CN104640695A - Optical film - Google Patents

Optical film Download PDF

Info

Publication number
CN104640695A
CN104640695A CN201380048580.5A CN201380048580A CN104640695A CN 104640695 A CN104640695 A CN 104640695A CN 201380048580 A CN201380048580 A CN 201380048580A CN 104640695 A CN104640695 A CN 104640695A
Authority
CN
China
Prior art keywords
film
embossed portion
blooming
base material
region
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201380048580.5A
Other languages
Chinese (zh)
Inventor
山本智弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Konica Minolta Opto Inc
Original Assignee
Konica Minolta Opto Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Opto Inc filed Critical Konica Minolta Opto Inc
Publication of CN104640695A publication Critical patent/CN104640695A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • G02B1/11—Anti-reflection coatings
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

An optical film (F) on which a cured sheet (2) has been formed on a film substrate (1) having a thickness of 10 to 40 [mu]m, wherein the regions from both end parts of the film substrate (1) in the width direction to 50 mm are specified as a first region (R1) and a second region (R2). The cured sheet (2) is formed on the film substrate (1) so as to cover 20 to 100% of the first region (R1) in the width direction and 20 to 100% of the second region (R2) in the width direction. The surface of the cured sheet (2) in the first region (R1) and the second region (R2) is knurled after formation of the cured sheet, whereby an uneven knurled part (3) is formed. The knurled part (3) is formed on the surface of the cured sheet (2) across 3 mm or more in the width direction from each end part of the cured sheet (2).

Description

Blooming
Technical field
The present invention relates to the blooming being formed with cured film on the film base material that thickness is thin.
Background technology
In recent years, except CRT (Cathode Ray Tube), exploitation has the various display unit such as LCD TV, plasma display, organic EL (Electro Luminescence) display, and their picture dimension maximizes.In this display unit, sometimes picture is directly touched with hand, or with thing contact, easily make picture produce damage.Therefore, generally for and prevent damage, the blooming that film base material is formed with hard conating (cured film) or the blooming that is formed with anti-reflection layer etc. further on hard conating are attached at the display frame of display unit.
In the manufacture of this blooming, the both ends being used in broadside are provided with the film base material of the bulky part of the membrane density being called as embossed portion or embossing portion (protuberance).By being pre-formed embossed portion to film base material, skew or the base material adhesion each other (attaching) of the film base material in core direction can be suppressed when the film base material of manufacture being wound in core.By forming hard conating on the surface of this film base material, the blooming with hard conating can be obtained.The blooming obtained is wound in core once again.
Here, when manufacturing the blooming with hard conating, such as, in patent document 1 and 2, be positioned at the mode in the outside of hard conating with the embossed portion of film base material, film base material forms hard conating, and then, the embossed portion of film base material adds further and forms other embossed portion.In this case, form the embossed portion added due to the concavo-convex of the embossed portion that first formed can be utilized, even if therefore the thickness of the jog of dandy roll is so not large, also easily high accuracy can form the embossed portion of required height.In addition, such as, in patent document 3, by hard conating is applied in the embossed portion of film base material, and forms fine projection at the back side of embossed portion and manufacture blooming.
But, in recent years, along with the slimming of display unit, also require the slimming of the blooming used.Here, the coil diameter when the blooming of manufacture being wound in core is a timing, compared with the situation of the blooming that the situation being wound around slim blooming is thicker with being wound around thickness, volume number can be made to increase.Therefore, as slim blooming, the blooming of voluminous strip (such as more than 3000m) can be manufactured.
But in patent document 1 and 2, owing to forming embossed portion than on the film base material of hard conating softness, deadweight time therefore because being wound around the blooming of strip, extruding force, embossed portion is becoming easy breakage.If embossed portion is damaged, then cannot suppress wrapping offset and the adhesion of blooming.In addition, in patent document 3, though think that the fine projection at the back side of embossed portion is the projection at the back side of the film base material being arranged at the substrate becoming hard conating, this projection is more soft than hard conating, therefore still when being wound around the blooming of strip, projection is easily damaged, cannot suppress wrapping offset etc.
Therefore, blooming is formed with also reliably can suppressing wrapping offset and adhesion when being desirably in the blooming being wound around the thinner strip of thickness.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-219272 publication (with reference to claim 1, (0028) section, Fig. 1 etc.)
Patent document 2: Japanese Unexamined Patent Publication 2009-223129 publication (with reference to (0026) section, Fig. 1 etc.)
Patent document 3: Japanese Unexamined Patent Publication 2004-347928 publication (with reference to claim 4, (0015) section etc.)
Summary of the invention
In view of the foregoing, the object of this invention is to provide a kind of blooming that also reliably can suppress wrapping offset and adhesion when being wound around the blooming of the thinner strip of thickness.
Above-mentioned purpose of the present invention is reached by following formation.
1. a blooming, is the blooming being formed with cured film on the film base material that thickness is 10 ~ 40 μm, it is characterized in that,
Each region of the both ends 50mm apart from above-mentioned film base material broadside is set to the 1st region and the 2nd region,
Above-mentioned cured film is that the mode of the scope of the scope of 20 ~ 100% of broadside to cover above-mentioned 1st region on above-mentioned film base material respectively and 20 ~ 100% of the broadside in above-mentioned 2nd region is formed,
Embossing processing is carried out to the surface of the respective above-mentioned cured film in above-mentioned 1st region and above-mentioned 2nd region being formed after above-mentioned cured film, thus forms concavo-convex embossed portion,
Above-mentioned embossed portion forms more than 3mm on the surface of described cured film from each end of this cured film along above-mentioned broadside.
2. the blooming as described in above-mentioned 1, is characterized in that, the height of above-mentioned embossed portion is 1 ~ 25 μm.
3. the blooming as described in above-mentioned 1 or 2, is characterized in that, the number of the protuberance of above-mentioned embossed portion is every 1cm 2it is 10 ~ 140.
4., as the blooming according to any one of above-mentioned 1 ~ 3, it is characterized in that, the elastic modelling quantity of above-mentioned cured film is more than 4.0GPa.
According to above-mentioned formation, carry out embossing processing by surface thickness being as thin as to the cured film on the film base material of 10 ~ 40 μm after forming cured film, form concavo-convex embossed portion.Embossed portion is not only utilize to be formed at the concavo-convex of film base material, owing to having the hardness of cured film, even if not easily because of deadweight, extruding force and damaged when being therefore wound around blooming yet.Thus, wrapping offset, the adhesion in core direction can also be suppressed when being wound around the thin and blooming of strip.
In addition, above-mentioned embossed portion forms more than 3mm in the broadside of film base material from end, therefore reliably can increase the patience to broadside (core direction), in addition, also reliably can guarantee the intensity of embossed portion.Its result, the wrapping offset in core direction when reliably can suppress the winding of thin blooming and adhesion.
In addition, cured film is that the mode of the scope of 20 ~ 100% of broadside to cover the 1st region and the 2nd region (region apart from each end 50mm of broadside) on film base material is respectively formed, and therefore the forming range of the cured film in the 1st region and the 2nd region is 10mm (being equivalent to 20% of 50mm) ~ 50mm (relative to 100% of 50mm) in broadside.Therefore, it is possible to reliably guarantee that the formation width of embossed portion is more than 3mm on the cured film surface in the 1st region and the 2nd region.
Accompanying drawing explanation
Fig. 1 is the sectional view of the concise and to the point formation of the blooming represented involved by embodiments of the present invention.
Fig. 2 is other sectional view formed representing above-mentioned blooming.
The cured film of the blooming of Fig. 1 and Fig. 2 is amplified the sectional view represented by Fig. 3.
Fig. 4 is the sectional view of the concise and to the point formation of the blooming representing embodiment 1.
Fig. 5 is the sectional view of the concise and to the point formation of the blooming representing embodiment 10.
Fig. 6 is the sectional view of the concise and to the point formation of the blooming representing embodiment 11.
Fig. 7 is the sectional view of the concise and to the point formation of the blooming representing embodiment 12.
Fig. 8 is the sectional view of the concise and to the point formation of the blooming representing embodiment 13.
Fig. 9 is the sectional view of the concise and to the point formation of the blooming representing comparative example 2.
Detailed description of the invention
Based on accompanying drawing, an embodiment of the invention are described, as described below.Should illustrate, in this manual, when number range is labeled as A ~ B, its number range comprises the value of lower limit A and upper limit B.
