CN109154688A - Polarization plates - Google Patents
Polarization plates Download PDFInfo
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- CN109154688A CN109154688A CN201780029708.1A CN201780029708A CN109154688A CN 109154688 A CN109154688 A CN 109154688A CN 201780029708 A CN201780029708 A CN 201780029708A CN 109154688 A CN109154688 A CN 109154688A
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- film
- protective film
- scar
- polarization plates
- polarizing film
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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Abstract
The object of the present invention is to provide be difficult to generate the slim polarization plates of the crackle of polarizing film.It is further an object that providing the polarization plates that can inhibit the generation of the bad orders such as cracked in polarizing film in the environment of high temperature repeatedly and low temperature.Polarization plates of the invention are to be laminated with first adhesive phase, the polarization plates of the first protective film with a thickness of 10 μm of polarizing films below and comprising cellulose-based resin; at least one party of above-mentioned first protective film in above-mentioned first protective film with the face of the above-mentioned polarizing film side in the face and above-mentioned first protective film of above-mentioned polarizing film opposite side has a scar, and above-mentioned scar is 0.001~500 μm long, wide 0.001~500 μm and deep 0.001~10 μm of scar and 0.001~10 μm and 0.001~1.0mm of area deep2Scar at least one party.
Description
Technical field
The present invention relates to one kind can the polarization plates used in various optical applications.
Background technique
In recent years, from the aspect of design, portability, the mobile terminal of smart phone etc is hastily promoting big
Picture, very thinization.In order to realize prolonged driving with limited thickness, used polarization plates are also required to realize high
Brightness, slimming.
In order to solve such requirement, following polarization plates were proposed, only configuration usually fits in polarizing film in side
The protective film formed by transparent resin on two sides, is additionally fitted with brightness enhancement film.For example, being disclosed successively layer in patent document 1
It is laminated with the protective film formed by transparent resin, the polarizing film for being adsorbed with iodine on polyvinyl alcohol film and being orientated, pressure adhesive
Slim and high brightness the polarization plates of layer, brightness enhancement film.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-039458 bulletin
Summary of the invention
Problem to be solved by the invention
However, it is that the filming of polarizing film promotes as a result, in the polarization plates being recorded in citation 1, if
Polarization plates are used in the environment of high temperature and low temperature repeatedly, then can be cracked in polarizing film.
Such as due to the foreign matter in the manufacturing process of polarization plates to being mixed into of the surface of protective film, be laminated protective film when it is different
Object be mixed into and the disposition of polarization plates etc. and scar can be generated near the end of polarization plate surface, may be due to the scar
Generate the crackle of above-mentioned polarizing film.
Due to the slimming along with polarization plates in recent years, it is easier to generate the crackle of polarizing film, therefore, it is desirable to have solution
Countermeasure.
Thus, the object of the present invention is to provide be difficult to generate the slim polarization plates of the crackle of polarizing film.In addition, this
The purpose of invention is, provides even if in the environment of high temperature repeatedly and low temperature using crackle, the leakage that can also inhibit polarizing film
The polarization plates of the generation of the bad orders such as light.
The method for solving problem
The present invention includes the following contents.
[1] a kind of polarization plates are to be laminated with first adhesive phase, with a thickness of 10 μm of polarizing films below and comprising fiber
The polarization plates of first protective film of prime system resin,
Above-mentioned first protective film is protected above-mentioned first protective film with the face of above-mentioned polarizing film opposite side and above-mentioned first
At least one party in the face of the above-mentioned polarizing film side of cuticula has scar,
Above-mentioned scar is 0.001~500 μm long, wide 0.001~500 μm and deep 0.001~10 μm of scar, Yi Jishen
0.001~10 μm and 0.001~1.0mm of area2Scar at least one party.
[2] according to the polarization plates recorded in [1], wherein be sequentially laminated with above-mentioned first adhesive phase, above-mentioned polarizing film and
Above-mentioned first protective film.
[3] according to the polarization plates recorded in [1] or [2], wherein above-mentioned first protective film above-mentioned first protective film with
The face of above-mentioned polarizing film opposite side has scar.
Invention effect
Even if polarization plates of the invention in the environment of high temperature repeatedly and low temperature, will not generate the light leakage of polarizing film, split
The ground such as line show good polarization characteristic.
In addition, polarization plates of the invention are slim and intensity, the polarization plates of excellent in te pins of durability.
Detailed description of the invention
Fig. 1 is to exemplify the figure of the schematic sectional view of layer composition of polarization plates of the invention.
Specific embodiment
It is illustrated hereinafter, attached drawing is suitably used to polarization plates of the invention, however the present invention is not limited to these
Embodiment.
In the present invention, polarization plates are laminated with first adhesive phase, protect with a thickness of 10 μm of polarizing films below and first
Film, their lamination order are not particularly limited.In one embodiment, as shown in Figure 1, polarization plates 100 of the invention can
To have the composition for being sequentially laminated with first adhesive phase 11, polarizing film 12 and the first protective film 13.It is only polarizing like this
In the case that the side of piece has protective film, it is easy to generate the crackle of polarizing film in the environment of high temperature repeatedly and low temperature, however
According to the present invention it is possible to effectively inhibit the crackle of polarizing film.
Polarizing film of the invention is that with a thickness of 10 μm or less and have the function that the light such as natural light are changed into rectilinearly polarized light
The component of energy.For example, polarizing film has 8 μm of thickness below.In addition, polarizing film of the invention can have 2 μm or more of thickness
Degree.In one embodiment, polarizing film can have 2 μm~8 μm of thickness.
In the past, polarizing film was thinner, more tended to be easy to generate significantly as caused by the scar for being present in polarization plates to inclined
The influence of the crackle of vibration piece.But using the present invention, can solve such problem, even the thin polarizing film of above range,
Polarization plates will not be cracked, and can show excellent optical characteristics.
First protective film of the invention the first protective film and polarizing film opposite side face and the first protective film it is inclined
At least one party in the face of vibration piece side has scar.Scar is long 0.001~500 μm, it is 0.001~500 μm and deep 0.001 wide~
10 μm of 0.001~10 μm and 0.001~1.0mm of area of scar and depth2Scar at least one party.
By making the first protective film that there is the scar of such size, even if in the environment of high temperature repeatedly and low temperature, this hair
Bright polarization plates will not generate light leakage, crackle etc., can show good polarization characteristic.Although its reason is not known simultaneously,
However you can think of it because, by making the first protective film that there is above-mentioned scar, thus repeatedly in the environment of high temperature and low temperature
The difference of the behavior of the behavior and polarizing film of first protective film becomes smaller, and can reduce the power for being applied to polarizing film.In addition, by making
First protective film of polarization plates has the scar of above range on its surface, applies heat punching in the environment of high temperature repeatedly and low temperature
When hitting, it is easy to discharge the stress inside polarization plates using scar as starting point.
By make the first protective film include cellulose-based resin, polarization plates of the invention can not generate further light leakage,
The ground such as crackle show good polarization characteristic.On the other hand, visual evil is likely to become more than the scar of above range itself
The reason of change.
Herein, " scar " of the invention as long as the size of scar is contained in above range, there is no limit for shape.Example
Such as, the scar for branch occurring comprising linear scar, the scar of polygon, curvilinear scar, multiple scars (such as abrades
Shape), recess (such as cylinder, polygon prism, circular cone, polygonal pyramid, taper) etc..
In addition, in " scar " of the invention, as long as the size of scar is contained in above range, the depth of scar, with
And width equidimension can be changed.For example, can have 6 μm of depth in some place of scar, in the another of scar
A place has 7 μm of depth.
Conventional method can be used in the measurement of the size of such scar, for example, the measurement using laser, benefit can be enumerated
With microscopical measurement.
The size of scar of the invention be the maximum scar that measurement is present in the first protective film, each side maximum value and
The size obtained.For example, the maximum scar of aggregate value of the length of scar, width, thickness is assumed to maximum wound in the present invention
Trace.
In addition, the area of so-called scar, refers to the area in the face for the plane for being parallel to the first protective film.
