minolta Opto), and “KC4UY” (manufactured by Konica Minolta Opto).
- the first protective film 10 and / or the second protective film 20 may be a protective film having an optical function such as a retardation film and a brightness enhancement film.
- a retardation film provided with an arbitrary retardation value by stretching a transparent resin film made of the above material (uniaxial stretching or biaxial stretching) or forming a liquid crystal layer or the like on the film. It can be.
- a surface treatment such as a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, and an antifouling layer is provided on the surface of the first protective film 10 and / or the second protective film 20 opposite to the polarizer 5.
- a layer (coating layer) can also be formed.
- the method for forming the surface treatment layer on the surface of the protective film is not particularly limited, and a known method can be used.
- the thickness of the first and second protective films 10 and 20 is preferably thin from the viewpoint of reducing the thickness of the polarizing plates 1 and 2, but if it is too thin, the strength is lowered and the workability is poor. Accordingly, the thickness of the first and second protective films 10 and 20 is preferably 5 to 90 ⁇ m, more preferably 5 to 60 ⁇ m, and still more preferably 5 to 50 ⁇ m.
- First and second adhesive layers As the adhesive forming the first and second adhesive layers 15 and 25, a water-based adhesive or a photo-curable adhesive can be used.
- the adhesive that forms the first adhesive layer 15 and the adhesive that forms the second adhesive layer 25 may be the same or different.
- water-based adhesive examples include an adhesive made of a polyvinyl alcohol-based resin aqueous solution and a water-based two-component urethane emulsion adhesive.
- a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is preferably used.
- Polyvinyl alcohol resins include vinyl alcohol homopolymers obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
- a polyvinyl alcohol copolymer obtained by saponifying a polymer or a modified polyvinyl alcohol polymer obtained by partially modifying the hydroxyl group thereof can be used.
- the water-based adhesive can include additives such as polyvalent aldehydes, water-soluble epoxy compounds, melamine compounds, zirconia compounds, and zinc compounds. When an aqueous adhesive is used, the thickness of the adhesive layer obtained therefrom is usually 1 ⁇ m or less.
- the bonding method between the polarizer 5 and the protective film using the water-based adhesive is not particularly limited, and the water-based adhesive is uniformly applied or poured onto one bonding surface, and the other is stacked on the coating surface.
- the method of pasting and drying by etc. is mentioned.
- the aqueous adhesive is applied at a temperature of 15 to 40 ° C. after the preparation, and the laminating temperature is usually in the range of 15 to 30 ° C.
- drying can be performed, for example, by introducing the bonded film into a drying furnace.
- the drying temperature (drying furnace temperature) is preferably 30 to 90 ° C.
- a protective film to become easy to peel from the polarizer 5 as it is less than 30 degreeC. If the drying temperature exceeds 90 ° C., the polarizing performance of the polarizer 5 may be deteriorated by heat.
- the drying time can be about 10 to 1000 seconds.
- a curing step for curing for about 12 to 600 hours at room temperature or slightly higher temperature, for example, a temperature of about 20 to 45 ° C.
- the curing temperature is generally set lower than the drying temperature.
- the photocurable adhesive refers to an adhesive that cures when irradiated with active energy rays such as ultraviolet rays.
- the thing containing resin and a photoreactive crosslinking agent can be mentioned.
- the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable acrylic monomer, and a photocurable urethane monomer, and oligomers derived from the photopolymerizable monomer.
- the photopolymerization initiator examples include those containing substances that generate active species such as neutral radicals, anion radicals, and cation radicals when irradiated with active energy rays such as ultraviolet rays.
- an adhesive containing a photocurable epoxy monomer and a photocationic polymerization initiator can be preferably used as the photocurable adhesive containing a polymerizable compound and a photopolymerization initiator.
- the method for bonding the polarizer 5 and the protective film using the photocurable adhesive is not particularly limited.
- interposing with a nip roll etc. is mentioned.
- the casting method is a method in which an adhesive is allowed to flow down and spread on the bonding surface while an object to be coated is moved in a substantially vertical direction, a substantially horizontal direction, or an oblique direction between the two.
- the thickness of the adhesive layer after being bonded using a nip roll or the like before drying or curing is preferably 5 ⁇ m or less and 0.01 ⁇ m or more.
- a drying process is performed as necessary (such as when the photocurable adhesive contains a solvent), and then light is irradiated by activating active energy rays.
- a curing step for curing the curable adhesive is performed.
- the light source of the active energy ray is not particularly limited, but an active energy ray having a light emission distribution at a wavelength of 400 nm or less is preferable.
- a microwave excitation mercury lamp, a metal halide lamp and the like are preferably used.
- the light irradiation intensity to the photocurable adhesive is appropriately determined depending on the composition of the photocurable adhesive, and the irradiation intensity in the wavelength region effective for activating the polymerization initiator is 0.1 to 6000 mW / cm 2. It is preferable to set to. When the irradiation intensity is 0.1 mW / cm 2 or more, the reaction time does not become too long, and when the irradiation intensity is 6000 mW / cm 2 or less, the light emitted from the light source and the light generated by the curing of the photocurable adhesive There is little risk of yellowing of the curable adhesive and deterioration of the polarizer.
- the light irradiation time to the photocurable adhesive is also determined appropriately depending on the composition of the photocurable adhesive, and the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 10 to 10,000 mJ / cm 2. It is preferable to set to. When the integrated light amount is 10 mJ / cm 2 or more, a sufficient amount of active species derived from the polymerization initiator can be generated to advance the curing reaction more reliably, and when it is 10000 mJ / cm 2 or less, the irradiation time is long. It does not become too much, and good productivity can be maintained.
- the thickness of the adhesive layer after irradiation with active energy rays is usually about 0.001 to 5 ⁇ m, preferably 0.01 to 2 ⁇ m, more preferably 0.01 to 1 ⁇ m.
- Adhesive layer On the first protective film 10 or the second protective film 20 in the polarizing plate 1 shown in FIG. 1 and on the polarizer 5 in the polarizing plate 2 shown in FIG.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is usually based on a (meth) acrylic resin, styrene resin, silicone resin or the like, and a crosslinking agent such as an isocyanate compound, an epoxy compound, or an aziridine compound is added thereto. It consists of an adhesive composition. Furthermore, it can also be set as the adhesive layer which contains microparticles
- the thickness of the pressure-sensitive adhesive layer can be 1 to 40 ⁇ m, but it is preferably applied thinly, as long as the properties such as processability and durability are not impaired, and specifically 3 to 25 ⁇ m.
- a thickness of 3 to 25 ⁇ m has good processability and is suitable for suppressing the dimensional change of the polarizer 5.
- the method of forming the pressure-sensitive adhesive layer is not particularly limited, and a pressure-sensitive adhesive composition (pressure-sensitive adhesive solution) containing each component including the above-mentioned base polymer is applied to the protective film surface or the polarizer surface.
- the pressure-sensitive adhesive layer may be formed by drying, or after forming the pressure-sensitive adhesive layer on the separator (release film), the pressure-sensitive adhesive layer may be transferred to the protective film surface or the polarizer surface.
- the protective film surface or the polarizer surface, or one or both surfaces of the pressure-sensitive adhesive layer may be subjected to a surface treatment such as corona treatment, if necessary. Good.
- the polarizing plate can further include another optical layer laminated on the protective film or the polarizer.
- a reflective polarizing film that transmits a certain kind of polarized light and reflects polarized light that exhibits the opposite properties
- a film with an antiglare function having a concavo-convex shape on the surface
- a film with a surface antireflection function A reflective film having a reflective function on the surface
- a transflective film having both a reflective function and a transmissive function
- a viewing angle compensation film is another optical layer laminated on the protective film or the polarizer.