(formation of blooming)
Fig. 1 is the sectional view along broadside of the concise and to the point formation of the blooming F representing present embodiment.Should illustrate, broadside refers to (TD direction, direction vertical with long side direction (throughput direction, MD direction: Machine Direction) in face; Transverse Direction).Blooming F is the hard coat film of the cured film 2 formed on film base material 1 as hard conating.The thickness of film base material 1 is 10 ~ 40 μm, is film substrate.Here, conveniently the following description, is set to the 1st region R1 and the 2nd region R2 by each region of the both ends 50mm apart from film base material 1 broadside.
Cured film 2 is made up of the active energy ray curable resin such as ultraviolet curing resin.Should illustrate, for the detailed content of the resin material of cured film 2, describe as rear.By suitably selecting or control the resin material of cured film 2 and the illuminate condition (exposure etc.) of active energy beam, the elastic modelling quantity of cured film 2 can be controlled.
Here, elastic modelling quantity refers to the proportionality coefficient of deformation and stress, and the material little relative to stress deformation represents that elastic modelling quantity is high and hard (material softness that elastic modelling quantity is little).When using active energy ray curable resin, added by the functional group number in this resin material and particle, condition of cure, the elastic modelling quantity of cured film 2 can be controlled.Such as, by irradiating 300mJ/cm to the active energy ray curable acrylate with more than 2 functional groups 2above dynamic rays energy line, can realize more than elastic modelling quantity 4.0GPa.
Cured film 2 is that the mode of the scope of the scope of 20 ~ 100% of broadside to cover the 1st region R1 on film base material 1 respectively and 20 ~ 100% of the broadside of the 2nd region R2 is formed.Fig. 1 be represent cured film 2 with cover the broadside of the 1st region R1 and the 2nd region R2 respectively 20% the mode of scope be formed at situation on film base material 1.In this case, at the 1st region R1 and the 2nd region R2, the length of the broadside of cured film 2 is 20% of 50mm, i.e. 10mm.
On the other hand, Fig. 2 is other sectional view along broadside formed representing blooming F.In the blooming F of Fig. 2, cured film 2 is that the mode of the scope of 100% of the broadside covering the 1st region R1 and the 2nd region R2 is respectively formed.In this case, at the 1st region R1 and the 2nd region R2, the length of the broadside of cured film 2 is 100% of 50mm, i.e. 50mm.
Therefore, are modes of the scope of 20 ~ 100% of broadside to cover the 1st region R1 and the 2nd region R2 on film base material 1 respectively when being formed in cured film 2, the length of the broadside of the cured film 2 of the 1st region R1 and the 2nd region R2 is 10 ~ 50mm.
Should illustrate, in Fig. 1 and Fig. 2, in film broadside, form cured film 2 from the 1st region R1 continuously to the 2nd region R2, but also can be formed discontinuously.Such as, cured film 2 also only can be formed at the 1st region R1 and the 2nd region R2, and is not formed between the 1st region R1 and the 2nd region R2.In this case, cured film 2 is not with the surface of diaphragm base material 1, and is only formed for the purpose of hard embossed portion 3 described later to be formed.In addition, also can with formed between the 1st region R1 and the 2nd region R2 cured film 2 and and this cured film 2 mode of being positioned at the interval of regulation in broadside form cured film 2 at the 1st region R1 and the 2nd region R2.
In addition, concavo-convex embossed portion 3 is formed with on the surface of the respective cured film 2 of the 1st region R1 and the 2nd region R2.Should illustrate, in Fig. 1 and Fig. 2, conveniently, for the purpose of the forming region of clear and definite embossed portion 3, be smooth stratiform diagram embossed portion 3, but in fact as shown in Figure 3, the surface of embossed portion 3 is concavo-convex with surface.This embossed portion 3 is the dandy roll heating of pattern by surface being had convex-concave and the embossing processing that presses in cured film 2 and is formed.That is, embossed portion 3 be after being formed by cured film embossing processing and formed.Now, by making the heating-up temperature of dandy roll higher than the glass transition temperature Tg of cured film 2, embossed portion 3 can not formed with cracking in cured film 2.Should illustrate, also can cured film 2 utilize the solidification of Ultraviolet radiation etc. before (such as under semi-cured state) crimping dandy roll, thereafter, make cured film material be solidified to form embossed portion 3 completely.
Each end of the broadside of embossed portion 3 on the surface of cured film 2 from cured film 2 is formed to more than 3mm along broadside.That is, in Fig. 1 and Fig. 2, when the formation width of the embossed portion 3 in cured film 2 is represented with d (mm), d >=3.
In addition, in the formation of Fig. 1, embossing is carried out to cured film 2 and adds man-hour, except cured film 2, also to the surface crimping dandy roll of film base material 1, thus form concavo-convex embossed portion 4 on the surface of film base material 1.Should illustrate, at the broadside both ends of film base material 1, can before formation cured film 2, carry out embossing processing in advance and form embossed portion, also can not form embossed portion.Film base material 1 is pre-formed embossed portion, adds on film base material 1 when embossed portion 3 is formed to cured film 2 and form (stacked) embossed portion 4.Certainly, as shown in Figure 2, when cured film 2 is formed to the end of film base material 1, only embossing processing is carried out to cured film 2 and only form embossed portion 3 (not forming embossed portion 4) on the surface of cured film 2.
As present embodiment, form embossed portion 3 by implementing embossing processing on the surface of cured film 2, embossed portion 3 can be formed with the hardness identical with cured film 2.Thus, even if be wound around film base material 1 when being as thin as the blooming F of 10 ~ 40 μm, also not easily because of its deadweight, extruding force and embossed portion 3 is damaged, the wrapping offset in core direction, adhesion can be suppressed.In addition, by suppressing adhesion, the generation of the black-tape that the uneven thickness of the broadside of blooming F also can be suppressed to cause (in the circumferential direction occur the striped of band shape).
In addition, by the 1st region R1 and the 2nd region R2 that is 50mm with the length in broadside respectively covering wide edge direction 20 ~ 100% the mode of scope form cured film 2, the forming range of cured film 2 as above-mentioned be 10 ~ 50mm in broadside.Thus, more than 3mm embossed portion 3 can be formed in broadside on the surface of the cured film 2 of the 1st region R1 and the 2nd region R2.Then, form embossed portion 3 by (in broadside to more than 3mm) like this on the surface of cured film 2, reliably can increase the patience to broadside and core direction.In addition, by broadside with the formation embossed portion on a large scale of more than 3mm 3, also reliably can guarantee the intensity of embossed portion 3.Its result, reliably can suppress wrapping offset and the adhesion in core direction when being wound around thin blooming F.
In addition, in present embodiment, the elastic modelling quantity of cured film 2 is more than 4.0GPa, and cured film 2 is hard, therefore by implementing embossing processing to the surface of cured film 2, reliably can realize the hard embossed portion 3 of the function playing above-mentioned suppression wrapping offset and adhesion.
In addition, the confficient of static friction of cured film 2 is low, smoothly and easily attach, the formation of the present embodiment of wrapping offset and adhesion therefore can be suppressed to be that the winding of the strip of the Film Optics film F of less than 70 μm and then less than 50 μm is very effective to the thickness under the state comprising cured film 2.So can while suppress wrapping offset and the adhesion of blooming F, the long size of carrying out blooming F is wound around, then thereafter, when using blooming F to make polarizer, the productivity ratio of polarizer can be made to improve.
In addition, Fig. 3 amplifies the sectional view representing cured film 2.In present embodiment, the height t of embossed portion 3 is 1 ~ 25 μm.Here, the height t of embossed portion 3 refers to the height (maximum height) of concavo-convex surface (surface of the cured film 2 before implementing embossing processing) to the protuberance 3a of embossed portion 3 never forming embossed portion 3 on the surface of cured film 2.The height t of embossed portion 3 can add by adjustment embossing the extruding force of dandy roll to cured film 2 used man-hour and control.
When the height t of embossed portion 3 is less than 1 μm, the effect that the wrapping offset that embossing 3 brings suppresses diminishes, and easily produces film adhesion each other when film is wound around.On the other hand, if the height t of embossed portion 3 is greater than 25 μm, then when film is wound around, the protuberance 3a of embossed portion 3 easily swings to inside broadside, easily produces warpage (distortion), be difficult to guarantee good volume appearance at the volume be wound around in the cross section of broadside.
Therefore, by making the height t of embossed portion 3 be the scope of 1 ~ 25 μm, wrapping offset when film can be suppressed to be wound around and adhesion, and suppress the distortion of volume and make volume appearance good.
In addition, in present embodiment, the number (density) of the protuberance 3a of the embossed portion 3 on cured film 2 surface is every 1cm 2it is 10 ~ 140.Should illustrate, the number of protuberance 3a can adjust by selecting suitable dandy roll to carry out embossing processing from the different multiple dandy rolls of the number of unit are of the protuberance becoming mould on surface.