That is, the area of scar can not consider the depth of scar, as long as merely measuring the plane sight in the first protective film
The area of the scar observed.It is calculated in addition, conventional method can be used in the area of scar.
Position present in scar is not particularly limited.For example, can randomly exist in the full scope of film surface
Scar.For example, scar is present in the surface end of the first protective film.
For example, scar is present in the face with polarizing film opposite side of the first protective film.In this case, scar for example with
0.001~500 μm long, wide 0.001~500 μm and deep 0.001~10 μm of size.
As long as in addition, scar is on the surface of the first protective film, there are at least one, can be in every 1mm2In 0.0001
~0.001 density exists.For example, in the case where the polarization plates of 65mm × 130mm size, there may be about 0.8~about
8.5 scars.If the number of scar exists more than such range, the haze value of polarization plates is increased, the optics of polarization plates
Characteristic may become inadequate.
In addition, the shape along the scar of the depth direction formation of the first protective film can be relative to the flat of the first protective film
The shape that face is vertically formed is also possible to the shape along inclined direction formed relative to the plane of the first protective film, also
It can be the shape for being combined with them.
The forming method of scar is not particularly limited, for example, also can use foreign matter in the manufacturing process because of polarization plates to
Foreign matter when being mixed into, protective film is laminated on the surface of protective film be mixed into and the disposition of polarization plates etc. and in polarization plate surface
End nearby generate scar.In addition, in the manufacture of polarization plates, such as can be arranged in the surface end of the first protective film
Given scar.In this case, scratch type hardometer etc. can be used, scar is set in the surface end of the first protective film.
As long as the size of scar of the invention is contained in above range, the size for being combined with following record can be
Scar.
The length of scar is 0.001~500 μm, is 0.001~400 μm in another way.It should be noted that sending out
In the case where the scar of raw warpage, curvilinear scar, the length of scar can be indicated with the total of the length of the scar.
The width of scar is 0.001~500 μm, is 0.001~400 μm in another way.
The depth of scar is 0.001~10 μm, is 1~10 μm in another way.
For example, length, width of scar etc. can not be measured in the case where concave scar, but with the face of scar
Calculate the size of scar.In this case, scar has 0.01~1.0mm2Area, such as with 0.1~0.50mm2Face
Product has 0.1~0.30mm in another way2Area.
In another embodiment, scar has 0.001~500 μm long, wide 0.001~500 μm and deep 0.001~10 μ
The size of m.
In another embodiment, the depth of scar is 0.001~10 μm, and has 0.01~1.0mm2Area.
[polarizing film]
Polarizing film of the invention generally has the axis of homology and absorption axiss.The transmission axis direction of such polarizing film is understood to make
The direction of vibration of transmitted light when natural light transmission-polarizing piece.On the other hand, the axis of homology of the absorption axiss of polarizing film and polarizing film
It is orthogonal.It should be noted that polarizing film generally can be stretched film, the absorption axis direction of polarizing film is consistent with its draw direction.
In the present invention, term " direction parallel with the transmission axis direction of polarizing film " indicates the transmission with above-mentioned polarizing film
The direction of axis direction parallel or substantially parallel (angulation is within ± 7 degree).
Polarizing film, which can be, to be made the polyvinyl alcohol resin layer absorption dichroism pigment by being uniaxially stretched and is orientated and obtains
Polarizing film.
As polyvinyl alcohol resin, resin obtained by being saponified polyvinyl acetate system resin can be used.As poly-
Vinyl acetate resin can be with other than it may be exemplified the polyvinyl acetate as the homopolymer of vinyl acetate
Illustrate the copolymer of vinyl acetate with monomer that can be copolymerized therewith.As can be with other lists of vinyl acetate copolymerization
Body, for example, unsaturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, acrylamide with ammonium etc..
The saponification degree of polyvinyl alcohol resin can be the range of 80 moles of % or more.The model of for example, 90 moles % or more
It encloses, is the range of 95 moles of % in another way.It is poly- that polyvinyl alcohol resin is also possible to the modification that a part has been modified
Vinyl alcohol, for example, by alkene such as polyvinyl alcohol resin ethylene and propylene；Acrylic acid, methacrylic acid and crotons
The unsaturated carboxylic acids such as acid；Resin obtained by Arrcostab and acrylamide of unsaturated carboxylic acid etc. are modified.Polyvinyl alcohol resin
Average degree of polymerization is, for example, 100~10000, is 1500~8000 in another way, is 2000~5000 in another way.
Polarizing film can for example manufacture as follows, that is, the former material film being made of polyvinyl alcohol resin is uniaxially stretched,
(dyeing processing) is dyed with dichroism pigment, (boric acid processing) is handled with boric acid aqueous solution, washes (washing process), be finally allowed to
It dries and manufactures.
Being uniaxially stretched for polyvinyl alcohol resin film can be carried out before the dyeing using dichroism pigment, can also be with benefit
It is simultaneously carried out, can also be carried out after the dyeing using dichroism pigment with the dyeing of dichroism pigment.Utilizing dichroism
In the case where being uniaxially stretched after the dyeing of pigment, this is uniaxially stretched can carry out before boric acid processing, can also be in boric acid
It is carried out in processing.In addition, can certainly be uniaxially stretched in these multiple stages.When implementation is uniaxially stretched, it can wear
It crosses between the different roller of peripheral speed and is stretched, also can use and stretched in the method for hot-rolling clamping.Furthermore it is possible to be
The dry type stretching stretched in an atmosphere is also possible to the wet type stretched in the state of being swollen using solvent
It stretches.The final stretching ratio of polyvinyl alcohol resin film is usually 4~8 times or so.
In dyeing processing, polyvinyl alcohol resin film is dyed with dichroism pigment, film is made to adsorb dichroism pigment.Dyeing
As long as processing is for example by polyvinyl alcohol resin film immersion in the aqueous solution containing dichroism pigment.As dichroism color
Element, specifically, using iodine or dichroic dye.
In the case where using iodine as dichroism pigment, generally use polyvinyl alcohol resin film immersion in containing iodine
And the method dyed in the aqueous solution of potassium iodide.The content of iodine in the aqueous solution is in every 100 mass parts water
0.01~0.5 mass parts or so, the content of potassium iodide be usually 0.5~10 mass parts or so in every 100 mass parts water.It should
The temperature of aqueous solution is usually 20~40 DEG C or so, in addition, dip time in the aqueous solution is usually 30~300 seconds left sides
It is right.
On the other hand, it in the case where using dichroic dye as dichroism pigment, generallys use polyethenol series
Resin film is impregnated in the aqueous solution comprising water-soluble dichroic dye and the method for dyeing.Dichroic dye in the aqueous solution
Content be in every 100 mass parts water be usually 1 × 10-3~1 × 10-2Mass parts or so.The aqueous solution can also contain sulfuric acid
The inorganic salts such as sodium.The temperature of the aqueous solution is usually 20~80 DEG C or so, in addition, dip time in the aqueous solution is usually
30~300 seconds or so.
Boric acid processing through hyperchromatic polyvinyl alcohol resin film immersion in boric acid aqueous solution for example by that will carry out.
The content of boric acid in boric acid aqueous solution be usually 2~15 mass parts or so, for example, 5~12 matter in every 100 mass parts water
Measure part.In the case where using iodine as dichroism pigment, which can contain potassium iodide.In boric acid aqueous solution
The content of potassium iodide be usually 2~20 mass parts or so, for example, 5~15 mass parts in every 100 mass parts water.Film is in boric acid
Dip time in aqueous solution is usually 100~1200 seconds or so, for example, 150 seconds or more, in another way for 200 seconds with
On.On the other hand, dip time such as 600 is the second hereinafter, being 400 seconds or less in another way.The temperature of boric acid aqueous solution
Usually 50 DEG C or more, for example, 50~85 DEG C.In boric acid aqueous solution, sulfuric acid, hydrochloric acid, acetic acid, Vitamin C can also be added
Acid etc. is used as pH adjusting agent.
To boric acid, treated that polyvinyl alcohol resin film usually implements washing process.