- DBEF (manufactured by 3M, Sumitomo 3M Co., Ltd. in Japan) can be used as a commercial product corresponding to a reflective polarizing film that transmits certain types of polarized light and reflects polarized light that exhibits the opposite properties.
- APF (manufactured by 3M, available from Sumitomo 3M Limited in Japan).
- the viewing angle compensation film examples include an optical compensation film in which a liquid crystal compound is applied to the substrate surface, and is oriented / fixed, a retardation film made of a polycarbonate resin, a retardation film made of a cyclic polyolefin resin, and the like. .
- WV film manufactured by Fujifilm Corporation
- NH film JX Nippon Mining & Metals. Energy Co., Ltd.
- NR Film manufactured by JX Nippon Oil & Energy Corporation
- the polarizer and polarizing plate of the present invention can be suitably produced by the method shown in FIG.
- the manufacturing method of the polarizing plate shown in FIG. (1) Resin layer forming step S10 in which a coating liquid containing a polyvinyl alcohol-based resin is applied to at least one surface of a base film and then dried to form a polyvinyl alcohol-based resin layer to obtain a laminated film.
- Stretching step S20 to stretch the laminated film to obtain a stretched film
- Dyeing step S30 to obtain a polarizing laminated film by dyeing the polyvinyl alcohol resin layer of the stretched film with a dichroic dye to form a polarizer
- 1st bonding process S40 which bonds a 1st protective film on the polarizer of a polarizing laminated film, and obtains a bonding film
- Peeling step S50 to peel and remove the base film from the bonded film to obtain a polarizing plate with a single-sided protective film, Are included in this order.
- Second bonding step S60 including. Hereinafter, each step will be described with reference to FIGS.
- this step is a step of obtaining a laminated film 100 by forming a polyvinyl alcohol-based resin layer 6 on at least one surface of the base film 30.
- the polyvinyl alcohol-based resin layer 6 is a layer that becomes the polarizer 5 through the stretching step S20 and the dyeing step S30.
- the polyvinyl alcohol-based resin layer 6 can be formed by applying a coating liquid containing a polyvinyl alcohol-based resin to one or both surfaces of the base film 30 and drying the coating layer.
- the method of forming a polyvinyl alcohol-based resin layer by such coating is advantageous in that a thin film polarizer 5 can be easily obtained.
- the base film 30 can be composed of a thermoplastic resin, and among them, it is preferably composed of a thermoplastic resin that is excellent in transparency, mechanical strength, thermal stability, stretchability, and the like.
- thermoplastic resins include, for example, polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins (norbornene resins, etc.); polyester resins; (meth) acrylic resins; cellulose triacetate, Cellulose ester resins such as cellulose diacetate; Polycarbonate resins; Polyvinyl alcohol resins; Polyvinyl acetate resins; Polyarylate resins; Polystyrene resins; Polyethersulfone resins; Polysulfone resins; Polyamide resins; System resins; and mixtures and copolymers thereof.
- the base film 30 may have a single-layer structure made of one resin layer made of one kind or two or more kinds of thermoplastic resins, or a plurality of resin layers made of one kind or two or more kinds of thermoplastic resins. A laminated multilayer structure may be used.
- the base film 30 is preferably made of a resin that can be stretched at a stretching temperature suitable for stretching the polyvinyl alcohol-based resin layer 6 when the laminated film 100 is stretched in the stretching step S20 described later.
- the chain polyolefin resin examples include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins.
- the base film 30 made of a chain polyolefin-based resin is preferable in that it is easily stretched stably at a high magnification.
- the base film 30 is composed mainly of a polypropylene resin (a polypropylene resin that is a propylene homopolymer or a copolymer mainly composed of propylene), a polyethylene resin (a polyethylene resin that is an ethylene homopolymer or ethylene). It is more preferable that it consists of a copolymer.
- the copolymer mainly composed of propylene which is one of the examples suitably used as the thermoplastic resin constituting the base film 30, is a copolymer of propylene and another monomer copolymerizable therewith.
- Examples of other monomers copolymerizable with propylene include ethylene and ⁇ -olefin.
- ⁇ -olefin an ⁇ -olefin having 4 or more carbon atoms is preferably used, and more preferably an ⁇ -olefin having 4 to 10 carbon atoms.
- Specific examples of the ⁇ -olefin having 4 to 10 carbon atoms include linear monoolefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; Branched monoolefins such as methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene; including vinylcyclohexane.
- the copolymer of propylene and other monomers copolymerizable therewith may be a random copolymer or a block copolymer.
- the content of the other monomer in the copolymer is, for example, 0.1 to 20% by weight, preferably 0.5 to 10% by weight.
- the content of other monomers in the copolymer can be determined by measuring infrared (IR) spectrum according to the method described on page 616 of "Polymer Analysis Handbook" (1995, published by Kinokuniya Shoten). Can be sought.
- polypropylene resin a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-1-butene random copolymer, or a propylene-ethylene-1-butene random copolymer is preferably used.
- the stereoregularity of the polypropylene resin is substantially isotactic or syndiotactic.
- the base film 30 made of a polypropylene-based resin having substantially isotactic or syndiotactic stereoregularity has relatively good handleability and excellent mechanical strength in a high temperature environment.
- the polyester-based resin is a resin having an ester bond, and is generally made of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol.
- a polyvalent carboxylic acid or a derivative thereof a divalent dicarboxylic acid or a derivative thereof can be used, and examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate.
- a divalent diol can be used, and examples thereof include ethylene glycol, propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol.
- polyester resin is polyethylene terephthalate, which is a polycondensate of terephthalic acid and ethylene glycol.
- Polyethylene terephthalate is a crystalline resin, but the one in a state before crystallization treatment is more easily subjected to treatment such as stretching. If necessary, it can be crystallized during stretching or by heat treatment after stretching.
- a copolymerized polyester having a crystallinity lowered (or made amorphous) by further copolymerizing another monomer with a polyethylene terephthalate skeleton is also preferably used.
- examples of such resins include those obtained by copolymerizing cyclohexanedimethanol and isophthalic acid. Since these resins are also excellent in stretchability, they can be suitably used.
- polyester resins other than polyethylene terephthalate and copolymers thereof include, for example, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate. , Polycyclohexanedimethyl naphthalate, and mixtures and copolymers thereof.
- the (meth) acrylic resin is a resin containing a compound having a (meth) acryloyl group as a main constituent monomer.
- Specific examples of the (meth) acrylic resin include, for example, poly (meth) acrylic acid esters such as polymethyl methacrylate; methyl methacrylate- (meth) acrylic acid copolymer; methyl methacrylate- (meth) acrylic acid Ester copolymer; methyl methacrylate-acrylate ester- (meth) acrylic acid copolymer; (meth) methyl acrylate-styrene copolymer (MS resin, etc.); methyl methacrylate and alicyclic hydrocarbon group And a copolymer with the compound (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.).
- a polymer based on a poly (meth) acrylic acid C 1-6 alkyl ester such as poly (meth) acrylic acid methyl is used, and more preferably methyl methacrylate is used as a main component (50 to 100). % Methyl methacrylate-based resin is used.
- Polycarbonate resin is an engineering plastic made of a polymer in which monomer units are bonded via a carbonate group, and is a resin having high impact resistance, heat resistance, flame retardancy, and transparency.
- the polycarbonate resin constituting the base film 30 may be a resin called a modified polycarbonate in which the polymer skeleton is modified in order to lower the photoelastic coefficient, a copolymerized polycarbonate with improved wavelength dependency, or the like.
- Polycarbonate resin is available in various products. Examples of commercially available polycarbonate-based resins are all “Panlite” (manufactured by Teijin Chemicals Ltd.), “Iupilon” (manufactured by Mitsubishi Engineering Plastics), “SD Polyca” (Sumitomo Dow). (Manufactured by Dow Chemical Co., Ltd.).