If the number of the protuberance 3a of embossed portion 3 is less than 10/cm 2, then the quantity of protuberance 3a is very few, cannot play the function of embossed portion 3 expeditiously, that is, the function of above-mentioned suppression wrapping offset and adhesion.On the other hand, if the number of protuberance 3a is greater than 140/cm 2, then the danger of film fracture uprises.That is, if the number of carrying out protuberance 3a is greater than 140/cm 2embossing processing, then the infringement given film base material 1 increases, and the intensity of the broadside of film base material 1 declines, and the danger of therefore film fracture uprises.
Therefore, by making the number of the protuberance 3a of embossed portion 3 be 10 ~ 140/cm 2, reliably can play the function of the embossed portion 3 suppressing wrapping offset and adhesion, and suppress the fracture of film.
Should illustrate, when film base material 1 forms cured film 2, if cured film material greatest limit is coated the end of film base material 1, then likely this cured film material around to film base material 1 the back side and also form cured film at this back side.In order to avoid this situation, preferably from the end apart from film base material 1, at least the position (with opposition side, end) inside broadside of 5mm is coated with cured film material and forms cured film 2.
Should illustrate, above, cured film 2 does not arrange the functional layer such as anti-reflection layer, but the situation arranging functional layer also can apply the formation of above-mentioned present embodiment.That is, by arranging functional layer in cured film 2, the cured film 2 simultaneously outside the broadside of this functional layer forming embossed portion 3, the wrapping offset etc. of blooming F can be suppressed.Should illustrate, embossed portion 3 can be formed at cured film 2 surface before the formation of functional layer, also can be formed after the formation of functional layer.
Especially in order to improve soil resistance layer (stain-proofing layer) containing fluorine system activating agent is set as functional layer time, easy generation wrapping offset etc., therefore in this case, formation cured film 2 being arranged the present embodiment of embossed portion 3 becomes very effective.
(detailed content of each layer)
Below, the detailed content of each layer of above-mentioned blooming F is described.
(hard conating)
Hard conating as above-mentioned cured film is formed by active energy ray curable resin.Active energy ray curable refers to and irradiates the resin of solidification through cross-linking reaction etc. by the dynamic rays of such as ultraviolet, electron beam, specifically, is the resin with ethylenic unsaturated group.Active energy ray curable resin comprises active energy ray curable isocyanurate derivative and the active energy ray curable resin except isocyanurate derivative.
< active energy ray curable isocyanurate derivative >
As the isocyanurate derivative of active energy ray curable, as long as have the compound of the structure of the ethylenic unsaturated group of bonding more than 1 on isocyanuric acid skeleton, have no particular limits, the compound in same a part with the ethylenic unsaturated group of more than 3 and the isocyanurate ring of more than 1 that preferred following general formula (1) represents.The kind of ethylenic unsaturated group is acryloyl group, methacryl, styryl, vinyl ether group, is more preferably methacryl or acryloyl group, is particularly preferably acryloyl group.
General formula (1)
L in formula 2for the linking group of divalent, be preferably the replacement of carbon atom bonding on isocyanurate ring or without the alkylene oxide group of the carbon number less than 4 replaced or poly-alkylene oxide group, be particularly preferably alkylene oxide group, separately can be identical or different.R 2represent hydrogen atom or methyl, separately can be identical or different.It is following that general formula (1) represents that concrete compound is shown in, but be not limited to them.
As other compound, isocyanuric acid diacrylate compounds can be enumerated, the isocyanuric acid ethyoxyl modified diacrylate that preferred following general formula (2) represents.
General formula (2)
In addition, as other, can enumerate the isocyanurate derivative of the active energy ray curable of 6-caprolactone modification, specifically, be the compound that following general formula (3) represents.
General formula (3)
The R of above-mentioned chemical structural formula 1~ R 3-on the functional group that represents with following a, b, c, R 1~ R 3in at least one be the functional group of b.
A:-H or-(CH 2) n-OH (n=1 ~ 10, preferred n=2 ~ 6)
B:-(CH 2) n-O-(COC 5h 10) m-COCH=CH 2(n=1 ~ 10, preferred n=2 ~ 6, m=2 ~ 8)
C:-(CH 2) n-O-R (R is (methyl) acryloyl group, n=1 ~ 10, preferred n=2 ~ 6)
The concrete compound that general formula (3) represents is shown in following, but is not limited to them.
As the commercially available product of isocyanuric acid triacrylate compound, such as, can enumerate chemical industry Co., Ltd. of Xin Zhong village A-9300 etc.As the commercially available product of isocyanuric acid diacrylate compounds, such as, can enumerate Toagosei Co., Ltd ARONIX M-215 etc.As the mixture of isocyanuric acid triacrylate compound and isocyanuric acid diacrylate compounds, such as, can enumerate Toagosei Co., Ltd ARONIX M-315, ARONIX M-313 etc.
As the isocyanurate derivative of the active energy ray curable of 6-caprolactone modification, chemical industry Co., Ltd. of Xin Zhong village A-9300-1CL, the Toagosei Co., Ltd ARONIX M-327 etc. as 6-caprolactone modification three-(third rare trimethylammonium) isocyanuric acid ester can be enumerated, but be not limited to them.
Active energy ray curable resin > beyond < isocyanurate derivative
As the active energy ray curable resin except isocyanurate derivative, preferably use ultraviolet hardening urethane acrylate system resin, ultraviolet hardening polyester acrylate system resin, ultraviolet hardening epoxy acrylate system resin, ultraviolet hardening polyalcohol acrylate system's resin or ultraviolet hardening epoxy resin etc.Wherein, ultraviolet hardening acrylic ester resin is preferably.
As ultraviolet hardening acrylic ester resin, be preferably polyfunctional acrylic ester.As this polyfunctional acrylic ester, be preferably selected from pentaerythrite polyfunctional acrylic ester, dipentaerythritol polyfunctional acrylic ester, the multifunctional methacrylate of pentaerythrite and the multifunctional methacrylate of dipentaerythritol.Here, polyfunctional acrylic ester refers in molecule the compound with more than 2 acryloxies or methacryloxy.
As the monomer of polyfunctional acrylic ester, such as, preferably can enumerate glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediyl ester, neopentylglycol diacrylate, trimethylolpropane triacrylate, methylolethane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, five glycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, glycerol tri-acrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester, ethylene glycol dimethacrylate, dimethacrylate, HDDMA, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate, tetramethylol methane trimethyl acrylic ester, tetramethylol methane tetramethyl acrylate, five glycerine trimethyl acrylic esters, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, glycerine trimethyl acrylic ester, dipentaerythritol trimethyl acrylic ester, dipentaerythritol tetramethyl acrylate, dipentaerythritol pentamethacrylates, dipentaerythritol hexamethacrylate etc.
As the active energy ray curable resin except isocyanurate derivative, monofunctional acrylate can be used.As monofunctional acrylate, isobornyl acrylate, acrylic acid 2-hydroxyl-3-phenoxy-propyl, the different stearyl ester of acrylic acid, benzyl acrylate, acrylic acid ethyl carbitol ester, acrylate, lauryl acrylate, Isooctyl acrylate monomer, tetrahydrofurfuryl acrylate, acrylic acid Shan Yu ester, acrylic acid 4-hydroxybutyl, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, cyclohexyl acrylate etc. can be enumerated.As monofunctional acrylate, can obtain from chemical industry Co., Ltd. of Xin Zhong village, Osaka Organic Chemical Industry Co., Ltd. etc.These compounds can individually use or be mixed with two or more.In addition, also can be the oligomer such as 2 aggressiveness, 3 aggressiveness of above-mentioned monomer.
The viscosity of polyfunctional acrylic ester is preferably below 3000mPas, more preferably below 2000mPas the viscosity of 25 DEG C.Should illustrate, above-mentioned viscosity is the value using Brookfield viscometer to measure under the condition of 25 DEG C.
In addition, when also using with active energy ray curable isocyanurate derivative and the active energy ray curable resin except isocyanurate derivative in hard conating, is (A) at active energy ray curable isocyanurate derivative (A) and active energy ray curable resin (B) except isocyanurate derivative except containing mass ratio: the scope of (B)=10:90 ~ 50:50 uses, and is preferred in film-strength (marresistance) excellence.
In order to promote the solidification of active energy ray curable resin, preferably in hard conating, contain Photoepolymerizationinitiater initiater.As the amount of Photoepolymerizationinitiater initiater, preferably Photoepolymerizationinitiater initiater by quality ratio: active energy ray curable resin=20:100 ~ 0.01:100.