Washing process in water for example by carrying out the polyvinyl alcohol resin film immersion handled through perboric acid.In water
Implement drying after washing, obtains polarizing film.The temperature of water in washing process is usually 5~40 DEG C or so, and dip time is usually 2
~120 seconds or so.Drying followed by is carried out usually using air drier, far infra-red heater.Its drying temperature is logical
It is often 40~100 DEG C, drying time is usually 120~600 seconds or so.
[protective film]
In one embodiment, the first protective film is pressed from both sides with polarizing film and is bonded across adhesive layer.The thickness of adhesive layer
Degree is, for example, 0.001 μm~10 μm.Well known material in the technical field can be used in adhesive layer.As formation adhesive layer
Bonding agent, water system bonding agent, active energy ray curable bonding agent can be used.By by the first protective film and polarizing film
Folder is bonded across adhesive layer, even if can also inhibit light leakage, the crackle of polarizing film in the environment of high temperature repeatedly and low temperature
Deng.
First protective film with a thickness of 5~90 μm, for example, 60 μm hereinafter, in another way be 30 μm or less.Pass through
There is thickness in such range, polarization plates of the invention can have excellent engineering properties and optical property.
For example, the first protective film can have given range in the absorption axis direction and transmission axis direction of polarizing film
Size changing rate.
(size changing rate in the absorption axis direction of polarizing film)
For example, by the direction (be sometimes also denoted as MD direction) parallel with the absorption axis direction of polarizing film of the first protective film
On, size changing rate under conditions of 85 DEG C of relative humidity 5% after 1 hour be set as protective film the direction MD size become
When rate (85 DEG C), the direction the MD size changing rate (85 DEG C) of protective film is preferably 0.06~0.25, more preferably 0.06~
0.20, further preferably 0.06~0.15.
By having size changing rate in such range, it can more efficiently inhibit the environment of high temperature repeatedly and low temperature
Under polarizing film crackle.
On the other hand, on the direction (MD direction) parallel with the absorption axis direction of polarizing film by protective film, 30
Size changing rate under conditions of DEG C relative humidity 95% after 0.5 hour is set as the direction the MD size changing rate of protective film
When (30 DEG C), (30 DEG C) of the direction MD size changing rate of protective film preferably -0.25~0.00, more preferably -0.15~
0.00.By having size changing rate in such range, in the environment of can more efficiently inhibiting high temperature repeatedly and low temperature
Polarizing film crackle.
In the present invention, the direction MD size under conditions of 85 DEG C of relative humidity 5% after 1 hour is measured according to following formula
Change rate.
Herein, for example, in the present invention, sometimes by the direction parallel with the absorption axis direction of polarizing film of protective film
Size changing rate under conditions of 85 DEG C of relative humidity 5% after 1 hour is denoted as the direction the MD size changing rate (85 of protective film
℃)。
[in formula, L0 refers to and polarizes the direction MD size changing rate (85 DEG C)=[(the L0-L85)/L0] × 100 of protective film
The film size for the film that process on the parallel direction of the absorption axis direction of piece (direction MD) (length direction or width direction) is cut,
L85 refers to parallel with the absorption axis direction of polarizing film after 1 hour under conditions of 85 DEG C of relative humidity 5%
Direction (direction MD) (length direction or width direction) film size.]
For example, in the case where measuring size (L0) in the direction MD when film is cut, under conditions of 85 DEG C of relative humidity 5%
After standing 1 hour, the size (L85) in the direction MD of film is also measured, calculates size changing rate.In addition, after manufacturing polarization plates from
Polarization plates remove polarizing film etc. and measure the direction (MD direction) parallel with the absorption axis direction of polarizing film of resulting protective film
Size (L0) in the case where, after standing 1 hour under conditions of 85 DEG C of relative humidity 5%, also measure and the absorption of polarizing film
The size (L85) in the parallel direction of axis direction (direction MD) calculates size changing rate.
The size changing rate (85 DEG C) calculated as described then means contraction if it is positive value, if it is negative value,
Then mean expansion.
It should be noted that in a mode, the direction parallel with the absorption axis direction of polarizing film of the first protective film
The draw direction that (direction MD) can be the first protective film, is furthermore also possible to length direction.
It is same as described above, in the present invention, change in size under conditions of 30 DEG C of relative humidity 95% after 0.5 hour
The calculating of rate is to measure to the film after measurement size changing rate (85 DEG C) according to following formula.
For example, in the present invention, it sometimes will be on the direction (direction MD) parallel with the absorption axis direction of polarizing film of protective film
The direction MD size changing rate under conditions of 30 DEG C of relative humidity 95% after 0.5 hour be denoted as the direction MD of protective film
Size changing rate (30 DEG C).
The direction MD size changing rate (30 DEG C)=[(L030- L30)/L0] × 100
[in formula, L030Refer to the measurement direction parallel with the absorption axis direction of polarizing film (direction MD) (length direction or width
Spend direction) on size changing rate (85 DEG C) after film size,
L30 refers to the absorption axis direction with polarizing film under conditions of 30 DEG C of relative humidity 95% after 0.5 hour
The film size in parallel direction (direction MD) (length direction or width direction).] for example, can be in measurement size changing rate (85
DEG C) after, it is placed 15 minutes in 23 DEG C of temperature, humidity 55%, then measures L030。
The direction the MD size changing rate (30 DEG C) calculated as described then means contraction if it is positive value, if it is
Negative value then means expansion.
The symbol of the size changing rate (85 DEG C) of protective film of the invention and the symbol of size changing rate (30 DEG C) can be all
It is identical symbol (positive and negative or zero), is also possible to different symbols.In a mode, the symbol of size changing rate (85 DEG C)
Number and the symbol of size changing rate (30 DEG C) be different symbol.
Polarization plates of the invention can be further suppressed because the first protective film has size changing rate in such range
Crackle, the light leakage generated under the conditions of hot conditions, how wet in polarizing film, can have more excellent durability.In addition, tool
Polarizing film can be thinned in the polarization plates of the standby protective film with such characteristic, and even if generates recess etc. on the surface of protective film
In the case where physical change, the crackle of polarizing film can also be inhibited.
(size changing rate on the direction vertical with the absorption axis direction of polarizing film)
For example, by the direction vertical with the absorption axis direction of polarizing film of the first protective film, i.e. with the transmission of polarizing film
On the parallel direction of axis direction (being also denoted as the direction TD sometimes) under conditions of 85 DEG C of relative humidity 5% after 1 hour
When size changing rate is set as the direction TD size changing rate (85 DEG C) of protective film, the direction the TD size changing rate (85 DEG C) of protective film
Preferably 0.05~0.25, more preferably 0.05~0.20.By in such range have size changing rate, can more added with
Effect ground inhibits the crackle of the polarizing film in the environment of high temperature repeatedly and low temperature.
On the other hand, on the direction (TD direction) parallel with the transmission axis direction of polarizing film by protective film at 30 DEG C
Size changing rate under conditions of relative humidity 95% after 0.5 hour is set as the direction the TD size changing rate (30 of protective film
DEG C) when, (30 DEG C) of the direction TD size changing rate of protective film preferably -0.25~0.00, more preferably -0.20~0.00.
By having size changing rate in such range, it can more efficiently inhibit the polarization in the environment of high temperature repeatedly and low temperature
The crackle of piece.
For example, the direction the TD size changing rate (30 DEG C) of the direction the TD size changing rate (85 DEG C) of protective film and protective film
Absolute value of the difference is for example preferably 0.20~0.50, more preferably 0.03~0.30.By in such range there is size to become
The absolute value of the difference of rate can more efficiently inhibit the crackle of the polarizing film in the environment of high temperature repeatedly and low temperature.
The difference of polarization plates of the invention because of the first protective film with size changing rate, size changing rate in such range
Absolute value, and the crackle generated under the conditions of hot conditions, how wet in polarizing film, light leakage can be further suppressed, can have
More excellent durability.In addition, the polarization plates for having the protective film with such characteristic can be thinned polarizing film, and even if
In the case where the surface of protective film generates the physical changes such as recess, the crackle of polarizing film can also be inhibited.