- polypropylene resins are preferably used from the viewpoints of stretchability and heat resistance.
- the matters described for the protective film are cited. Further, the chain polyolefin resin, polyester resin, (meth) acrylic resin, and polycarbonate resin as described above in relation to the base film 30 can also be used as a constituent material of the protective film.
- any suitable additive may be added to the base film 30 in addition to the thermoplastic resin described above.
- suitable additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, and coloring agents.
- the content of the thermoplastic resin in the base film 30 is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. . When the content of the thermoplastic resin in the base film 30 is less than 50% by weight, the high transparency inherent in the thermoplastic resin may not be sufficiently exhibited.
- the thickness of the base film 30 can be determined as appropriate, but generally it is preferably 1 to 500 ⁇ m, more preferably 1 to 300 ⁇ m, further preferably 5 to 200 ⁇ m, from the viewpoint of workability such as strength and handleability. Most preferred is 150 ⁇ m.
- the coating liquid is preferably a polyvinyl alcohol resin solution obtained by dissolving polyvinyl alcohol resin powder in a good solvent (for example, water).
- a good solvent for example, water
- the coating liquid may contain additives such as a plasticizer and a surfactant as necessary.
- a plasticizer polyol or a condensate thereof can be used, and examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol.
- the blending amount of the additive is preferably 20% by weight or less of the polyvinyl alcohol resin.
- the coating liquid is applied to the base film 30 by a wire bar coating method; a roll coating method such as reverse coating or gravure coating; a die coating method; a comma coating method; a lip coating method; a spin coating method;
- the method can be appropriately selected from a method such as a fountain coating method, a dipping method, and a spray method.
- the coating liquid When the coating liquid is applied to both surfaces of the base film 30, it can be performed one side at a time using the above-described method, or the base material can be formed using a dipping method, a spray coating method, or other special equipment. It is also possible to apply to both sides of the film 30 simultaneously.
- the drying temperature and drying time of the coating layer are set according to the type of solvent contained in the coating solution.
- the drying temperature is, for example, 50 to 200 ° C., preferably 60 to 150 ° C.
- the drying temperature is preferably 80 ° C. or higher.
- the drying time is, for example, 2 to 20 minutes.
- the polyvinyl alcohol-based resin layer 6 may be formed only on one side of the base film 30 or on both sides. When formed on both sides, curling of the film that can occur during the production of the polarizing laminated film 300 (see FIG. 6) can be suppressed, and two polarizing plates can be obtained from one polarizing laminated film 300. It is also advantageous in terms of plate production efficiency.
- the thickness of the polyvinyl alcohol resin layer 6 in the laminated film 100 is preferably 3 to 30 ⁇ m, and more preferably 5 to 20 ⁇ m. If it is the polyvinyl alcohol-type resin layer 6 which has the thickness in this range, after the extending process S20 and the dyeing process S30 which will be described later, the dyeability of the dichroic dye is excellent, the polarization performance is excellent, and the thickness is sufficiently small. A polarizer 5 (with a thickness of 10 ⁇ m or less) can be obtained. When the thickness of the polyvinyl alcohol-based resin layer 6 exceeds 30 ⁇ m, the thickness of the polarizer 5 may exceed 10 ⁇ m. Moreover, when the thickness of the polyvinyl alcohol-based resin layer 6 is less than 3 ⁇ m, the film becomes too thin after stretching and the dyeability tends to deteriorate.
- At least the surface of the base film 30 on the side where the polyvinyl alcohol resin layer 6 is formed is provided. Corona treatment, plasma treatment, flame (flame) treatment or the like may be performed.
- a polyvinyl alcohol-based material is provided on the substrate film 30 via a primer layer or an adhesive layer.
- the resin layer 6 may be formed.
- the primer layer can be formed by applying a primer layer forming coating solution to the surface of the substrate film 30 and then drying it.
- the primer layer forming coating solution contains a component that exhibits a certain degree of strong adhesion to both the base film 30 and the polyvinyl alcohol-based resin layer 6.
- the primer layer-forming coating solution usually contains a resin component that imparts such adhesion and a solvent.
- a thermoplastic resin excellent in transparency, thermal stability, stretchability and the like is preferably used, and examples thereof include (meth) acrylic resins and polyvinyl alcohol resins. Among these, polyvinyl alcohol resins that give good adhesion are preferably used.
- polyvinyl alcohol resin examples include polyvinyl alcohol resins and derivatives thereof.
- Polyvinyl alcohol resin derivatives include polyvinyl formal, polyvinyl acetal, etc., as well as polyvinyl alcohol resins modified with olefins such as ethylene and propylene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid. Denatured; modified with alkyl ester of unsaturated carboxylic acid; modified with acrylamide.
- solvent a general organic solvent or an aqueous solvent capable of dissolving the resin component.
- solvents include, for example, aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and isobutyl acetate; Chlorinated hydrocarbons such as trichloroethylene and chloroform; alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol.
- the primer layer is formed using a primer layer forming coating solution containing an organic solvent
- the base film 30 may be dissolved, so the solvent is selected in consideration of the solubility of the base film 30. It is preferable to do.
- the primer layer is preferably formed from a coating solution containing water as a solvent.
- a crosslinking agent may be added to the primer layer forming coating solution.
- a suitable crosslinking agent is appropriately selected from known ones such as organic and inorganic based on the type of thermoplastic resin to be used. Examples of the crosslinking agent include epoxy-based, isocyanate-based, dialdehyde-based, and metal-based crosslinking agents.
- epoxy-based crosslinking agent either one-component curable type or two-component curable type can be used.
- Isocyanate-based crosslinking agents include tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane-tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylenebis (4-phenylmethane) triisocyanate, isophorone diisocyanate, and ketoximes thereof.
- a block thing or a phenol block thing etc. are mentioned.
- dialdehyde-based cross-linking agent examples include glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, maleidialdehyde, phthaldialdehyde and the like.
- metal-based crosslinking agent examples include metal salts, metal oxides, metal hydroxides, and organometallic compounds.
- metal salt, metal oxide, and metal hydroxide examples include divalent or higher valent metals such as magnesium, calcium, aluminum, iron, nickel, zirconium, titanium, silicon, boron, zinc, copper, vanadium, chromium, and tin. Examples thereof include salts, oxides and hydroxides of metals having a valence.
- An organometallic compound is a compound having in the molecule at least one structure in which an organic group is bonded directly to a metal atom or an organic group is bonded through an oxygen atom, a nitrogen atom, or the like.
- the organic group means a monovalent or polyvalent group containing at least a carbon atom, and can be, for example, an alkyl group, an alkoxy group, an acyl group, or the like.
- the bond does not mean only a covalent bond, but may be a coordinate bond by coordination such as a chelate compound.
- organometallic compound examples include an organotitanium compound, an organozirconium compound, an organoaluminum compound, and an organosilicon compound.
- An organometallic compound may be used individually by 1 type, and may use 2 or more types together.
- organic titanium compounds include titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; titanium acetylacetonate, titanium tetraacetylacetonate And titanium chelates such as polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, and titanium ethyl acetoacetate; and titanium acylates such as polyhydroxytitanium stearate.
- titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate
- titanium acetylacetonate titanium tetraacetylacetonate
- organic zirconium compound examples include zirconium normal propionate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate and the like.
- Examples of the organic aluminum compound include aluminum acetylacetonate and aluminum organic acid chelate.
- Examples of the organic silicon compound include compounds in which the ligands exemplified above for the organic titanium compound and the organic zirconium compound are bonded to silicon.
- polymeric crosslinking agents such as methylolated melamine resins and polyamide epoxy resins can also be used.
- polyamide epoxy resins include “Smilease Resin 650 (30)” and “Smilease Resin 675” (both trade names) sold by Taoka Chemical Co., Ltd.