As Photoepolymerizationinitiater initiater, specifically, acetophenone, benzophenone, dihydroxy benaophenonel, Michler's keton, α-amyl group oxime ester (α-ア ミ ロ キ シ system エ ス テ Le), thioxanthones etc. and their derivative can be enumerated, but be not particularly limited in them.
In addition, in order to prevent adhesion, improve marresistance etc., preferably inorganic or organic particulate is made an addition to active energy ray curable resin.As inorganic particles, silica, titanium oxide, aluminium oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconia, magnesia, calcium carbonate, talcum, clay, calcined kaolin, baked calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate can be enumerated.Particularly preferably use silica, titanium oxide, aluminium oxide, zirconia, magnesia etc.
These inorganic particles improve marresistance while the transparency of maintenance blooming, are preferably coated to the organic principle with reactive functional groups in the part on surface.The mode of the organic principle with reactive functional groups is coated to as the part on surface, such as, the hydroxyl can enumerating the surface making to be present in metal oxide microparticle and the compound comprising the organic principles such as silane coupler react and the mode of a part of bonding organic principle on surface; Organic principle is attached to be present in the mode of the hydroxyl on the surface of metal oxide microparticle by the interaction of hydrogen bond etc.; And the mode etc. containing the inorganic particles of more than 1 or 2 in polymer particle.
In addition, as organic fine particles, polymethylacrylic acid methacrylate resin powder, styrene system toner, plexiglass powder, silicon system toner, polystyrene resin powder, polycarbonate resin powder, benzoguanamine system toner, melamine series toner, polyolefin-based resins powder, polyester based resin powder, polyamide series resin powder, polyimides system toner, polyvinyl fluoride system toner etc. can be used.
As preferred organic fine particles, crosslinked polystyrene particle can be enumerated (such as, combine and grind chemistry SX-130H, SX-200H, SX-350H processed), polymethyl methacrylate system particle (such as, combine grind chemical MX150, MX300 processed), fluoroacrylic resin particulate.As fluoroacrylic resin particulate, such as, can enumerate Nippon Paint system: the commercially available products such as FS-701.In addition, as acrylic particles, such as, Nippon Paint system can be enumerated: S-4000, as acrylicstyrene particle, such as, Nippon Paint system can be enumerated: S-1200, MG-251 etc.
The average grain diameter of these fine-particle powders has no particular limits, and is preferably 0.01 ~ 5 μm, is particularly preferably 0.01 ~ 1.0 μm.In addition, also the different particulate of two or more particle diameter can be contained.The average grain diameter of particulate such as can be measured by laser diffraction formula particle size distribution device.
Ultraviolet curable resin composition preferably coordinates particulate in the mode being 10 ~ 400 mass parts relative to resin combination 100 mass parts with the ratio of particulate, more preferably 50 ~ 200 mass parts.
In addition, the hard conating involved by present embodiment be easy to get calmly the closely sealed aspect of the interlayer of hard conating and film base material set out preferably the hard conating coating composition with solvent dilution is coated with on film base material by following method, dry, solidify and arrange.As solvent, be preferably ketone or ester class.As ketone, methyl ethyl ketone, acetone, cyclohexanone, methyl iso-butyl ketone (MIBK) etc. can be enumerated, in addition, as ester class, methyl acetate, ethyl acetate, butyl acetate, propyl acetate etc. can be enumerated, but be not limited to them.As other solvent, alcohols (ethanol, methyl alcohol, butanols, normal propyl alcohol, isopropyl alcohol, DAA), hydro carbons (toluene, dimethylbenzene, benzene, cyclohexane), dihydroxylic alcohols ethers (propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethylene glycol list propyl ether etc.) etc. preferably can be used.
By using these solvents in the scope of 20 ~ 200 mass parts, as the excellent in stability of coating composition relative to active energy ray curable resin 100 mass parts.
In addition, the coating weight of hard conating coating composition can be 0.1 ~ 40 μm in wet coating thickness, is preferably 0.5 ~ 30 μm, and for dried film thickness, average film thickness 0.1 ~ 30 μm, is preferably 1 ~ 20 μm, is particularly preferably 4 ~ 15 μm.
Can by using gravure coater, dip coaterd, reverse coating machine, line rod coating machine, known coating process such as mould (extruding) painting machine, ink-jet method etc., after the hard conating coating composition forming hard conating is coated with, carry out drying, carry out UV solidification process, as required UV solidification heated further and form hard conating.
Process as UV solidification the light source used, then can use ad lib as long as produce ultraviolet light source.Such as, Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, carbon arc lamp, metal halide lamp, xenon lamp etc. can be used.Illuminate condition is different according to respective lamp, and the exposure of dynamic rays is generally 50 ~ 1000mJ/cm 2, be preferably 100 ~ 500mJ/cm 2.
In addition, when irradiating dynamic rays, the throughput direction imparting tension force preferably to film carries out, and preferably also gives tension force while carry out to broadside on one side further.The tension force given is preferably 30 ~ 300N/m.There is no particular limitation for the method for imparting tension force, can give tension force on back flow roll to throughput direction, also can give tension force with stenter to broadside or biaxially oriented.The more excellent film of flatness can be obtained thus.
In order to give static electricity resistance, hard conating also can contain conductive agent.As preferred conductive agent, metal oxide particle or pi-conjugated system electric conductive polymer can be enumerated.In addition, ionic liquid also can be used as conductive compound and preferably uses.In addition, from the view point of the viewpoint of coating and the uniform dispersiveness of particulate, in hard conating, also nonionic surfactant, anion surfactant and the fluoro-silicone grafted polymers such as silicone based surfactants, fluorine system surfactant or polyoxyether can be contained.Fluoro-silicone grafted polymers refers to the polymer of the polysiloxanes and/or organopolysiloxane grafting that at least make fluorine resin and comprise siloxanes and/or organosiloxane monomer and the copolymer obtained.As commercially available product, ZX-022H, ZX-007C, ZX-049, ZX-047-D etc. that Fuji changes into Industrial Co., Ltd can be enumerated.In addition, these compositions preferably add in the scope of 0.01 ~ 3 quality % relative to the solid constituent in coating fluid.
Hard conating can be 1 layer, also can be multilayer.In order to easily control the hard painting of hard conating, mist degree, arithmetic surface roughness Ra, hard conating can be divided into more than 2 layers and arrange.In addition, hard conating also can be arranged at the two sides of film base material.
The thickness of the superiors when arranging more than 2 layers hard conatings is preferably the scope of 0.05 ~ 2 μm.More than 2 layers stacked also can to overlap to form simultaneously.Simultaneously overlapping to refer to without drying process is coated with the hard conating of more than 2 layers with the form of wet on wet and forms the method for hard conating on base material.Can be successively overlapping by extrusion coated machine with stacked 2nd hard conating of the form of wet on wet without drying process on the 1st hard conating, or simultaneously overlapping with the slit coater with multiple slit (slot die).
The pencil hardness as hardness number of hard conating is more than H, is more preferably more than 4H.If more than 4H, then in the polarizer chemical industry sequence of liquid crystal indicator, not only be difficult to produce damage, and when using as the skin covering of the surface base material being used for greatly the large-scale liquid crystal indicator of outdoor application or numerical digit label liquid crystal indicator, the film-strength of excellence be also shown.Pencil hardness is that the blooming made damping under the condition of temperature 23 DEG C, relative humidity 55%, after more than 2 hours, is used JIS (Japanese Industrial Standards Committee; JISC) the test pencil of JIS S 6006 defined of one of standard, carry out the value measured according to the evaluating pencil hardness method of JIS K5400 defined.
< mist degree >
The haze value of the blooming of present embodiment is preferably less than 1% for transparent blooming.By making haze value be less than 1%, the liquid crystal indicator that maximizes or the sufficient brightness when outdoor application such as numerical digit label, high contrast can be obtained.Haze value can measure according to JIS K7105 and JIS K7136.
In addition, the blooming of present embodiment also can have anti-glare.Anti-glare refers to the blear function of image or the outer light reflected by the hard conating by blooming, when making the visuality of reflection image decline and use blooming in liquid crystal display etc., without the need to taking notice of mirroring of reflection image.Have in the blooming of anti-glare, total haze value is preferably 3% ~ 40%.In addition, surface haze value (mist degree that the surface scattering of film causes) is preferably 3 ~ 40%, and internal haze value (mist degree that scattering-in causes) is preferably less than 35%.