First protective film is the film comprising cellulose-based resin.In some mode, the first protective film is as described later, be with
Film of the cellulose-based resin as principal component.First protective film can be the list using resins such as cellulose-based resins as principal component
Tunic is also possible to the multilayer film with the layer using resins such as cellulose-based resins as principal component.
Herein, term " principal component " refers to, relative to 100 mass parts of resin component in the first protective film, to be greater than 50
Mass parts are to be to be contained in amounts more than 90 mass parts more than 80 mass parts, in another way in another way
Resin component in one protective film.
The two sides or one side of these monofilms or multilayer film can be implemented to be surface-treated.
The surface treatment, which can be, utilizes sided corona treatment, saponification process, heat treatment, ultraviolet light irradiation, electron beam irradiation etc.
Surface it is modified.Alternatively, it is also possible to being formed using the film of coating, the vapor deposition of macromolecule, metal etc. etc..
For example, the first protective film can also form hard conating, antiglare layer, anti-reflection layer, anti-static electricity interference layer and stain-proofing layer
Equal surface-treated layers (coat).As the method for forming surface-treated layer in protection film surface, well known method can be used.
For example, the first protective film can have hard conating with the face of above-mentioned polarizing film opposite side.For example, by making the first protective film
With hard conating, can inhibit to scrape rub etc. in polarization plate surface generation.It should be noted that in the present invention, as long as scraping
The size of scar etc. is that would not have an impact to polarization plates in the scope of the present invention.But typically, rub warp is scraped
Ordinary wave and broad spectrum can preferably inhibit the generation for scraping rub etc..
In one embodiment, the first protective film be set to the hard conating in the face of polarizing film opposite side have 1~
10 μm of thickness.For example, thickness of the thickness of hard conating less than the first protective film.
In another way, the ratio of the thickness of the thickness of hard conating and the first protective film is the range of 0.9:1~0.01:1.
If the ratio of the thickness of the thickness of hard conating and the first protective film is above-mentioned range, resulting polarization plates are anti-
In the environment (such as under cooling thermal impact environment) of multiple hot conditions and cryogenic conditions, the contraction that polarizing film generates etc. stress by
Protective film inhibits, it is difficult to crack in polarizing film, therefore become the more excellent polarization plates of durability.
In the case where the first protective film has the surface-treated layers such as hard conating, the first protective film for example can be above-mentioned the
The surface treatment layer surface of one protective film being configured at the face of above-mentioned polarizing film opposite side, for example, in surface-treated layer can
Depending on side surface, there is 0.001~500 μm long, wide 0.001~500 μm and deep 0.001~10 μm of scar and deep 0.001
~10 μm and 0.001~1.0mm of area2Scar at least one party.
In the case where the first protective film has the surface-treated layers such as hard conating, the city for having carried out hard coating can be used
The protective film sold.In this case, scar of the invention can be set to surface-treated layer, such as can be in the visual of surface-treated layer
Scar is arranged in side surface.
First protective film can be the transparent resin film being made of the thermoplastic resin comprising cellulose-based resin.Cellulose
It is resin is, for example, the fibers such as cellulosic triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate
Plain ester system resin.
In addition, the first protective film can also include other thermoplastic resins on the basis of cellulose-based resin, such as
Include the polyolefin-based resins such as the chain polyolefin-based resins being selected from by taking polypropylene-based resin as an example and cyclic polyolefin hydrocarbon system resin；
The polyester based resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate (PBT)；It is poly-
Carbonic ester system resin；(methyl) acrylic resin in plexiglass；Or their at least two or more
Mixture etc..Alternatively, it is also possible to use the copolymer at least two or more the monomer for constituting above-mentioned resin.In a mode
In, for cellulose-based resin mass ratio shared in protective film entirety, protective film is integrally being set as to 100 mass %'s
In the case of, it is as an example 50 mass % or more, is 70 mass % or more in another way, is 90 matter in another way
Measure % or more.
Cellulose esters system resin is usually the ester of cellulose and fatty acid.It, can as the concrete example of cellulose esters system resin
To enumerate cellulosic triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc..In addition, can also
To use resin obtained by their copolymerization, a part of hydroxyl used to resin obtained by others substituent groups modification.They work as
In, such as can choose cellulosic triacetate (triacetyl cellulose: TAC).Cellulosic triacetate has many products in city
It is sold on, it is also advantageous in terms of obtaining easiness, cost.The example of the commercially available product of cellulosic triacetate is with trade name
Indicate there be " FUJITAC (registered trademark) TD80 ", " FUJITAC (registered trademark) sold by Fuji Photo Film Co., Ltd.
TD80UF ", " FUJITAC (registered trademark) TD80UZ " and " FUJITAC (registered trademark) TD40UZ ", Minolta plants of Konica
TAC film " KC8UX2M ", " KC2UA " and " KC4UY " of formula commercial firm etc..
For example, the first protective film comprising cellulose-based resin be also possible to implement produced film stretch processing and
The film obtained.In order to obtain the film with desired optical characteristics, mechanical property, it is sometimes desirable to carry out stretch processing.As drawing
Processing is stretched, can be enumerated and be uniaxially stretched, is biaxial stretch-formed etc..As draw direction, the mechanical flow side of unstretching film can be enumerated
To (MD), orthogonal direction (TD), with the direction of mechanical flow direction (MD) oblique etc..It is biaxial stretch-formed to can be along two
It is biaxial stretch-formed while draw direction simultaneously stretches, be also possible to along assigned direction stretch after along another direction stretch by
It is secondary biaxial stretch-formed.
Cyclic polyolefin hydrocarbon system resin is usually the general name of resin being polymerize using cyclic olefin as polymerized unit, such as can be with
Enumerate Japanese Unexamined Patent Publication 1-240517 bulletin, Japanese Unexamined Patent Publication 3-14882 bulletin, Japanese Unexamined Patent Publication 3-122137 bulletin
The resin recorded in.If enumerating the concrete example of cyclic polyolefin hydrocarbon system resin, for cyclic olefin open loop (co) polymer,
(representative example is nothing to the copolymer of the chain olefins such as addition polymer, ethylene and the propylene of cyclic olefin and cyclic olefin
Advise copolymer) and by they with unsaturated carboxylic acid, its it is derivative modified obtained by graft polymers and their hydrogenation
Object etc..Wherein, it is preferable to use having used the orbornene-baseds lists such as norbornene, polycyclic orbornene-based monomer as cyclic olefin
The norbornene resin of body.
Cyclic polyolefin hydrocarbon system resin has various products to sell on the market.Commercially available product as cyclic polyolefin hydrocarbon system resin
Example indicates with trade name, have by TOPAS ADVANCED POLYMERS GmbH production, in Japan by Poly
Plastics Co., Ltd. sale " TOPAS " (registered trademark), by JSR Corp. sale " Arton " (registered trademark),
By " Zeonor " (registered trademark) and " Zeonex " (registered trademark) of the sale of Japanese ZEON Co., Ltd., by three well strain formula meetings
" Apel " (registered trademark) etc. of society's sale.
Alternatively, it is also possible to use the commercially available product of manufactured cyclic polyolefin resin film as protective film.As commercially available
The example of product, is indicated with trade name, can enumerate by JSR Corp. sale " Arton Film " (" Arton " be JSR
The registered trademark of Co., Ltd.), by Sekisui Chemical Co., Ltd sale " Escena " (registered trademark) and " SCA40 ",
By " Zeonor Film " (registered trademark) etc. of the sale of Japanese ZEON Co., Ltd..
Polymethacrylates and polyacrylate (are merged sometimes claim below by polymethacrylates and polyacrylate
Make (methyl) acrylic resin.) can easily be obtained from market.
As (methyl) acrylic resin, for example, alkyl methacrylate or alkyl acrylate is equal
Polymers, alkyl methacrylate and copolymer of alkyl acrylate etc..As alkyl methacrylate, specifically,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate etc. can be enumerated, in addition, as alkyl acrylate,
Specifically, methyl acrylate, ethyl acrylate, propyl acrylate etc. can be enumerated.As (methyl) acrylic resin,
The resin sold on the market as general (methyl) acrylic resin can be used.As (methyl) acrylic acid series tree
The resin referred to as impact resistance (methyl) acrylic resin can be used in rouge.