- a polyvinyl alcohol-based resin is used as a resin component for forming the primer layer
- a polyamide epoxy resin, a methylolated melamine resin, a dialdehyde-based crosslinking agent, a metal chelate compound-based crosslinking agent, or the like is preferably used as the crosslinking agent.
- the ratio of the resin component to the crosslinking agent in the primer layer forming coating solution is within the range of about 0.1 to 100 parts by weight of the crosslinking agent with respect to 100 parts by weight of the resin component. And the like, and it is preferable to select from the range of about 0.1 to 50 parts by weight.
- the primer layer forming coating solution preferably has a solid content concentration of about 1 to 25% by weight.
- the thickness of the primer layer is preferably about 0.05 to 1 ⁇ m, more preferably 0.1 to 0.4 ⁇ m.
- the thickness is less than 0.05 ⁇ m, the effect of improving the adhesion between the base film 30 and the polyvinyl alcohol-based resin layer 6 is small, and when the thickness is more than 1 ⁇ m, it is disadvantageous for thinning the polarizing plate.
- the method of applying the primer layer forming coating solution to the base film 30 can be the same as the coating solution for forming the polyvinyl alcohol-based resin layer.
- the primer layer is applied to the surface (one surface or both surfaces of the base film 30) to which the coating liquid for forming the polyvinyl alcohol-based resin layer is applied.
- the drying temperature and drying time of the coating layer comprising the primer layer forming coating solution are set according to the type of solvent contained in the coating solution.
- the drying temperature is, for example, 50 to 200 ° C., preferably 60 to 150 ° C. When the solvent contains water, the drying temperature is preferably 80 ° C. or higher.
- the drying time is, for example, 30 seconds to 20 minutes.
- the order of coating on the base film 30 is not particularly limited.
- the base film 30 is provided.
- the polyvinyl alcohol-based resin layer 6 may be formed on both sides, or after the primer layer and the polyvinyl alcohol-based resin layer 6 are sequentially formed on one surface of the base film 30, A primer layer and a polyvinyl alcohol-based resin layer 6 may be sequentially formed on the other surface of the base film 30.
- this process consists of extending
- the stretched film 200 is obtained.
- the stretching process is usually uniaxial stretching.
- the stretching ratio of the laminated film 100 can be appropriately selected depending on the desired polarization characteristics, but is preferably more than 5 times and not more than 17 times, more preferably more than 5 times the original length of the laminated film 100. 8 times or less.
- the draw ratio is 5 times or less, the polyvinyl alcohol-based resin layer 6 is not sufficiently oriented, so that the degree of polarization of the polarizer 5 may not be sufficiently high.
- the draw ratio exceeds 17 times, the film is likely to be broken during stretching, and the thickness of the stretched film 200 becomes unnecessarily thin, and the workability and handleability in subsequent processes may be reduced.
- the stretching process is not limited to one-stage stretching, and can be performed in multiple stages.
- all of the multistage stretching processes may be performed continuously before the dyeing process S30, or the second and subsequent stretching processes may be performed simultaneously with the dyeing process and / or the crosslinking process in the dyeing process S30.
- the stretching treatment may be longitudinal stretching that extends in the film longitudinal direction (film transport direction), and may be lateral stretching or oblique stretching that extends in the film width direction.
- the longitudinal stretching method include inter-roll stretching using a roll, compression stretching, stretching using a chuck (clip), and the like
- examples of the lateral stretching method include a tenter method.
- the stretching treatment either a wet stretching method or a dry stretching method can be adopted. However, it is preferable to use the dry stretching method because the stretching temperature can be selected from a wide range.
- the stretching temperature is set to be equal to or higher than the temperature at which the polyvinyl alcohol-based resin layer 6 and the entire base film 30 can be stretched, and preferably the phase transition temperature (melting point or glass transition temperature) of the base film 30. It is in the range of ⁇ 30 ° C. to + 30 ° C., more preferably in the range of ⁇ 30 ° C. to + 5 ° C., and still more preferably in the range of ⁇ 25 ° C. to + 0 ° C.
- the phase transition temperature means the highest phase transition temperature among the phase transition temperatures exhibited by the plurality of resin layers.
- the stretching temperature is lower than the phase transition temperature of ⁇ 30 ° C., it is difficult to achieve a high-magnification stretching of more than 5 times, or the fluidity of the base film 30 is too low and the stretching process tends to be difficult.
- the stretching temperature exceeds + 30 ° C. of the phase transition temperature, the fluidity of the base film 30 is too large and stretching tends to be difficult.
- the drawing temperature is within the above range, and more preferably 120 ° C. or higher. This is because when the stretching temperature is 120 ° C. or higher, there is no difficulty in the stretching treatment even at a high stretching ratio of more than 5 times.
- a zone heating method for example, a method in which hot air is blown and heated in a stretching zone such as a heating furnace adjusted to a predetermined temperature
- a heater heating method a method in which infrared heaters, halogen heaters, panel heaters, etc. are installed above and below the laminated film 100 and heated by radiant heat.
- the zone heating method is preferable from the viewpoint of the uniformity of the stretching temperature.
- the two nip roll pairs may be installed in the temperature-controlled stretching zone or outside the stretching zone, but they are installed outside the stretching zone to prevent adhesion between the laminated film 100 and the nip roll. Is preferred.
- the stretching temperature means the atmospheric temperature in the zone (for example, in the heating furnace) in the case of the zone heating method, and means the atmospheric temperature in the furnace in the case of heating in the furnace also in the heater heating method. Moreover, in the case of the method of heating roll itself, the surface temperature of a roll is meant.
- a preheat treatment step for preheating the laminated film 100 may be provided.
- the preheating method the same method as the heating method in the stretching process can be used.
- preheating may be performed at any timing before passing through the upstream nip roll, during passing, or after passing.
- preheating is preferably performed at a timing before passing through the hot roll.
- preheating is preferably performed at a timing before increasing the distance between chucks.
- the preheating temperature is preferably in the range of ⁇ 50 ° C. to ⁇ 0 ° C. of the stretching temperature, and more preferably in the range of ⁇ 40 ° C. to ⁇ 10 ° C. of the stretching temperature.
- a heat setting treatment step may be provided after the stretching treatment in the stretching step S20.
- the heat setting process is a process in which heat treatment is performed at a temperature equal to or higher than the crystallization temperature while maintaining a tension state in a state where the end of the stretched film 200 is held by a clip. By this heat setting treatment, crystallization of the polyvinyl alcohol-based resin layer 6 ′ is promoted.
- the temperature of the heat setting treatment is preferably in the range of ⁇ 0 ° C. to ⁇ 80 ° C. of the stretching temperature, and more preferably in the range of ⁇ 0 ° C. to ⁇ 50 ° C. of the stretching temperature.
- this step is a step in which a polarizer 5 is obtained by dyeing the polyvinyl alcohol resin layer 6 ′ of the stretched film 200 with a dichroic dye and adsorbing and orienting it. Through this step, a polarizing laminated film 300 in which the polarizer 5 is laminated on one side or both sides of the base film 30 ′ is obtained.
- the dyeing step can be performed by immersing the entire stretched film 200 in a solution (dye solution) containing a dichroic dye.
- a solution in which the above dichroic dye is dissolved in a solvent can be used.
- a solvent for the dyeing solution water is generally used, but an organic solvent compatible with water may be further added.
- the concentration of the dichroic dye in the dyeing solution is preferably 0.01 to 10% by weight, more preferably 0.02 to 7% by weight, and further preferably 0.025 to 5% by weight. preferable.
- iodine When iodine is used as the dichroic dye, it is preferable to further add an iodide to the dyeing solution containing iodine because the dyeing efficiency can be further improved.
- iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. Is mentioned.