(film base material)
Film base material is sent out from easily producing, and is preferably the cellulose esters mesenterys such as tri cellulose acetate membrane, cellulose-acetate propionate film, cellulose diacetate film, cellulose acetate-butyrate film.As other film, PETG can be used in film base material, the polyester mesenterys such as PEN, Merlon mesentery, polyarylate mesentery, polysulfones (also comprising polyether sulfone) mesentery, polyethylene film, polypropylene screen, glassine paper, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl alcohol film, styrene-based film, norbornene resin mesentery, polymethylpentene film, polyether-ketone film, polyether-ketone acid imide film, PA membrane, fluororesin film, nylon membrane, cyclo-olefin-polymer films, polymethyl methacrylate film, acrylic film etc.Also can be used together the resin forming above-mentioned film.
The refractive index of film base material is preferably 1.30 ~ 1.70, is more preferably 1.40 ~ 1.65.Refractive index can use the Abbe refractomecer 2T of Atago Inc. to measure with the method for JIS K7142.
< cellulose esters mesentery >
When cellulose esters mesentery is cellulose triacetate, preferably use the film of average acetylation degree (bonding acetic acid amount) 54.0 ~ 62.5%, preferably average acetylation degree is the tri cellulose acetate membrane of 58.0 ~ 62.5% further.If average acetylation degree is little, then change in size is large, and the degree of polarization of polarizer declines.If average acetylation degree is large, then decline to the solubility of solvent, productivity ratio declines.
It is 2.80 ~ 2.95 that film base material preferably contains degree of substitution with acetyl group, and number-average molecular weight (Mn) is more than 125000 and is less than the cellulose triacetate A of 155000.In addition, cellulose triacetate A preferable weight-average molecular weight (Mw) is more than 265000 and is less than 310000, and Mw/Mn is 1.9 ~ 2.1.
In addition; from improving the aspect of pencil hardness, be preferably 2.75 ~ 2.90 to cellulose triacetate A and with degree of substitution with acetyl group and number-average molecular weight (Mn) be more than 155000 and be less than 180000, Mw be more than 290000 and be less than 360000, Mw/Mn be 1.8 ~ 2.0 cellulose triacetate B.And during with cellulose triacetate A and cellulose triacetate B, preferably by quality ratio, cellulose triacetate A: the scope of cellulose triacetate B=100:0 ~ 20:80.
Except cellulose triacetate; following cellulose esters can be used, namely there is the acyl group alternatively base of carbon number 2 ~ 4, the substitution value of acetyl group is set to X; when the substitution value of propiono or bytyry is set to Y, meet following formula (I) and (II) simultaneously.
Formula (I) 2.6≤X+Y≤3.0
Formula (II) 0≤X≤2.5
Wherein, be preferably cellulose-acetate propionate, be wherein preferably 1.9≤X≤2.5,0.1≤Y≤0.9.The mensuration of acyl substitution can according to ASTM (American Society for Testing and Materials; Test material association of the U.S.) the ASTM D817-96 of one of the plan standard of surely issuing carries out.In addition, also preferably cellulose diacetate can be used.
Number-average molecular weight (Mn) and the molecular weight distribution (Mw) of cellulose esters can use high performance liquid chromatograph to measure.Condition determination is as described below.
Solvent: carrene
Chromatographic column: Shodex K806, K805, K803G (Showa Denko K. K's chromatographic column 3 is connected and uses)
Chromatogram column temperature: 25 DEG C
Sample solution concentration: 0.1 quality %
Detector: RI Model 504 (GL Sciences Inc.)
Pump: L6000 (Hitachi Ltd.'s system)
Flow: 1.0ml/min
Calibration curve: polystyrene standard STK standard polystyrene (Tosoh Co., Ltd. system)
Use the calibration curve utilizing 13 sample makings of Mw=1000000 ~ 500.13 samples are preferably to use at equal intervals substantially.
< ester compounds >
From the aspect of resistance to excellent moisture permeability, cellulose esters mesentery is preferably containing ester compounds.As ester compounds, preferably have the aklylene glycol of phthalic acid, adipic acid, at least one benzene monocarboxylic acid and at least one carbon number 2 ~ 12 is reacted and obtain the ester compounds of structure.
As benzene monocarboxylic acid composition, such as have benzoic acid, p-tert-butyl benzoic acid, adjacent toluic acid, a toluic acid, to toluic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid etc., the mixture that they can use a kind respectively or be mixed with two or more.Most preferably be benzoic acid.
As the aklylene glycol composition of carbon number 2 ~ 12, there is ethylene glycol, 1, 2-propane diols, 1, ammediol, 1, 2-butanediol, 1, 3-butanediol, 1, 2-propane diols, 2-methyl 1, ammediol, 1, 4-butanediol, 1, 5-pentanediol, 2, 2-dimethyl-1, ammediol (neopentyl glycol), 2, 2-diethyl-1, ammediol (3, 3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1, 3 propane diols (3, 3-dihydroxymethyl heptane), 3-methyl isophthalic acid, 5-pentanediol 1, 6-hexylene glycol, 2, 2, 4-trimethyl 1, 3-pentanediol, 2-ethyl 1, 3-hexylene glycol, 2-methyl 1, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-octacosanol etc., these glycol can use as one kind or two or more mixture.Be particularly preferably 1,2-PD.
Above-mentioned ester compounds also can have adipic acid residue and the phthalic acid residue structure as final compound.
Above-mentioned ester compounds as required by under the existence of esterification catalyst, can mix 10 ~ 25 hours, carries out esterification and manufacture in the temperature range of such as 180 ~ 250 DEG C.
And then, as ester compounds, aromatic series terminal esterifications compound also can be used.The exemplary compounds of aromatic series terminal esterifications compound is shown in following, but is not limited to them.
In addition, as ester compounds, also sugar ester based compound can be enumerated.Sugar ester based compound is the compound all or part of esterification of the OH base of the sugar such as following monose, disaccharides, trisaccharide or oligosaccharides obtained, and as illustrating more specifically, can enumerate the compound etc. that general formula (4) represents.
General formula (4)
In formula, R 1~ R 8represent replace or without the carbon number 2 ~ 22 replaced alkyl-carbonyl or to replace or without the aryl carbonyl of carbon number 2 ~ 22 replaced.R 1~ R 8can be the same or different.
Below, the compound (compound 4-1 ~ compound 4-23) that general formula (4) represents more specifically is shown, but is not limited to them.
General formula (4)
In above-mentioned ester compounds, number-average molecular weight is preferably 300 ~ 2000, is more preferably 400 ~ 1500.In addition, acid number is preferably 0.08 ~ 0.50mgKOH/g.Hydroxyl value is preferably below 25mgKOH/g, is more preferably below 15mgKOH/g.
Above-mentioned ester compounds preferably containing 1 ~ 35 quality %, particularly preferably contains 5 ~ 30 quality % in film base material.If within the scope of this, then also do not ooze out, and the transparency is excellent.
Cellulose esters mesentery also can contain thermoplastic acrylic resin and cellulose ester resin.
Also methacrylic resin is comprised in acrylic resin.As acrylic resin, be not particularly limited, preferably by the methyl methacrylate units of 50 ~ 99 quality % and can forming with other monomeric unit of its copolymerization of 1 ~ 50 quality %.As can other monomer of copolymerization, the α such as alkyl acrylate, acrylic acid, methacrylic acid that the carbon number can enumerating alkyl number is the alkyl methacrylate of 2 ~ 18, the carbon number of alkyl number is 1 ~ 18, beta-unsaturated acid, maleic acid, fumaric acid, itaconic acid etc. contain the α such as aromatic ethenyl compound, acrylonitrile, methacrylonitrile such as unsaturated group dicarboxylic acids, styrene, AMS, alpha, beta-unsaturated nitriles, maleic anhydride, maleimide, N-substituted maleimide amine, glutaric anhydride etc.They also can be used alone, the monomer that also two or more kinds may be used and using.
Among them, from the view point of resistance to pyrolytic, the mobility of copolymer, preferred methyl acrylate, ethyl acrylate, n-propyl, n-butyl acrylate, sec-butyl acrylate, 2-EHA etc., particularly preferably use methyl acrylate, n-butyl acrylate.
In addition, the weight average molecular weight (Mw) of acrylic resin is preferably in the scope of 80000 ~ 500000, more preferably 110000 ~ 500000.The weight average molecular weight of acrylic resin can comprise condition determination, passes through gel permeation chromatography.In addition, as commercially available product, DELPET 60N, 80N (Asahi Chemical Corp's system), DIANAL BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd's system), KT75 (Deuki Kagaku Kogyo Co., Ltd's system) etc. can be enumerated.Also two or more kinds may be used for acrylic resin.