(methyl) acrylic resin is usually the polymer using methacrylate as main body.Metha crylic tree
Rouge can be a kind of homopolymer of methacrylate, be also possible to methacrylate and other methacrylates or propylene
The copolymer of acid esters etc..As methacrylate, methyl methacrylate, ethyl methacrylate, methyl-prop can be enumerated
The alkyl methacrylates such as olefin(e) acid butyl ester, the carbon atom number of alkyl are usually 1~4 or so.Alternatively, it is also possible to use methyl
The cycloalkyl methacrylates, first such as acrylic acid ring pentyl ester, cyclohexyl methacrylate, methacrylate (メ タ Network リ Le)
The methacrylic acids cycloalkyl-alkyl such as the aryl methacrylates such as base phenyl acrylate, methacrylic acid cyclohexylmethyl ester,
The methacrylic acids aralkyl ester such as benzyl methacrylate.
As other the above-mentioned polymerizable monomers that can constitute (methyl) acrylic resin, for example, acrylic acid
Polymerizable monomer other than ester, methacrylate and acrylate.As acrylate, alkyl acrylate can be used,
Its concrete example includes methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, propylene
The alkyl such as sour isobutyl ester, tert-butyl acrylate, 2-EHA, cyclohexyl acrylate, acrylic acid 2- hydroxy methacrylate
Carbon atom number be 1~8 alkyl acrylate.The carbon atom number of alkyl is, for example, 1~4.In (methyl) acrylic resin
In, one kind can be only used alone in acrylate, also can be used together two or more.
As the polymerizable monomer other than methacrylate and acrylate, for example, having one in the molecule
More officials of the monofunctional monomer of the carbon-to-carbon double bond of a polymerism, the in the molecule carbon-to-carbon double bond at least two polymerisms
Energy monomer, however it is preferable to use monofunctional monomers.The concrete example of monofunctional monomer includes styrene, α-methylstyrene, ethylene
The styrenic monomers such as base toluene, halogenated styrenes, hydroxy styrenes；The vinyl cyanides such as acrylonitrile, methacrylonitrile；Propylene
The unsaturated acids such as acid, methacrylic acid, maleic anhydride, itaconic anhydride；N- methylmaleimido, N- cyclohexyl maleimide
The maleimides such as amine, N-phenylmaleimide；The allyl alcohols such as methallyl alcohol, allyl alcohol；Vinyl acetate, vinyl chloride,
Ethylene, propylene, 4-methyl-1-pentene, 2- hydroxymethyl -1- butylene, methyl vinyl ketone, N- ethenyl pyrrolidone
The other monomers such as ketone, N- vinyl carbazole.
In addition, the concrete example of polyfunctional monomer include ethylene glycol dimethacrylate, butanediol dimethylacrylate,
The how unsaturated carboxylate of the polyalcohols such as trimethylolpropane trimethacrylate；Allyl acrylate, allyl methacrylate,
The alkenyl esters of the unsaturated carboxylic acids such as allyl cinnamate；Diallyl phthalate, diallyl maleate, cyanuric acid alkatriene
The aromatic polyenes based compounds such as the polyenoid base esters of the polyacids such as propyl ester, triallyl isocyanurate, divinylbenzene.Methyl-prop
One kind can be only used alone in polymerizable monomer other than olefin(e) acid ester and acrylate, also can be used together two or more.
On the basis of total monomer amount, alkyl methacrylate is the preferred monomer composition of (methyl) acrylic resin
50~100 mass %, alkyl acrylate are 0~50 mass %, and the polymerizable monomer other than them is 0~50 mass %,
In another way, alkyl methacrylate is 50~99.9 mass %, and alkyl acrylate is 0.1~50 mass %, they
Polymerizable monomer in addition is 0~49.9 mass %.
In addition, (methyl) acrylic resin can be in macromolecule master from the aspect of the durability that film can be improved
There is ring structure in chain.Ring structure is preferably the heterocycle structures such as cyclic acid anhydride structure, cyclic imide structure, lactone ring structure.
Specifically, the cyclic acid anhydrides structures such as glutaric anhydride structure, succinic anhydride structure, glutarimide structure, fourth two can be enumerated
The lactones ring structures such as the cyclic imides such as imide structure structure, butyrolactone, valerolactone.Increase the ring structure in main chain
The glass transition temperature of (methyl) acrylic resin more can be improved in content.Cyclic acid anhydride structure, cyclic imide structure
It can use the method imported and there is maleic anhydride, maleimide etc. the monomer of cyclic structure be copolymerized, using poly-
Dehydration/separating methanol condensation reaction imports the method for cyclic acid anhydride structure, reacts amino-compound and import cyclic annular acyl Asia after conjunction
Method of amine structure etc. imports.Resin (polymer) with lactone ring structure can use following method to obtain, that is,
After polymer of the preparation with hydroxyl and ester group in macromolecular chain, the hydroxyl and ester in resulting polymer are made using heating
Base as needed in the presence of the catalyst of organic phosphorus compound etc cyclizative condensation and form lactone ring structure.
Polymer with hydroxyl and ester group in macromolecular chain for example can be by using 2- (methylol) acrylic acid first
Ester, 2- (methylol) ethyl acrylate, 2- (hydroxymethyl) isopropyl acrylate, 2- (methylol) n-butyl acrylate,
There is 2- (methylol) tert-butyl acrylate etc. (methyl) acrylate of hydroxyl and ester group to obtain as a part of monomer
It arrives.The more specific preparation method of polymer with lactone ring structure is for example recorded in Japanese Unexamined Patent Publication 2007-254726 public affairs
In report.
By making the monomer composition free radical polymerization comprising monomer as described above, (methyl) acrylic acid series can be prepared
Resin.Monomer composition may include solvent, polymerization initiator as needed.
(methyl) acrylic resin also may include other resins other than above-mentioned (methyl) acrylic resin.It should
The containing ratio of other resins is, for example, 0~70 mass %, is 0~50 mass % in another mode, in yet another mode
In be 0~30 mass %.The resin for example can be polyethylene, polypropylene, ethylene-propylene copolymer, poly- (4- methyl-
1- amylene) etc. olefin polymers；The polymer containing halogen system such as vinyl chloride, vinyl chloride resin；Polystyrene, styrene-first
The styrenics such as base methyl acrylate copolymer, styrene-acrylonitrile copolymer；Polyethylene terephthalate,
The polyester such as polybutylene terephthalate (PBT), polyethylene naphthalate；It is formed by aromatic diol and aromatic dicarboxylic acid
Polyarylate；The Biodegradable polyesters such as polylactic acid, poly-succinic fourth diester；Polycarbonate；Nylon 6, nylon66 fiber, nylon 610
Equal polyamide；Polyacetals；Polyphenylene oxide；Polyphenylene sulfide；Polyether-ether-ketone；Polyethers nitrile；Polysulfones；Polyether sulfone；Polyoxy benzene methyl (Port リ オ
キシペンジレン)；Polyamidoimide etc..
From the viewpoint of from the impact resistance, film formation property of raising film, (methyl) acrylic resin can contain rubber granule
Son.Rubber particles can be the particle only formed by the layer of display caoutchouc elasticity, be also possible to the layer one with display caoutchouc elasticity
Play the particle of the also multilayered structure with other layers.As rubber elastomer, for example, olefin-based elastomeric polymer, two
Alkene system elastomeric polymer, styrenic-diene system elastocopolymer, acrylic flexible polymer etc..Wherein, from light resistance and
, it is preferable to use acrylic flexible polymer from the viewpoint of the transparency.
Acrylic flexible polymer can be it is based on alkyl acrylate, wrapped on the basis of whole amount of monomer
The polymer of the Component units from alkyl acrylate containing 50 mass % or more.Acrylic flexible polymer can be
The homopolymer of alkyl acrylate, be also possible to comprising 50 mass % or more from alkyl acrylate Component units,
With the copolymer of the 50 mass % Component units below from other polymerizable monomers.