- the concentration of iodide in the dyeing solution is preferably 0.01 to 20% by weight. Of the iodides, it is preferable to add potassium iodide.
- the ratio of iodine to potassium iodide is preferably in the range of 1: 5 to 1: 100, more preferably in the range of 1: 6 to 1:80. Preferably, it is in the range of 1: 7 to 1:70.
- the immersion time of the stretched film 200 in the dyeing solution is usually in the range of 15 seconds to 15 minutes, preferably 30 seconds to 3 minutes.
- the temperature of the dyeing solution is preferably in the range of 10 to 60 ° C., more preferably in the range of 20 to 40 ° C.
- sucked to a polyvinyl alcohol-type resin layer can be orientated favorably.
- the dyeing step S30 is performed after the laminated film 100 is subjected to at least some stretching treatment. That is, the stretched film 200 obtained by subjecting the stretching process to the target magnification in the stretching process S20 can be used for the dyeing process S30, and after performing the stretching process at a lower ratio than the target in the stretching process S20. In the dyeing step S30, the stretching process can be performed until the total stretching ratio reaches the target ratio.
- the dyeing step S30 can include a cross-linking treatment step performed subsequent to the dyeing treatment.
- the crosslinking treatment can be performed by immersing the dyed film in a solution containing a crosslinking agent (crosslinking solution).
- a crosslinking agent conventionally known substances can be used, and examples thereof include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde.
- a crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
- the crosslinking solution can be a solution in which a crosslinking agent is dissolved in a solvent.
- a solvent for example, water can be used, but an organic solvent compatible with water may be further included.
- the concentration of the crosslinking agent in the crosslinking solution is preferably in the range of 1 to 20% by weight, more preferably in the range of 6 to 15% by weight.
- the crosslinking solution can contain iodide.
- iodide By adding the iodide, the polarization performance in the plane of the polarizer 5 can be made more uniform.
- iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. Is mentioned.
- the concentration of iodide in the cross-linking solution is preferably 0.05 to 15% by weight, and more preferably 0.5 to 8% by weight.
- the immersion time of the dyed film in the crosslinking solution is usually 15 seconds to 20 minutes, preferably 30 seconds to 15 minutes.
- the temperature of the crosslinking solution is preferably in the range of 10 to 90 ° C.
- the crosslinking treatment can be performed simultaneously with the dyeing treatment by blending a crosslinking agent in the dyeing solution. Further, a stretching process may be performed during the crosslinking process.
- the specific mode for carrying out the stretching treatment during the crosslinking treatment is as described above. Moreover, you may perform the process immersed in a crosslinking solution 2 or more times using 2 or more types of crosslinking solutions from which a composition differs.
- the washing process usually includes a water washing process.
- the water washing treatment can be performed by immersing the film after the dyeing treatment or after the crosslinking treatment in pure water such as ion exchange water or distilled water.
- the water washing temperature is usually in the range of 3 to 50 ° C., preferably 4 to 20 ° C.
- the immersion time in water is usually 2 to 300 seconds, preferably 3 to 240 seconds.
- the washing step may be a combination of a water washing step and a washing step with an iodide solution.
- liquids such as methanol, ethanol, isopropyl alcohol, butanol, and propanol can be appropriately contained in the cleaning liquid used in the water cleaning step and / or the cleaning process using the iodide solution.
- any appropriate method such as natural drying, blow drying, and heat drying can be adopted.
- the drying temperature is usually 20 to 95 ° C.
- the drying time is usually about 1 to 15 minutes.
- a polarizing laminated film 300 including the polarizer 5 is obtained.
- the polarizer 5 is manufactured according to the manufacturing method shown in FIG. 3, when measuring the absorbance characteristic of the polarizer 5 (absolute value of the difference between the absorbance A 700 and the absorbance A 450 ), A polarizing laminated film 300 in which a base film 30 ′ is laminated as a sample can be used. There is no substantial difference between the polarizer 5 alone and the polarizing laminated film 300 in terms of absorbance characteristics.
- this process bonds the 1st protective film 10 on the polarizer 5 of the polarizing laminated film 300, ie, the surface on the opposite side to the base film 30 'side of the polarizer 5. As shown in FIG. It is the process of obtaining the bonding film 400.
- the first protective film 10 is usually bonded onto the both-side polarizer 5.
- these first protective films 10 may be the same type of protective film or different types of protective films.
- the first protective film 10 can be bonded to the polarizer 5 via the first adhesive layer 15.
- the bonding method using the adhesive that forms the first adhesive layer 15 and the adhesive between the protective film and the polarizer 5 is as described above.
- the 1st protective film 10 and the polarizer 5 can also be bonded through the adhesive layer as mentioned above.
- the surface of the first protective film 10 on the side of the polarizer 5 is subjected to plasma treatment, corona treatment, ultraviolet ray in order to improve the adhesion with the polarizer 5.
- Surface treatment (easy adhesion treatment) such as irradiation treatment, flame (flame) treatment, and saponification treatment can be performed, and among them, plasma treatment, corona treatment or saponification treatment is preferable.
- plasma treatment or corona treatment is usually performed.
- a saponification process is normally performed.
- the saponification treatment include a method of immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.
- Peeling step S50 This process is a process of peeling and removing the base film 30 ′ from the bonding film 400 obtained by bonding the first protective film 10.
- the single-side protective film-attached polarizing plate 2 shown in FIG. 2 in which the first protective film 10 is laminated on one side of the polarizer 5 is obtained.
- the polarizing laminated film 300 has the polarizer 5 on both surfaces of the base film 30 ′, and the first protective film 10 is bonded to both the polarizers 5, one sheet is obtained by the peeling step S 50.
- Two polarizing plates 2 with a single-sided protective film are obtained from the polarizing laminated film 300.
- the method for peeling and removing the base film 30 ′ is not particularly limited, and can be peeled by the same method as the peeling step of a separator (peeling film) performed with a normal pressure-sensitive adhesive polarizing plate.
- Substrate film 30 ' may peel immediately as it is after 1st bonding process S40, and after 1st bonding process S40, it will wind up in roll shape once, and will peel off, unwinding in the subsequent process. May be.
- 2nd bonding process S60 This process bonds the 2nd protective film 20 on the polarizer 5 of the polarizing plate 2 with a single-sided protective film, ie, the surface on the opposite side to the 1st protective film 10 bonded in 1st bonding process S40. And it is the process of obtaining the polarizing plate 1 with a double-sided protective film as shown in FIG.
- the second protective film 20 can be bonded to the polarizer 5 through the second adhesive layer 25.
- the bonding method using the adhesive that forms the second adhesive layer 25 and the adhesive between the protective film and the polarizer 5 is as described above.
- the 2nd protective film 20 and the polarizer 5 can also be bonded through the adhesive layer as mentioned above.
- About the surface treatment (easy adhesion process) in bonding of the 2nd protective film 20 the content described about 1st bonding process S40 is quoted.
- the main example is a) Potassium iodide concentration in the crosslinking solution used for the crosslinking treatment in the dyeing step S30, b) Stretch ratio of the polyvinyl alcohol-based resin layer, neck-in ratio during stretching, stretching temperature, c) Water washing temperature in water washing step after crosslinking treatment in dyeing step S30, immersion time in water, d) Drying temperature and drying time in the drying step after the water washing step in the dyeing step S30, e) In the case where the protective film is bonded to the polarizer 5 using the aqueous adhesive in the first bonding step S40 and / or the second bonding step S60, the drying temperature and drying in the drying step after bonding are performed. time.
- the crosslinking solution is used after the dyeing process in the dyeing step S30. It is preferable that the amount of potassium iodide in the second crosslinking solution is 10 parts by weight or less, more preferably 7 parts by weight or less with respect to 100 parts by weight of water. Preferably, the amount is 5 parts by weight or less.