< additive >
For the purpose of the fragility improving film base material, also acrylic particles can be contained.As the example of the commercially available product of acrylic particles, such as, METABLEN W-341 (C2) (Mitsubishi Rayon Co., Ltd's system), Chemisnow MR-2G (C3), MS-300X (C4) (Soken Chemical & Engineering Co., Ltd.'s system) etc. can be enumerated.
Acrylic particles preferably contains in the scope of 0.5% ~ 30% relative to the gross mass of the resin forming film base material.
(particulate)
Film base material also can containing the particulate except acrylic particles.As the particulate except acrylic particles, from the view point of flatness, storage stability, the inorganic particles such as preferred silica, titanium dioxide, aluminium oxide, zirconia, calcium carbonate, calcium carbonate, talcum, clay, calcined kaolin, baked calcium silicate, afwillite, alumina silicate, magnesium silicate and calcium phosphate.
In these inorganic particles, low from the viewpoint of turbidity, preferred silica.Silica is thought of as preferably from the aspect having flatness and mist degree concurrently by the particulate having carried out hydrophobization process.Preferably more than 2 particulates replaced by hydrophobic substituting group in 4 silanol bases, more preferably more than 3 particulates be substituted.Hydrophobic substituting group is preferably methyl.The primary particle size of silica is preferably below 20nm, is more preferably below 10nm.
The particulate of silica such as can with AEROSIL R972, R972V, R974, R812,200,200V, 300, the trade name of R202, OX50, TT600 (more than, Japanese AEROSIL Co., Ltd. system) is commercially available and use.Zirconic particulate such as can be commercially available and use with the trade name of AEROSIL R976 and R811 (more than, Japanese AEROSIL Co., Ltd. system).Among them, AEROSIL 200V, AEROSIL R972V, owing to being kept by the mist degree of film base material reducing the effect of coefficient of friction greatly while low, therefore particularly preferably, most preferably use AEROSIL R812.In film base material, at least the coefficient of kinetic friction in the face of side is preferably 0.2 ~ 1.0.
(other additive)
In order to improve mobility, the flexibility of composition, in film base material, also plasticizer can be added.As plasticizer, phthalic compounds, fatty acid cpds, trimellitic acid compound, phosphate cpd, acrylic acid series polymeric compounds or epoxy compound etc. can be enumerated.
As acrylic acid series polymeric compounds, the homopolymers of preferred acrylic or methacrylic acid alkyl ester or copolymer.As the monomer of acrylate, such as, methyl acrylate can be enumerated, ethyl acrylate, propyl acrylate is (different, just), butyl acrylate (just, different, secondary, uncle), amyl acrylate (just, different, secondary), Hexyl 2-propenoate (just, different), heptylacrylate (just, different), 2-ethyl hexyl acrylate (just, different), acrylic acid ester in the ninth of the ten Heavenly Stems (just, different), acrylic acid tetradecane ester (just, different), acrylic acid (2-ethylhexyl) ester, acrylic acid (6-caprolactone) ester, acrylic acid (2-hydroxyethyl) ester, acrylic acid (2-hydroxypropyl) ester, acrylic acid (3-hydroxypropyl) ester, acrylic acid (4-hydroxybutyl) ester, acrylic acid (2-hydroxybutyl) ester, acrylic acid (2-methoxy ethyl) ester, acrylic acid (2-ethoxyethyl group) ester etc., or aforesaid propylene acid esters is changed into the compound of methacrylate.Acrylic acid series polymeric compounds is homopolymers or the copolymer of above-mentioned monomer, and methyl acrylate monomer units preferably has more than 30 quality %, and in addition, methyl methacrylate monomer unit preferably has more than 40 quality %.The particularly preferably homopolymers of methyl acrylate or methyl methacrylate.
Can select according to purposes or and use with these plasticizer.In addition, the addition of plasticizer is preferably 0.5 ~ 30 mass parts relative to film base material 100 mass parts.
Film base material is also preferably containing ultra-violet absorber.As the ultra-violet absorber used, the ultra-violet absorber etc. of BTA system, 2-dihydroxy benaophenonel system or phenyl salicytate system can be enumerated.Such as, 2-(5-methyl-2-hydroxy phenyl) BTA, 2-[2-hydroxyl-3 can be illustrated, two (the α of 5-, α-dimethylbenzyl) phenyl]-2H-BTA, 2-(3,5-bis--tert-butyl group-2-hydroxy phenyl) triazole type, ESCALOL 567, the 2-hydroxyl-4-octyloxybenzophenone such as BTA, the benzophenones such as 2,2 '-dihydroxy-4-methoxy benzophenones.Here, in ultra-violet absorber, molecular weight be more than 400 ultra-violet absorber be higher boiling be difficult to volatilization, high-temperature molding time be also difficult to disperse, therefore effectively can improve weatherability by the interpolation of small amount.
Be the ultra-violet absorber of more than 400 as molecular weight, 2-[2-hydroxyl-3 can be enumerated, two (the α of 5-, α-dimethylbenzyl) phenyl]-2 benzotriazole, 2, 2-di-2-ethylhexylphosphine oxide [4-(1, 1, 3, the 3-tetrabutyl)-6-(2H-BTA-2-base) phenol] etc. BTA system, two (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) the hindered amine system such as sebacate, and 2-(3, 5-bis--tertiary butyl-4-hydroxy benzyl)-2-n-butylmalonic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester, 1-[2-[3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionyloxy] ethyl]-4-[3-(3, 5-bis--tert-butyl-hydroxy phenyl) propionyloxy]-2, 2, 6, 6-tetramethyl piperidine etc. jointly has the ultra-violet absorber of the mixed stocker of the structure of hindered phenol and hindered amine in molecule, they can be used alone, or and use with two or more.Among them, the particularly preferably 2-[two (α of 2-hydroxyl-3,5-, α-dimethylbenzyl) phenyl]-2 benzotriazole, 2,2-di-2-ethylhexylphosphine oxides [4-(1,1,3, the 3-tetrabutyl)-6-(2H-BTA-2-base) phenol].
And then, in order to improve pyrolytic, hot tinting during processing and forming, in film base material, also various antioxidant can be added.In addition, also can add antistatic agent and give antistatic performance to film base material.
Also the flame-proof acrylic based resin composition of phosphorus flame retardant can be had by collaboration in film base material.As phosphorus flame retardant used herein, a kind or mixture of more than two kinds being selected from red phosphorus, triaryl phosphate, diaryl phosphate, aryl phosphate, arylphosphonic acid compound, aryl oxidized phosphine compound, condensation aryl phosphate ester, halogenated alkyl phosphate, halogen-containing condensed phosphoric acid esters, halogen-containing condensation phosphonate ester, halogen-containing phosphite ester etc. can be enumerated.
As concrete example, triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenyl-phosphonic acid, three (β-chloroethyl) phosphate, three (two chloropropyls) phosphate, three (tribromo neopentyl) phosphate etc. can be enumerated.
Based on the utilization to outdoor application such as numerical digit labels, owing to needing higher brightness, film base material needs can bear the use under environment at higher temperature.If the tension force softening point of film base material is 105 DEG C ~ 145 DEG C, then can be judged as showing sufficient heat resistance and preferably, particularly preferably controlling at 110 DEG C ~ 130 DEG C.
As the concrete assay method of tension force softening point, such as, TENSILON testing machine (ORIENTEC Inc. can be used, RTC-1225A), blooming is cut into 120mm (indulging) × 10mm (wide), while with the tension force stretching of 10N while persistently overheating with the programming rate of 30 DEG C/min, measure the temperature becoming the moment of 9N for 3 times, obtain tension force softening point by its mean value.
In addition, from the viewpoint of heat resistance, the glass transition temperature (Tg) of film base material is preferably more than 110 DEG C.Be more preferably more than 120 DEG C.Be particularly preferably more than 150 DEG C.
Should illustrate, glass transition temperature mentioned here refers to and uses means of differential scanning calorimetry analyzer (Perkin Elmer Inc. DSC-7 type) with programming rate 20 DEG C/min mensuration, the intermediate point glass transition temperature (Tmg) obtained according to JIS K7121 (1987).
In addition, when especially using film base material in the liquid crystal indicator of outdoor application, the size changing rate (%) of film base material is preferably less than 0.5%, is preferably less than 0.3% further.
In addition, in film base material, the defect of the diameter in face more than 5 μm is preferably 1/10cm 2below.Be more preferably 0.5/10cm 2below, more preferably 0.1/10cm 2below.Here, defect refers to the cavity (foaming defect) in the film produced due to the evaporation sharply of solvent in the drying process of solution film-forming; Foreign matter (foreign matter defect) in the film caused because of the foreign matter be mixed in the foreign matter in masking stoste, masking; And the part of the surface configuration such as the transfer printing of roll marks or scratch change.In addition, the scope of defect for representing its diameter time circular in defect, is determined with microscopic examination by following method when not being circle, is set to its maximum diameter (external diameter of a circle) by the diameter of defect.