As constitute acrylic flexible polymer alkyl acrylate usually using its alkyl carbon atom number be 4~
8 compound.If enumerating the example of other above-mentioned polymerizable monomers, for example, methyl methacrylate, methacrylic acid second
The alkyl methacrylates such as ester；The styrenic monomers such as styrene, ring-alkylated styrenes；The insatiable hungers such as acrylonitrile, methacrylonitrile
With the unsaturated carboxylic acids such as monofunctional monomers and (methyl) allyl acrylate, (methyl) methallyl acrylate such as nitrile
Alkenyl esters；The diene base ester of the binary acid such as diallyl maleate；The glycol such as aklylene glycol two (methyl) acrylate are not
The polyfunctional monomers such as saturated carboxylic acid diester.
Rubber particles comprising acrylic flexible polymer preferably have the more of the layer of acrylic flexible polymer
The particle of layer structure.Specifically, can enumerate has in the outside of the layer of acrylic flexible polymer with methacrylic acid
The particle of 2 layers of structure of the polymeric layer of the hard based on Arrcostab, also in the inside of the layer of acrylic flexible polymer
The particle of the 3-tier architecture of polymeric layer with the hard based on alkyl methacrylate.
Constitute be formed in acrylic flexible polymer layer outside or inside hard polymeric layer, with methyl
The example of the monomer composition in polymer based on alkyl acrylate, with the example act as (methyl) acrylic resin
Out, the example of the monomer composition of polymer based on alkyl methacrylate it is identical, particularly preferred use is with methyl
Monomer composition based on methyl acrylate.
The acrylic rubber elastomer particle of such multilayered structure for example can use Japanese Patent Publication 55-27576
The method manufacture recorded in bulletin.
From the viewpoint of the film formation property, the impact resistance of film, the lubricity of film surface of (methyl) acrylic resin, rubber
Average grain diameter in micelle preferably up to rubber elastomer layer (layer of acrylic flexible polymer) contained therein is in
The range of 10~350nm.The average grain diameter is, for example, 30nm or more, is 50nm or more in another way.On the other hand, partial size
For example, 300nm is hereinafter, be 280nm or less in another way.
Rubber particles until the average grain diameter of rubber elastomer layer (layer of acrylic flexible polymer) it is as follows
Ground measurement.That is, membranization is mixed into (methyl) acrylic resin and carries out by such rubber particles, if by its section oxygen
The only coloring of rubber elastomer layer and approximate circle, (methyl) acrylic acid series tree of mother layer are then observed in the aqueous solution dyeing for changing ruthenium
Rouge is not colored.Thus, thin slice is prepared from the film section dyed as described using ultramicrotome etc., utilizes electronics
The micro- sem observation thin slice.Hereafter, 100 are randomly extracted through hyperchromatic rubber particles, calculates respective partial size (until rubber
The diameter of glue elastomer layer) after, using its arithmetic mean of instantaneous value as above-mentioned average grain diameter.Due to being measured using such method,
Therefore resulting above-mentioned average grain diameter is arithmetic mean diameter.
Belong to polymer that outermost layer is hard based on methyl methacrylate and is packed in rubber wherein
In the case where the rubber particles of elastomer layer (layer of acrylic flexible polymer), if be mixed into as parent
In (methyl) acrylic resin, then the outermost layer of rubber particles is mixed with (methyl) acrylic resin as parent.Cause
This, if its section dyed with ruthenium-oxide, and is observed using electron microscope, then can be to eliminate outermost shape
The form of the particle of state observes rubber particles.Specifically, belong to internal layer be acrylic flexible polymer, outer layer be with
In the case where the rubber particles of 2 layers of structure of the polymer of the hard based on methyl methacrylate, the acrylic acid series of internal layer
Elastomeric polymer portion is colored and is observed in the form of the particle of single layer structure.In addition, being with methyl belonging to innermost layer
The polymer of hard based on methyl acrylate, middle layer are acrylic flexible polymer, outermost layer is with metering system
In the case where the rubber particles of the 3-tier architecture of the polymer of hard based on sour methyl esters, then with the particle centre portion of innermost layer
It point is not colored, the form of the particle for 2 layers of structure that only the acrylic flexible polymer part of middle layer is colored is observed.
From the viewpoint of the film formation property, the impact resistance of film, the lubricity of film surface of (methyl) acrylic resin, rubber
Micelle, such as can be on the basis of the total amount of (methyl) acrylic resin with composition (methyl) acrylic resin film
It is 45 mass % hereinafter, in another way in another way with 3 mass % or more and 60 mass % ratio cooperation below
For 35 mass % or less.If rubber elastomer particle is more than 60 mass %, the change in size of film becomes larger, and heat resistance reduces.
On the other hand, if rubber elastomer particle is less than 3 mass %, the winding although heat resistance of film is good, when being film-made
Property it is poor, have productivity reduce the case where.It should be noted that using the layer one with display caoutchouc elasticity in the present invention
Rise also with other layers multilayered structure particle as rubber elastomer particle in the case where, will be by the layer of display caoutchouc elasticity
Quality of the quality of the part constituted with the layer on the inside of it as rubber elastomer particle.For example, having used above-mentioned 3 layers to tie
In the case where the acrylic rubber elastomer particle of structure, by the acrylic rubber elastomeric polymer portion of middle layer with it is most interior
Matter of the total quality of the polymer moieties of the hard based on methyl methacrylate of layer as rubber elastomer particle
Amount.If being dissolved in the acrylic rubber elastomer particle of above-mentioned 3-tier architecture in acetone, the acrylic acid series of middle layer
The polymer moieties of the hard based on methyl methacrylate of rubber elastic polymers part and innermost layer are as insoluble
Component residue, therefore can easily find out the acrylic rubber elastomer for being aggregated in 3-tier architecture of middle layer and innermost layer
Shared mass ratio in particle.
In the case where (methyl) acrylic resin film includes rubber particles, when production of the film it is used contain rubber
(methyl) the acrylic resin composition of particle is in addition to can be by utilizing (methyl) acrylic resin and rubber particles
Other than melting mixing etc. is obtained by mixing, it can also utilize and first make rubber particles, become (methyl) in the presence
The method of the monomer composition polymerization of the raw material of acrylic resin obtains.
Known film-forming method can be used in the production of (methyl) acrylic resin film.(methyl) acrylic acid
Resin film can have multilayered structure, and (methyl) acrylic resin film of multilayered structure can be used general known various
Method, such as use supply head (フ ィ ー De Block ロ ッ Network) method, use the method for branch manifold die head.Wherein, from can obtain
From the aspect of obtaining the good film of surface texture, such as preferably following method, that is, folder is laminated across supply head, from T shape
Multilayered molten extrusion molding is carried out in die head, is film-made at least one side of resulting stacking membranoid substance with roller or with contact.Especially
It is from the viewpoint of the surface smoothness and lustrous surface of raising (methyl) acrylic resin film, preferably make it is above-mentioned into
The two sides that membranoid substance is laminated obtained by row multilayered molten extrusion molding contacts and the method for membranization with roller surface or belt surface.Herein
In the roller or band of Shi Suoyong, for the roller surface or belt surface contacted with (methyl) acrylic resin, in order to (methyl) third
Olefin(e) acid resin film surface assigns flatness, and preferably its surface is mirror surface.
In protective film, common additive, such as ultraviolet absorbing agent, organic based dye, pigment, inorganic can be contained
It is pigment, antioxidant, anti-static electricity interference agent, surfactant etc..Wherein, it from the aspect of improving weatherability, uses more
Ultraviolet absorbing agent.
Can have in the one side opposite with the fitting face of the first protective film of polarizing film by hardening resin composition
The layer that solidfied material is formed.Hardening resin composition is not particularly limited, however for example, the solvable system of solvent, water soluble
The resin combinations such as system, aqueous dispersion, solvent-free system.In addition, the curing method as hardening resin composition, can enumerate
Thermohardening type or active energy ray-curing.There is the layer formed by the solidfied material of the hardening resin composition
In the case of, it can more efficiently inhibit the polarizing film crackle in the environment of high temperature repeatedly and low temperature.