- the absorbance ratio A 700 / A 450 of the polarizing plates 1 and 2 and the absorbance difference of the polarizer 5 after the 100 ° C. test are not dependent only on a), but also depend on, for example, the above b) to e). Therefore, it is necessary to adjust the absorbance ratio A 700 / A 450 and the absorbance difference finally obtained while controlling these b) to e).
- the final total draw ratio of the polyvinyl alcohol-based resin layer is 6.0 times or less. Preferably there is.
- the final total draw ratio of the polyvinyl alcohol-based resin layer is preferably more than 5 times. If the stretching temperature is too high, crystallization of the polyvinyl alcohol-based resin proceeds excessively and it becomes difficult to control the absorbances A 700 and A 450 , so that the stretching temperature is preferably 170 ° C. or lower.
- the difference in absorbance of the polarizer 5 after the test tends to be 0.11 or less.
- the water washing temperature is preferably in the range of 5 to 15 ° C.
- the immersion time in water is preferably about 5 to 30 seconds.
- Example 1 (1) Primer layer forming step Polyvinyl alcohol powder (“Z-200” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1100, saponification degree 99.5 mol%) was dissolved in 95 ° C. hot water, A polyvinyl alcohol aqueous solution having a concentration of 3% by weight was prepared. The resulting aqueous solution was mixed with a crosslinking agent (“Smiles Resin 650” manufactured by Taoka Chemical Co., Ltd.) at a ratio of 5 parts by weight to 6 parts by weight of the polyvinyl alcohol powder to form a primer layer forming coating solution. Got.
- a crosslinking agent (“Smiles Resin 650” manufactured by Taoka Chemical Co., Ltd.)
- an unstretched polypropylene (PP) film (melting point: 163 ° C.) having a thickness of 90 ⁇ m is prepared as a base film, and after corona treatment is performed on one surface thereof, the above-described corona treatment surface is subjected to a microgravure coater.
- the primer layer-forming coating solution was applied and dried at 80 ° C. for 10 minutes to form a primer layer having a thickness of 0.2 ⁇ m.
- the stretched film prepared in the above (3) is about 30 ° C. dyed aqueous solution containing iodine and potassium iodide (containing 0.6 parts by weight iodine and 10 parts by weight potassium iodide per 100 parts by weight water). After the polyvinyl alcohol resin layer was dyed for 180 seconds, the excess dye solution was washed away with pure water at 10 ° C.
- a crosslinking treatment was performed by immersing in a crosslinking aqueous solution (containing 9.5 parts by weight of boric acid and 4 parts by weight of potassium iodide per 100 parts by weight of water) for 60 seconds. Thereafter, the film was washed with pure water at 10 ° C. for 10 seconds, and finally dried at 40 ° C. for 300 seconds to obtain a polarizing laminated film comprising a base film / primer layer / polarizer.
- a first protective film [triacetylcellulose (TAC), which was subjected to saponification treatment on the bonding surface, A transparent protective film (“KC4UY” manufactured by Konica Minolta Opto Co., Ltd.)] was bonded and crimped by passing between a pair of bonding rolls. Subsequently, it is dried in an oven at 80 ° C. for 2 minutes, and is bonded onto the polarizer layer to obtain a bonded film having a layer structure of first protective film / adhesive layer / polarizer / primer layer / base film. (First bonding step).
- TAC triacetylcellulose
- a transparent protective film (“KC4UY” manufactured by Konica Minolta Opto Co., Ltd.)
- the base film was peeled and removed from the obtained laminated film (peeling process).
- the base film was easily peeled off to obtain a polarizing plate with a single-sided protective film comprising the first protective film / adhesive layer / polarizer / primer layer.
- a second protective film [cyclic polyolefin-based film] obtained by applying a corona treatment to the bonding surface on the surface opposite to the first protective film of the obtained polarizing plate with a single-side protective film, using an ultraviolet curable adhesive.
- a transparent protective film made of resin (“ZF14” manufactured by Nippon Zeon Co., Ltd.)
- the adhesive layer is cured by ultraviolet irradiation, and the first protective film / adhesive layer / polarizer / primer layer
- a polarizing plate with a double-sided protective film having a layer configuration of / adhesive layer / second protective film was obtained.
- Example 2 A polarizing plate with a double-sided protective film was produced in the same manner as in Example 1 except that the content of potassium iodide in the second aqueous crosslinked solution was 5 parts by weight per 100 parts by weight of water.
- Example 3 A polarizing plate with a double-sided protective film was produced in the same manner as in Example 1 except that the content of potassium iodide in the second aqueous crosslinked solution was 6 parts by weight per 100 parts by weight of water.
- Example 4 The content of potassium iodide in the second cross-linking aqueous solution is 7 parts by weight per 100 parts by weight of water, and the washing time with pure water at 10 ° C. after the immersion treatment in the second cross-linking aqueous solution is 60 seconds.
- a polarizing plate with a double-sided protective film was produced.
- Example 1 A polarizing plate with a double-sided protective film was produced in the same manner as in Example 1 except that the content of potassium iodide in the second aqueous crosslinked solution was 8 parts by weight per 100 parts by weight of water.
- a polarizing plate with a double-sided protective film was produced in the same manner as in Example 1 except that the content of potassium iodide in the second aqueous crosslinked solution was 10 parts by weight per 100 parts by weight of water.
- the absorbances A 700 and A 450 include measured values obtained when the polarizer and the Glan-Thompson prism are in the crossed Nicols position, and The average value with the measured value in the direction rotated 90 degrees was adopted.
- Lv1 Level without any redness
- Lv2 Level that keeps a black state and cannot visually recognize redness
- Lv3 It looks like the color is slightly lighter than the one before the heat test, but there is almost no redness
- Lv4 The level that has changed to reddish overall
- Lv5 Level completely changed to red.