Defect be bubble or foreign matter time, the size of the shade when scope of defect is the viewed in transmitted light defect with differential interference microscope.When defect is the change of the surface configuration such as transfer printing or scratch of roll marks, the scope of defect confirms size with the viewed in reflected light defect of differential interference microscope.Should illustrate, during with viewed in reflected light, if the size of defect is indefinite, then aluminium or platinum evaporation be observed in surface.
In order to high production rate obtain the film of the grade excellence represented with this defect frequency, effectively by polymer solution high-precision filtration before being about to cast, improve the cleannes of casting machine periphery, and drying condition after stage ground setting cast, efficient and suppress foaming and make it dry.
If the number of defect is more than 1/10cm 2, then sometimes after such as operation add when man-hour etc. tension force being applied to film, film is that basic point ruptures with defect, and productivity ratio declines.In addition, if the diameter of defect is more than 5 μm, then sometimes by polarizer observation etc. with visual confirmation, sometimes bright spot can be produced as during optics.
In addition, though with visual cannot confirm defect time, hard conating coating composition cannot be coated with equably when sometimes forming hard conating on this film, become defect (coating disappearance).
In addition, film base material is in the mensuration according to JIS K7127 (1999), and the elongation at break at least one direction is preferably more than 10%, is more preferably more than 20%.
There is no particular limitation for the upper limit of elongation at break, is actually about 250%.Increase elongation at break, effectively suppress the defect in foreign matter or the film caused by foaming.
The thickness of film base material is preferably more than 10 μm.Be more preferably more than 20 μm.
There is no particular limitation for the upper limit of the thickness of film base material, and during with the membranization of solution film-forming method, from the view point of coating, foaming, solvent seasoning etc., the upper limit is about 250 μm.Should illustrate, the thickness of film base material suitably can be selected according to purposes.
Therefore, the thickness of the film base material of present embodiment is preferably 10 ~ 250 μm, is more preferably 20 ~ 100 μm.Should illustrate, from the view point of the filming of optics, be particularly preferably 10 ~ 40 μm.
For film base material, its full light transmittance is preferably more than 90%, is more preferably more than 93%.In addition, as the upper limit of reality, be about 99%.In order to reach the transparency of the excellence represented with this full light transmittance, effectively not introducing the additive, the copolymer composition that absorb visible ray, being removed the foreign matter in polymer by high-precision filtration and making the diffusion of the light of film inside or absorb to reduce.
In addition, the length of delay of film base material be preferably wavelength 590nm face in length of delay Ro be 0 ~ 50nm, the length of delay Rth of thickness direction is-10 ~ 50nm scope.By using the film base material with the length of delay of this scope to form blooming, when blooming being such as used for contact panel component parts, the interference fringe caused by birefringence can be suppressed well.
Should illustrate, above-mentioned Ro and Rth is the value defined with following formula (I) and (II).
Formula (I) Ro=(nx-ny) × d
Formula (II) Rth={ (nx+ny)/2-nz} × d
Wherein, in formula, nx represents the axial refractive index of delay in the face of film base material, and ny represents the refractive index in direction vertical with retardation axis in the face of film base material, and nz represents the refractive index of the thickness direction of film base material, and d represents the thickness (nm) of film base material.Above-mentioned length of delay can use such as KOBRA-21ADH (prince measures machine Co., Ltd.) 23 DEG C, obtain to measure wavelength 590nm under the environment of 55%RH.
Length of delay can by adjustment such as the thickness of the kind of above-mentioned ester compounds, plasticizer, addition and film base material or stretching conditions.
In addition, effectively: the surface roughness of the film contact site (coated substrate in chill roll, stack, drum, band, solution film-forming, conveying roller etc.) when reducing masking and reduce the surface roughness on film surface; By the refractive index reducing acrylic resin, the diffusion of the light on film surface or reflection are reduced.
(masking of film base material)
Then, the example of the film-forming method of film base material is described, but the present invention is not limited to this.
As the film-forming method of film base material, the autofrettages such as inflation method, T modulus method, rolling process, cutting method, casting, emulsion process, pressure sintering can be used.From the view point of the optical defect etc. suppressing painted, suppress foreign matter defect, suppress mold profile etc., preferably utilize the masking of casting.Utilize in the masking of casting and have solution-casting method and melt casting method.
(organic solvent)
To forming coating medium (ド ー プ when manufacturing film base material with solution-casting method) as long as the solvent of useful organic solvent dissolving cellulos ester system resin, other additive simultaneously then can use ad lib.
Such as, as chlorine-based organic solvent, can carrene be enumerated, as chlorine-free organic solvent, methyl acetate, ethyl acetate, pentyl acetate, acetone, oxolane, DOX, Isosorbide-5-Nitrae-two can be enumerated alkane, cyclohexanone, Ethyl formate, 2,2,2-trifluoroethanols, 2,2,3,3-hexafluoro-1-propyl alcohol, 1,3-bis-fluoro-2-propyl alcohol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propyl alcohol, 2,2,3, the fluoro-1-propyl alcohol of 3,3-five, nitroethane etc., can preferably use carrene, methyl acetate, ethyl acetate, acetone.
Except above-mentioned organic solvent, the aliphatic alcohol of the straight or branched of the carbon number 1 ~ 4 of coating medium preferably containing 1 ~ 40 quality %.If the ratio of the alcohol in coating medium uprises, then tablet (ウ ェ Block) gelation, easily peels off from metal support, in addition, when the ratio of alcohol is few, can promote the dissolving of the acrylic resin in chlorine-free organic solvent system, cellulose ester resin.
In the solvent of the especially preferred aliphatic alcohol at the straight or branched containing carrene and carbon number 1 ~ 4, acrylic resin, cellulose ester resin and acrylic particles 3 kinds is dissolved the coating medium composition at least adding up to 15 ~ 45 quality %.
As the aliphatic alcohol of the straight or branched of carbon number 1 ~ 4, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol can be enumerated.Among them, from stability, boiling point also lower, the drying property also good grade of coating medium, preferred alcohol.
(solution-casting method)
Film base material can be manufactured by solution-casting method.In solution-casting method, undertaken by following operation: make resin and additive be dissolved in solvent and prepare the operation of coating medium, by the operation of coating medium at the metal support upper of banded or drum type, the coating medium of cast is carried out dry operation as tablet, the operation of tablet is peeled off from metal support, by the operation that tablet stretches or width keeps, operation dry further, by the operation that the film completed is wound around.
For the concentration of the cellulose esters system resin in coating medium, concentration is more high more can reduce the drying load after being cast in metal support, so preferably, if but the excessive concentration of cellulose esters system resin, then load when filtering increases, and filtering accuracy is deteriorated.As taking into account their concentration, be preferably 10 ~ 35 quality %, more preferably 15 ~ 25 quality %.
Metal support in cast (casting) operation is preferably effects on surface and has carried out the accurately machined supporter of minute surface, as metal support, preferably uses the drum surperficial plating fine finishining obtained in stainless steel band or casting material.
The width of casting can be set to 1 ~ 4m.The temperature that the surface temperature of the metal support of cast operation is set as the boiling of-50 DEG C ~ solvent and does not foam.Therefore the higher rate of drying can accelerating tablet of temperature is preferably, if but too high, then tablet foaming sometimes, flatness is deteriorated sometimes.
The temperature of metal support preferably suitably determines in the scope of 0 ~ 100 DEG C, more preferably 5 ~ 30 DEG C.Or make tablet gelation by cooling, peeling off from metal support under the state containing a large amount of residual solvent is also method for optimizing.
The method controlling the temperature of metal support has no particular limits, and has the method for blowing warm air or cold wind, makes the method for the rear-face contact of warm water and metal support.Use warm water effectively to conduct heat, therefore to become time of uniform temperature short for the temperature of metal support, for preferably.
When using warm air, consider that the temperature of the tablet caused by evaporation latent heat of solvent declines, sometimes use the warm air of more than solvent boiling point, although and also prevent foaming from using the wind of the temperature higher than target temperature.Changing the temperature of metal support and the temperature of dry wind particularly preferably in being poured between stripping, effectively carrying out drying.