In some mode, polarization plates of the invention can have between polarizing film and first adhesive phase by solidifying
Property resin combination solidfied material formed layer.
The thickness of the layer formed by the solidfied material of hardening resin composition is preferably 0.1 μm~10 μm hereinafter, more preferably
It is 0.5 μm~5 μm.
(adhesive phase)
As the adhesive for forming first adhesive phase, known adhesive is properly selected, as long as tool
Have in hot environment that polarization plates are exposed, hygrothermal environment or repeatedly high temperature and low temperature in the environment of will not generate removing etc.
The adhesive of the cementability of degree.Specifically, acrylic adhesive, silicone-based adhesive, rubber series can be enumerated
Acrylic adhesive can be used for example from the aspect of the transparency, weatherability, heat resistance, processability in adhesive etc..
In adhesive, as needed, tackifier, plasticizer, glass fibre, bead, metal can be mated properly into
Powder, by the filler of the formation such as other inorganic powders, pigment, colorant, filler, antioxidant, ultraviolet absorbing agent, prevent it is quiet
The various additives such as electrical interference agent, silane coupling agent.
Adhesive phase is usually by forming the solution coating of adhesive on release sheet and and dry.To on release sheet
Coating for example can using reversion coating, the rolling methods such as intaglio plate coating, spin-coating method, silk screen rubbing method, spray rubbing method, impregnate
Method, spray-on process etc..Release sheet equipped with adhesive phase is utilized ands being the method etc. by being transferred.The thickness of adhesive phase
Degree is usually 3~100 μm or so, for example, 5~50 μm.
For example, storage modulus at 23 DEG C of adhesive phase is 0.01MPa~1MPa.If the storage modulus of adhesive phase
It less than 0.01MPa, then can not inhibit the contraction of polarization plates when hot test, have and be easy to generate becoming for the bad orders such as removing
Gesture.In addition, if the storage modulus of adhesive phase is greater than 1MPa, when cold shock testing adhesive can not alleviate glass with
The strain generated between polarization plates has the tendency that being easy to cracking in polarization plates.
In one embodiment, storage modulus at 80 DEG C of adhesive phase is 0.01MPa~1MPa.
It is available to press from both sides the liquid crystal display panel that polarization plates of the invention are fitted in liquid crystal cells across first adhesive phase.Separately
Outside, polarization plates are fitted in across first adhesive phase by display of organic electroluminescence, available organic electroluminescence hair by folder
Electro-optical display device.It is preferred that polarization plates of the invention to be fitted in the visible side of liquid crystal cells.
[embodiment]
Hereinafter, provide embodiment and more specific description is carried out to the present invention, however the present invention is not limited by these examples.
In example, indicates that the % of content or usage amount and part are described as long as no special, be exactly quality criteria.
[manufacture of polarizing film]
Thick 20 μm of polyvinyl alcohol film (99.9 moles of average degree of polymerization about 2,400, saponification degree % or more) is utilized into dry type
Tensile uniaxial is stretched as about 5 times, and further keeps tense situation constant, after impregnating 1 minute in 60 DEG C of pure water, at 28 DEG C
It is impregnated 60 seconds in the aqueous solution that iodine/potassium iodide/water mass ratio is 0.05/5/100.Thereafter, at 72 DEG C in potassium iodide/boron
It is impregnated 300 seconds in the aqueous solution that acid/water mass ratio is 8.5/8.5/100.Next after cleaning 20 seconds with 26 DEG C of pure water,
65 DEG C of dryings obtain 7 μm of thickness of the polarizing film for being adsorbed with iodine on polyvinyl alcohol film and being orientated.
[first adhesive phase]
Used implement demoulding processing with a thickness of 38 μm of polyethylene terephthalate film (stripping film)
Demoulding process face is laminated with the commercially available adhesive sheet of thick 20 μm of acrylic adhesive layer.In acrylic adhesive,
Do not cooperate urethane acrylate oligomer.The storage modulus of the adhesive phase of stripping film is eliminated from adhesive sheet
It is 0.05MPa at 23 DEG C, is 0.04MPa at 80 DEG C.
[the first protective film -1]
The tri acetyl cellulose membrane (20 μm thick) of Konica Minolta Co. Ltd. system is prepared.
[the first protective film -2]
Prepare that there is hard conating (7 μm thick), tri acetyl cellulose membrane (Co., Ltd. TOPPAN on surface
TOMOEGAWA OPTICAL FILMS system, 25KCHC-TC, 32 μm of thickness).
[the first protective film -3]
The cycloolefin resin film (Japanese ZEON Co. Ltd. system) with a thickness of 13 μm is prepared.
[the first protective film -4]
The cycloolefin resin film (Japanese ZEON Co., Ltd.) with a thickness of 23 μm is prepared.
(measurement of size changing rate)
The direction the MD size changing rate (85 DEG C) of protective film is determined according to following formula.
[in formula, L0 refers to and polarizes the direction MD size changing rate (85 DEG C)=[(the L0-L85)/L0] × 100 of protective film
The film size for the film that process on the parallel direction of the absorption axis direction of the piece length direction of protective film (direction MD) is cut,
L85 refers to parallel with the absorption axis direction of polarizing film after 1 hour under conditions of 85 DEG C of relative humidity 5%
The direction length direction of protective film (direction MD) film size.]
In addition, determining the direction the MD size changing rate (30 DEG C) of protective film according to following formula.
The direction MD size changing rate (30 DEG C)=[(L030- L30)/L0] × 100
[in formula, L030Refer to the direction parallel with the absorption axis direction of polarizing film the length direction of protective film (direction MD)
On measurement size changing rate (85 DEG C) after film size,
L30 refers to the absorption axis direction with polarizing film under conditions of 30 DEG C of relative humidity 95% after 0.5 hour
The film size in the parallel direction length direction of protective film (direction MD).] in addition, after measuring size changing rate (85 DEG C),
23 DEG C of temperature, humidity 55% are placed 15 minutes, and L0 is then measured30。
It has been carried out similarly the measurement of the direction the TD size changing rate (85 DEG C) of protective film.In Examples and Comparative Examples,
Determine the size changing rate (85 DEG C) in the width direction (direction parallel with the transmission axis direction of polarizing film) of protective film.Separately
Outside, the direction the TD size changing rate (30 DEG C) of protective film is similarly determined.
The result of the resulting size changing rate of said protection film 1~4 will be shown in table 1.
[table 1]
[table 1]
[preparation of water system bonding agent]
Relative to 100 parts of water, dissolve 3 parts of carboxy-modified polyvinyl alcohol (KL-318 of Co., Ltd. Kuraray), to
In the aqueous solution, daiamid epoxy system additive (Chemtex plants of formula meetings of Sumika as soluble epoxide compound are added
The aqueous solution of the Sumirez Resin (registered trademark) 650 (30) of society, solid component concentration 30%) 1.5 parts, as water system
Bonding agent.
[production of polarization plates A]
In the one side of above-mentioned polarizing film, the first protective film -1 is laminated across water system bonding agent in folder.It is dry at 80 DEG C after stacking
Dry 5 minutes, thus the first protective film is bonded with polarizing film.In polarizing film and the face opposite side that is bonded the first protective film
Face is bonded the first adhesive phase that is laminated on stripping film, produces that be sequentially laminated with the first protective film, polarizing film and first viscous
The polarization plates A-1 of mixture layer.
It should be noted that so that the transmission axis direction of the polarizing film side parallel with width direction (direction TD) of protective film
Formula fitting.
Similarly, the first protective film -1 will be replaced and be set as polarization plates using the polarization plates that the first protective film -2 makes
A-2.
In addition, the first protective film -1 will be replaced and be set as polarization plates A- using the polarization plates that the first protective film -3 makes
3, the first protective film -1 will be replaced and be set as polarization plates A-4 using the polarization plates that the first protective film -4 makes.