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Abstract
Description
[1] 厚みが10μm以下の偏光子を含み、
波長700nmでの吸光度A700と波長450nmでの吸光度A450との比A700/A450が0.85以上である、偏光板。
[3] 前記偏光子は、100℃で30分間熱処理したときの、波長700nmでの吸光度A700と波長450nmでの吸光度A450との差の絶対値が0.11以下である[1]又は[2]に記載の偏光板。
100℃で30分間熱処理したときの、波長700nmでの吸光度A700と波長450nmでの吸光度A450との差の絶対値が0.11以下である偏光子。
[6] 偏光子の少なくとも一方の面に貼合される保護フィルムをさらに含む[1]~[3]及び[5]のいずれかに記載の偏光板。
(1)偏光板の基本的構成
図1は、本発明に係る偏光板の層構成の一例を示す概略断面図である。図1に示される偏光板1のように、本発明の偏光板は、厚み10μm以下の偏光子5と、その一方の面に第1接着剤層15を介して積層される第1保護フィルム10と、他方の面に第2接着剤層25を介して積層される第2保護フィルム20とを備えるものであることができる。偏光板1は、第1保護フィルム10及び/又は第2保護フィルム20上に積層される他の光学機能層や粘着剤層等をさらに有していてもよい。
第1の実施形態において本発明の偏光板は、厚みが10μm以下の偏光子を含み、波長700nmでの吸光度A700(以下、単に「吸光度A700」ともいう。)と波長450nmでの吸光度A450(以下、単に「吸光度A450」ともいう。)との比A700/A450が0.85以上である。かかる吸光特性を示す本発明の偏光板は、偏光子5の厚みが10μm以下と小さいために比較的厚みの大きい従来の偏光子(35μm程度)に比べて偏光子5への水分の出入が格段に速く、赤変を生じやすいにもかかわらず、耐熱試験(通常、80~85℃で500~750時間)に供しても赤変が生じにくく、ニュートラルな表示を保つことができ、耐熱性に優れている。このような高耐熱性(赤変のしにくさ)は、偏光板を液晶表示装置のような表示装置などに適用し、実使用に供される場合においても長期にわたって持続する。
吸光度=-log(T/T0)
により求められる。
偏光板又は偏光子の偏光性能は、主に単体透過率及び偏光度と呼ばれる数値で表すことができ、それぞれ下記式:
単体透過率(λ)=0.5×(Tp(λ)+Tc(λ))
偏光度(λ)=100×(Tp(λ)-Tc(λ))/(Tp(λ)+Tc(λ))
で定義される。
偏光子5は、一軸延伸されたポリビニルアルコール系樹脂層に二色性色素を吸着配向させたものであることができる。本発明において偏光子5の厚みは10μm以下であり、好ましくは7μm以下である。偏光子5の厚みを10μm以下とすることにより偏光板1,2の薄膜化を実現できる一方、本発明によれば、このような薄膜の偏光子5を用いる場合であっても耐熱試験下での赤変を効果的に抑制することができる。
ケン化度(モル%)=100×(水酸基の数)÷(水酸基の数+酢酸基の数)
で定義される。ケン化度は、JIS K 6726(1994)に準拠して求めることができる。ケン化度が高いほど、水酸基の割合が高いことを示しており、従って結晶化を阻害する酢酸基の割合が低いことを示している。
第1保護フィルム10及び第2保護フィルム20はそれぞれ、熱可塑性樹脂、例えば、鎖状ポリオレフィン系樹脂(ポリプロピレン系樹脂等)、環状ポリオレフィン系樹脂(ノルボルネン系樹脂等)のようなポリオレフィン系樹脂;セルローストリアセテート、セルロースジアセテートのようなセルロースエステル系樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートのようなポリエステル系樹脂;ポリカーボネート系樹脂;(メタ)アクリル系樹脂;又はこれらの混合物、共重合物等からなる透明樹脂フィルムであることができる。第1保護フィルム10と第2保護フィルム20は、互いに同種の保護フィルムであってもよいし、異種の保護フィルムであってもよい。
第1及び第2接着剤層15,25を形成する接着剤としては、水系接着剤又は光硬化性接着剤を用いることができる。第1接着剤層15を形成する接着剤と第2接着剤層25を形成する接着剤とは同種であってもよいし、異種であってもよい。
図1に示される偏光板1における第1保護フィルム10又は第2保護フィルム20上、図2に示される偏光板2における偏光子5上に、偏光板を他の部材(例えば液晶表示装置に適用する場合における液晶セル)に貼合するための粘着剤層を積層してもよい。粘着剤層を形成する粘着剤は通常、(メタ)アクリル系樹脂、スチレン系樹脂、シリコーン系樹脂などをベースポリマーとし、そこに、イソシアネート化合物、エポキシ化合物、アジリジン化合物のような架橋剤を加えた粘着剤組成物からなる。さらに微粒子を含有して光散乱性を示す粘着剤層とすることもできる。
本発明の偏光子及び偏光板は、図3に示される方法によって好適に製造することができる。図3に示される偏光板の製造方法は、下記工程:
(1)基材フィルムの少なくとも一方の面にポリビニルアルコール系樹脂を含有する塗工液を塗工した後、乾燥させることによりポリビニルアルコール系樹脂層を形成して積層フィルムを得る樹脂層形成工程S10、
(2)積層フィルムを延伸して延伸フィルムを得る延伸工程S20、
(3)延伸フィルムのポリビニルアルコール系樹脂層を二色性色素で染色して偏光子を形成することにより偏光性積層フィルムを得る染色工程S30、
(4)偏光性積層フィルムの偏光子上に第1保護フィルムを貼合して貼合フィルムを得る第1貼合工程S40、
(5)貼合フィルムから基材フィルムを剥離除去して片面保護フィルム付の偏光板を得る剥離工程S50、
をこの順で含む。
(6)片面保護フィルム付偏光板の偏光子面に第2保護フィルムを貼合する第2貼合工程S60、
を含む。以下、図4~図7を参照しながら各工程について説明する。
図4を参照して、本工程は、基材フィルム30の少なくとも一方の面にポリビニルアルコール系樹脂層6を形成して積層フィルム100を得る工程である。このポリビニルアルコール系樹脂層6は、延伸工程S20及び染色工程S30を経て偏光子5となる層である。ポリビニルアルコール系樹脂層6は、ポリビニルアルコール系樹脂を含有する塗工液を基材フィルム30の片面又は両面に塗工し、塗工層を乾燥させることにより形成することができる。このような塗工によりポリビニルアルコール系樹脂層を形成する方法は、薄膜の偏光子5を得やすい点で有利である。
基材フィルム30は熱可塑性樹脂から構成することができ、中でも透明性、機械的強度、熱安定性、延伸性等に優れる熱可塑性樹脂から構成することが好ましい。このような熱可塑性樹脂の具体例は、例えば、鎖状ポリオレフィン系樹脂、環状ポリオレフィン系樹脂(ノルボルネン系樹脂等)のようなポリオレフィン系樹脂;ポリエステル系樹脂;(メタ)アクリル系樹脂;セルローストリアセテート、セルロースジアセテートのようなセルロースエステル系樹脂;ポリカーボネート系樹脂;ポリビニルアルコール系樹脂;ポリ酢酸ビニル系樹脂;ポリアリレート系樹脂;ポリスチレン系樹脂;ポリエーテルスルホン系樹脂;ポリスルホン系樹脂;ポリアミド系樹脂;ポリイミド系樹脂;及びこれらの混合物、共重合物を含む。
塗工液は、好ましくはポリビニルアルコール系樹脂の粉末を良溶媒(例えば水)に溶解させて得られるポリビニルアルコール系樹脂溶液である。ポリビニルアルコール系樹脂の詳細は、上述のとおりである。
上記塗工液を基材フィルム30に塗工する方法は、ワイヤーバーコーティング法;リバースコーティング、グラビアコーティングのようなロールコーティング法;ダイコート法;カンマコート法;リップコート法;スピンコーティング法;スクリーンコーティング法;ファウンテンコーティング法;ディッピング法;スプレー法等の方法から適宜選択することができる。
プライマー層は、プライマー層形成用塗工液を基材フィルム30の表面に塗工した後、乾燥させることにより形成することができる。プライマー層形成用塗工液は、基材フィルム30とポリビニルアルコール系樹脂層6との両方にある程度強い密着力を発揮する成分を含む。プライマー層形成用塗工液は通常、このような密着力を付与する樹脂成分と溶媒とを含有する。樹脂成分としては、好ましくは透明性、熱安定性、延伸性等に優れる熱可塑樹脂が用いられ、例えば、(メタ)アクリル系樹脂、ポリビニルアルコール系樹脂等が挙げられる。中でも、良好な密着力を与えるポリビニルアルコール系樹脂が好ましく用いられる。