Made polarization plates are cut into 100mm × 60mm.The stripping film in first adhesive phase is removed, folder is across the
One adhesive phase fits in polarization plates on alkali-free glass (Corning corporation, EAGLE XG (registered trademark)).For distance
The position for fitting to the end 1.0mm of the polarization plates on the glass, using scratch type hardometer (German Erichsen corporation,
318 bulb diameter 0.75mm of model) load that applies 5N to the surfaces of polarization plates, impart pressing scar.That is, being protected to above-mentioned first
Cuticula imparts pressing scar with the face of polarizing film opposite side.The depth for pressing scar is 2~5 μm hereinafter, diameter is
(area of scar is about 0.071mm to 0.3mm2)。
In addition, also produce respectively distance is fitted to the end 1.0mm of the other polarization plates on glass position,
Apply the sample of the load of 10N and 20N using surface of the scratch type hardometer to polarization plates.Apply the load of 10N and makes
Pressing scar depth be 5~8 μm, diameter be 0.4mm (area of scar is about 0.13mm2).Apply the load of 20N and makes
The depth of the pressing scar of work is 11~15 μm, and diameter is that (area of scar is about 0.28mm to 0.6mm2)。
For applying the load of 5N, 10N or 20N, there are the polarization plates of pressing scar on surface, 85 DEG C of temperature are implemented
And the cooling thermal impact environmental test (250 circulations) of -40 DEG C (each 30 minutes are 1 circulation).
[cooling thermal impact environmental test]
Cooling thermal impact environmental test is to be filled in the state of fitting in polarization plates on glass plate using cold shock testing
Set (ProductName " TSA-71L-A-3 " sold by ESPEC Co., Ltd.), by 30 minutes (85 DEG C) retention times of hot conditions,
30 minutes cryogenic conditions (- 40 DEG C) retention times carried out as 1 circulation.It should be noted that the temperature transition time is set
It is 1 minute, when the 0 minute temperature transition time in temperature transition, does not import ambient atmos, setting generates optical component
The condition of moisture condensation.By the circulation repeatedly 250 circulation and implement test.Determined as shown below.Result is indicated
In table 2.
[judgement]
After carrying out cooling thermal impact environmental test (recurring number: 250 times), it visually confirmed the presence or absence of light leakage.It will be with examination
Before testing compared to without variation, test after do not generate under Nicol crossed the sample of light leakage and be set as "○", by after test
The sample that light leakage is generated under Nicol crossed is set as "×".
[table 2]
[table 2]
According to the result it is found that polarization plates of the invention have the effect of in cooling thermal impact environmental test it is excellent.That is, root
According to the present invention, even if polarization plates of the invention will not crack in polarizing film in the environment of high temperature repeatedly and low temperature
Deng good appearance being kept, in addition, leakage will not be generated by enclosing the liquid crystal display device of polarization plates of the invention in visible side
Light.
Industrial availability
According to the present invention, even if in the environment of high temperature repeatedly and low temperature, polarization plates of the invention will not generate light leakage,
Crackle etc. can show good polarization characteristic.In addition, polarization plates of the invention are slim and intensity, excellent in te pins of durability
Polarization plates.
The explanation of symbol
11 first adhesive phases, 12 polarizing films, 13 first protective films, 100 polarization plates.
Claims (3)
1. a kind of polarization plates are to be laminated with first adhesive phase, with a thickness of 10 μm of polarizing films below and comprising cellulose-based tree
The polarization plates of first protective film of rouge,
First protective film is in face of first protective film with the polarizing film opposite side and first protective film
The polarizing film side face at least one party have scar,
The scar is 0.001 μm~500 μm long, 0.001 μm wide~500 μm and deep 0.001 μm~10 μm of scar, Yi Jishen
0.001 μm~10 μm and area 0.001mm2~1.0mm2Scar at least one party.
2. polarization plates according to claim 1, wherein
It is sequentially laminated with the first adhesive phase, the polarizing film and first protective film.
3. polarization plates according to claim 1 or 2, wherein
First protective film has scar in first protective film and the face of the polarizing film opposite side.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-098193 | 2016-05-16 | ||
| JP2016098193A JP6700964B2 (en) | 2016-05-16 | 2016-05-16 | Polarizer |
| PCT/JP2017/014503 WO2017199632A1 (en) | 2016-05-16 | 2017-04-07 | Polarizing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109154688A true CN109154688A (en) | 2019-01-04 |
| CN109154688B CN109154688B (en) | 2021-03-23 |
Family
ID=60325126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780029708.1A Active CN109154688B (en) | 2016-05-16 | 2017-04-07 | Polarizing plate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6700964B2 (en) |
| KR (1) | KR102418731B1 (en) |
| CN (1) | CN109154688B (en) |
| TW (1) | TWI722177B (en) |
| WO (1) | WO2017199632A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7411520B2 (en) * | 2020-09-02 | 2024-01-11 | 日東電工株式会社 | Polarizing plate, polarizing plate with retardation layer, and organic electroluminescent display device |
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| JP2005350492A (en) | 2004-06-08 | 2005-12-22 | Konica Minolta Opto Inc | Coated film having coated layer by using cellulose ester film as supporting body, protective film for polarized plate, combination of productive film for polarized plate and polarized plate |
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| JP5747464B2 (en) | 2010-08-30 | 2015-07-15 | コニカミノルタ株式会社 | Cellulose acylate laminated film, polarizing plate, and liquid crystal display device |
| TWI647476B (en) * | 2014-07-29 | 2019-01-11 | 日商住友化學股份有限公司 | Polarizing plate, polarizing plate with adhesive and liquid crystal display device |
-
2016
- 2016-05-16 JP JP2016098193A patent/JP6700964B2/en active Active
-
2017
- 2017-04-07 KR KR1020187034556A patent/KR102418731B1/en active IP Right Grant
- 2017-04-07 CN CN201780029708.1A patent/CN109154688B/en active Active
- 2017-04-07 WO PCT/JP2017/014503 patent/WO2017199632A1/en active Application Filing
- 2017-04-26 TW TW106113930A patent/TWI722177B/en active
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| WO1998005984A1 (en) * | 1996-08-05 | 1998-02-12 | Teijin Limited | Orientated film having pores |
| JP2006021459A (en) * | 2004-07-09 | 2006-01-26 | Konica Minolta Opto Inc | Method for producing optical film |
| JP2007045071A (en) * | 2005-08-11 | 2007-02-22 | Konica Minolta Opto Inc | Manufacturing method of optical film, optical film, and polarizing plate using the film |
| JP2007052333A (en) * | 2005-08-19 | 2007-03-01 | Konica Minolta Opto Inc | Surface-roughened optical film, method for producing the same, polarizing plate and image display device |
| JP2008069240A (en) * | 2006-09-13 | 2008-03-27 | Fujifilm Corp | Optical film, method for producing the same, polarizing plate, optical compensation film, antireflection film, and liquid crystal displaying |
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| JP2010039458A (en) * | 2008-07-11 | 2010-02-18 | Sumitomo Chemical Co Ltd | Polarizing plate, manufacturing method therefor, and composite polarizing plate using the same |
| JP2010064327A (en) * | 2008-09-10 | 2010-03-25 | Fujifilm Corp | Film, method for manufacturing the same, polarizing plate, and liquid crystal display |
| JP2010164733A (en) * | 2009-01-15 | 2010-07-29 | Dainippon Printing Co Ltd | Optical film for protecting polarizer and method for producing the film, polarizing plate and display apparatus |
| CN104583821A (en) * | 2012-08-31 | 2015-04-29 | 日东电工株式会社 | Polarizing film having pressure-sensitive adhesive layer, and image display device |
| WO2016006384A1 (en) * | 2014-07-10 | 2016-01-14 | 住友化学株式会社 | Polarization plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6700964B2 (en) | 2020-05-27 |
| CN109154688B (en) | 2021-03-23 |
| TWI722177B (en) | 2021-03-21 |
| WO2017199632A1 (en) | 2017-11-23 |
| KR102418731B1 (en) | 2022-07-11 |
| JP2017207557A (en) | 2017-11-24 |
| KR20190007435A (en) | 2019-01-22 |
| TW201741701A (en) | 2017-12-01 |
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