図5を参照して、本工程は、基材フィルム30及びポリビニルアルコール系樹脂層6からなる積層フィルム100を延伸して、延伸された基材フィルム30’及びポリビニルアルコール系樹脂層6’からなる延伸フィルム200を得る工程である。延伸処理は通常、一軸延伸である。
図6を参照して、本工程は、延伸フィルム200のポリビニルアルコール系樹脂層6’を二色性色素で染色してこれを吸着配向させ、偏光子5とする工程である。本工程を経て基材フィルム30’の片面又は両面に偏光子5が積層された偏光性積層フィルム300が得られる。
図7を参照して、本工程は、偏光性積層フィルム300の偏光子5上、すなわち、偏光子5の基材フィルム30’側とは反対側の面に第1保護フィルム10を貼合して貼合フィルム400を得る工程である。偏光性積層フィルム300が基材フィルム30’の両面に偏光子5を有する場合は通常、両面の偏光子5上にそれぞれ第1保護フィルム10が貼合される。この場合、これらの第1保護フィルム10は同種の保護フィルムであってもよいし、異種の保護フィルムであってもよい。
本工程は、第1保護フィルム10を貼合して得られた貼合フィルム400から基材フィルム30’を剥離除去する工程である。この工程を経て、偏光子5の片面に第1保護フィルム10が積層された図2に示される片面保護フィルム付偏光板2が得られる。偏光性積層フィルム300が基材フィルム30’の両面に偏光子5を有し、これら両方の偏光子5に第1保護フィルム10を貼合した場合には、この剥離工程S50により、1枚の偏光性積層フィルム300から2枚の片面保護フィルム付偏光板2が得られる。
本工程は、片面保護フィルム付偏光板2の偏光子5上、すなわち第1貼合工程S40にて貼合した第1保護フィルム10とは反対側の面に、第2保護フィルム20を貼合し、図1に示されるような両面保護フィルム付の偏光板1を得る工程である。
以上のような製造方法によって両面保護フィルム付偏光板1又は片面保護フィルム付偏光板2を作製する場合において、当該製造方法における各種処理は、偏光板1,2の吸光度比A700/A450や、100℃試験後の偏光子5の吸光度差(吸光度A700と吸光度A450との差の絶対値)に影響を与えるいくつかの因子を含んでいる。その主な例を挙げれば、
a)染色工程S30の架橋処理に用いる架橋溶液のヨウ化カリウム濃度、
b)ポリビニルアルコール系樹脂層の延伸倍率、延伸時のネックイン率、延伸温度、
c)染色工程S30における架橋処理後の水洗浄工程での水洗浄温度、水への浸漬時間、
d)染色工程S30における水洗浄工程後の乾燥工程での乾燥温度、乾燥時間、
e)第1貼合工程S40及び/又は第2貼合工程S60にて水系接着剤を用いて保護フィルムを偏光子5に貼合する場合において、貼合後の乾燥工程での乾燥温度、乾燥時間。
(1)プライマー層形成工程
ポリビニルアルコール粉末(日本合成化学工業(株)製の「Z-200」、平均重合度1100、ケン化度99.5モル%)を95℃の熱水に溶解し、濃度3重量%のポリビニルアルコール水溶液を調製した。得られた水溶液に架橋剤(田岡化学工業(株)製の「スミレーズレジン650」)をポリビニルアルコール粉末6重量部に対して5重量部の割合で混合して、プライマー層形成用塗工液を得た。
ポリビニルアルコール粉末((株)クラレ製の「PVA124」、平均重合度2400、ケン化度98.0~99.0モル%)を95℃の熱水に溶解し、濃度8重量%のポリビニルアルコール水溶液を調製し、これをポリビニルアルコール系樹脂層形成用塗工液とした。
上記(2)で作製した積層フィルムに対して、フローティングの縦一軸延伸装置を用いて160℃で5.8倍の自由端一軸延伸を実施し、延伸フィルムを得た。延伸後のポリビニルアルコール系樹脂層の厚みは6.1μmであった。
上記(3)で作製した延伸フィルムを、ヨウ素とヨウ化カリウムとを含む30℃の染色水溶液(水100重量部あたりヨウ素を0.6重量部、ヨウ化カリウムを10重量部含む。)に約180秒間浸漬してポリビニルアルコール系樹脂層の染色処理を行った後、10℃の純水で余分な染色水溶液を洗い流した。
ポリビニルアルコール粉末((株)クラレ製の「KL-318」、平均重合度1800)を95℃の熱水に溶解し、濃度3重量%のポリビニルアルコール水溶液を調製した。得られた水溶液に架橋剤(田岡化学工業(株)製の「スミレーズレジン650」)をポリビニルアルコール粉末2重量部に対して1重量部の割合で混合し、接着剤水溶液とした。
第2架橋水溶液におけるヨウ化カリウムの含有量を、水100重量部あたり5重量部としたこと以外は、実施例1と同様にして両面保護フィルム付偏光板を作製した。
第2架橋水溶液におけるヨウ化カリウムの含有量を、水100重量部あたり6重量部としたこと以外は、実施例1と同様にして両面保護フィルム付偏光板を作製した。
第2架橋水溶液におけるヨウ化カリウムの含有量を、水100重量部あたり7重量部とし、第2架橋水溶液への浸漬処理後の10℃の純水での洗浄時間を60秒間としたこと以外は、実施例1と同様にして両面保護フィルム付偏光板を作製した。
第2架橋水溶液におけるヨウ化カリウムの含有量を、水100重量部あたり8重量部としたこと以外は、実施例1と同様にして両面保護フィルム付偏光板を作製した。
第2架橋水溶液におけるヨウ化カリウムの含有量を、水100重量部あたり10重量部としたこと以外は、実施例1と同様にして両面保護フィルム付偏光板を作製した。
(1)100℃試験後の偏光子の吸光度差の測定
実施例及び比較例で得られた偏光子(保護フィルムを貼合する前の偏光性積層フィルムの状態)を100℃のオーブンに30分投入した後、吸光光度計(日本分光(株)製の「V7100」)を用いて、波長700nmでの吸光度A700と波長450nmでの吸光度A450を測定し、これらの差の絶対値を求めた。結果を表1に示す。吸光光度計V7100には偏光分離素子であるグラントムソンプリズムが入っているため、吸光度A700及びA450には、偏光子とグラントムソンプリズムとがクロスニコル位置であるときの測定値と、そこから90度回した方位での測定値との平均値を採用した。
実施例及び比較例で得られた両面保護フィルム付偏光板について、上記(1)と同様にして(ただし、100℃試験は実施していない。)、吸光度A700及びA450を測定し、吸光度比A700/A450を求めた。結果を表1に示す。
実施例及び比較例で得られた偏光子(保護フィルムを貼合する前の偏光性積層フィルムの状態)について、吸光光度計(日本分光(株)製の「V7100」)を用いて、視感度補正単体透過率(Ty)及び視感度補正偏光度(Py)を測定した。結果を表1に示す。測定の際、偏光性積層フィルムは、その偏光子側に入射光が入射されるようにセットした。
実施例及び比較例で得られた両面保護フィルム付偏光板から長さ10cmの短冊状試料を2つ切り出し、これらの試料をガラス板の両面に粘着剤を用いて貼合した。この際、第2保護フィルム「ZF14」側がガラス板側になるようにし、かつ、両面に配置した試料はクロスニコルの位置関係となるようにした。試料を貼合したガラス板を85℃のオーブンに500時間投入した後、オーブンから取り出し、暗室にてバックライト上で赤変の目視評価を行った。赤変のレベルの指標は、下記に示すとおりである。Lv3までを合格とした。結果を表1に示す。
Lv2:真っ黒の状態を保ち、目視で赤変が認識できないレベル、
Lv3:耐熱試験前のものと並べてみるとやや色が薄くなったように見えるが赤変はほとんどないレベル、
Lv4:全体的に赤っぽく変色してしまっているレベル、
Lv5:完全に赤に変色してしまっているレベル。
Claims (6)
- 厚みが10μm以下の偏光子を含み、
波長700nmでの吸光度A700と波長450nmでの吸光度A450との比A700/A450が0.85以上である、偏光板。 - 前記吸光度A450が0.42以下である請求項1に記載の偏光板。
- 前記偏光子は、100℃で30分間熱処理したときの、波長700nmでの吸光度A700と波長450nmでの吸光度A450との差の絶対値が0.11以下である請求項1又は2に記載の偏光板。
- 厚みが10μm以下であり、
100℃で30分間熱処理したときの、波長700nmでの吸光度A700と波長450nmでの吸光度A450との差の絶対値が0.11以下である偏光子。 - 請求項4に記載の偏光子を含む偏光板。
- 偏光子の少なくとも一方の面に貼合される保護フィルムをさらに含む請求項1~3及び5のいずれか1項に記載の偏光板。
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