In order to make cellulose esters mesentery show good flatness, residual solvent amount when peeling off tablet from metal support is preferably 10 ~ 150 quality %.The preferable range of the lower limit of residual solvent amount is 20 ~ 40 quality %, is particularly preferably 20 ~ 30 quality %.The preferable range of the upper limit of residual solvent amount is 60 ~ 130 quality %, is particularly preferably 70 ~ 120 quality %.Should illustrate, residual solvent amount is defined by following formula.
Residual solvent amount (quality %)={ (M-N)/N} × 100
Here, M is the quality extracting any time in the mill or after manufacturing the sample that tablet or film obtain, and N is the quality heated after 1 hour with 115 DEG C by M.
In addition, in the drying process of cellulose ester membrane or cellulose ester resin acrylic resin film, preferably tablet is peeled off from metal support, further drying, make residual solvent amount be below 1 quality %, more preferably below 0.1 quality %, is particularly preferably below 0 ~ 0.01 quality %.
In stretching process, can to the throughput direction of tablet (film) (MD direction; Machine Direction) and broadside (the TD direction vertical with it; Transverse Direction) successively or side by side stretch.2 mutually orthogonal axial stretching ratios are preferably finally set in 1.0 ~ 2.0 times, MD direction, in the scope in 1.07 ~ 2.0 times, TD direction respectively, preferably in 1.0 ~ 1.5 times, MD direction, carry out in the scope in 1.07 ~ 2.0 times, TD direction.Such as, it is poor to enumerate multiple roller applying peripheral speed, utilizes the method that roller peripheral speed difference stretches in MD direction betwixt; Fix the two ends of tablet with cloth gripper or needle plate, Directional Extension and the method that stretches in MD direction are being advanced in the interval of cloth gripper or needle plate; Similarly extending transversely and TD direction stretch method; Or simultaneously at MD/TD Directional Extension in the method etc. that MD/TD both direction stretches.
These width of film making process keep or the stretching of broadside is carried out preferably by stenter, can be pin stenter also can be clip stenters.Film conveyance tension in the film making process waited in stenter also depends on temperature, but is preferably 120N/m ~ 200N/m, more preferably 140N/m ~ 200N/m, most preferably is 140N/m ~ 160N/m.
When the glass transition temperature of film base material is set to Tg DEG C, temperature during stretched film is (Tg-30) ~ (Tg+100) DEG C, be more preferably (Tg-20) ~ (Tg+80) DEG C, more preferably (Tg-5) ~ (Tg+20) DEG C.
The glass transition temperature of film base material can by forming the rate control of the material category of film and the material of formation.Glass transition temperature during film base material dry is preferably more than 110 DEG C, and then, be more preferably more than 120 DEG C.In addition, the glass transition temperature of film base material is preferably less than 190 DEG C, and then, be more preferably less than 170 DEG C.Now, the glass transition temperature of film base material can be obtained by the method etc. recorded in JIS K7121.
If temperature during stretched film is set to more than 150 DEG C and stretching ratio is set to more than 1.15 times, then surface is moderately roughened, is therefore preferred.By film surface moderately the roughened slickness that not only makes improve, and improving the adaptation of Surface Machining, especially hard conating, is therefore preferred.The arithmetic average roughness Ra on the surface of film base material is preferably 2.0nm ~ 4.0nm, is more preferably 2.5nm ~ 3.5nm.
In film drying process, generally adopt roller drying mode (alternately passed through by tablet at the multiple roller configured up and down and make the mode of its drying), carry tablet while make the mode of its drying with stenter.
(melt casting method)
Film base material also can pass through melt casting method masking.Melt casting method refers to and will comprise the composition heating and melting of the additive such as resin and plasticizer to the temperature of display mobility, thereafter, by the fused mass cast comprising cellulose esters of mobility.Melt casting method also comprises film formation material heating, after showing its mobility, extrudes the method for masking on drum or on endless belt.
More specifically, the method for forming of heating and melting can be categorized as and melt extrude the method for forming, extrusion forming method, inflation method, injection moulding, blow molding method, drawing and forming method etc.In these methods of forming, from the aspect of mechanical strength and surface accuracy etc., preferably melt extrude the method for forming.Melt extrude the preferably usually mixing in advance and granulating of used multiple raw material.
Granulating can use known method to carry out.Such as, dried fibres element ester, plasticizer, other additive can be supplied to extruder with feeding machine, use single shaft or biaxial extruder mixing, extrude as linear from die head, carry out water-cooled or Air flow, carry out cutting and granulating.
Additive can be supplied to extruder forward slip value, also can be supplied to extruder with respective feeding machine respectively.
The a small amount of additive such as particle, antioxidant in order to mix equably, preferably mixing in advance.
Extruder preferably can with the mode granulating suppressing shearing force not make resin deterioration (molecular weight and molecular weight, painted, gel generation etc.), and as far as possible at the extruder of low temperature process.Such as, when biaxial extruder, preferably use the screw rod of deep channel type, rotate along equidirectional.From mixing uniformity, be preferably engagement type.
The particle as above obtained is used to be filmed.Raw-material powder is directly supplied to extruder with feeding machine with can not certainly carrying out granulating, direct masking.
Melt temperature when extruding above-mentioned particle by using the extruder of single shaft or biaxial type is set to about 200 ~ 300 DEG C, with filtrations such as the filters of leaf dish-type after removing foreign matter, be cast for membranaceous from T-shaped die head, with chill roll and Elastic Contact roller clamping film, make it solidify on chill roll.
During from feed hopper to extruder transfer material, preferably under vacuo or decompression under, prevent oxidation Decomposition etc. under non-active gas atmosphere.In addition, the flow of extruding of particle preferably imports gear pump etc. and stably carries out.
In addition, the filter that the removing of foreign matter uses preferably uses stainless steel fibre sintered filter.Stainless steel fibre sintered filter is compression after the state becoming intricately to be wound around stainless steel fibre system, the equipment of integration by contact position sintering, can change density, adjustment filtering accuracy according to the rugosity of this fiber and decrement.
The additive such as plasticizer or particle can in advance with mixed with resin, also can be mixed in the midway of extruder.In order to add equably, preferably use the mixing arrangements such as static mixer.
Tg ~ the Tg+110 DEG C of film is preferably with chill roll and the film temperature contacting roller side during Elastic Contact roller clamping film.The Elastic Contact roller used with this object can be used in surface and have elastomeric known roller.Elastic Contact roller is also referred to as holds pressure rotary body under the arm, preferably can use disclosed in No. 3194904, Japan Patent, No. 3422798, Japan Patent, No. 2002-36332, Japanese Unexamined Patent Publication, No. 2002-36333, Japanese Unexamined Patent Publication etc. and contact roller.In addition, commercially available Elastic Contact roller can also be used.
During from chill roll stripping film, preferably control tension force and prevent the distortion of film.
In addition, the film as above obtained, preferably by after the operation contacted with chill roll, utilizes stretched operation to stretch.The method stretched preferably can use known roller stretching-machine, stenter etc.Draft temperature preferably carries out in the temperature range of Tg ~ Tg+60 DEG C of resin usually forming film.
Before the film made being wound around, cutting tip and be cut into the width becoming goods, in order to the attaching in preventing from being wound around, scratch, also can implement embossing processing (embossing processing) to two ends.Embossing processing can be heated by the dandy roll of pattern surface with convex-concave and press on film to carry out.Should illustrate, the grip portion of the cloth gripper at film both ends cannot use as goods due to film distortion usually, recycles so cut.
(functional layer)
In the blooming of present embodiment, antistatic backing, back coating, anti-reflection layer, easily slip layer, adhesive linkage can be set, the functional layer such as barrier layer.
(back coating)
In order to prevent curling, be close to, the blooming of present embodiment also can film base material with arrange hard conating opposition side, side face on back coating is set.
As the particle of inorganic compound making an addition to back coating, silica, titanium dioxide, aluminium oxide, zirconia, calcium carbonate, calcium carbonate, talcum, clay, calcined kaolin, baked calcium silicate, acidifying tin, indium oxide, zinc oxide, ITO, afwillite, alumina silicate, magnesium silicate and calcium phosphate can be enumerated.
The amount of the particle contained in back coating is preferably 0.1 ~ 50 quality % relative to binding agent.As binding agent, the cellulose ester resins such as preferred cellulose diacetate.
In addition, the increase of mist degree when arranging back coating is preferably less than 1.5%, and more preferably less than 0.5%, be particularly preferably less than 0.1%.
(anti-reflection layer)
The blooming of present embodiment can be coated with anti-reflection layer on the upper strata of hard conating thus as the antireflection film with anti-external light reflection function.
Anti-reflection layer preferably consider refractive index, thickness, the number of plies, layer order etc. and stacked to make to reduce reflectivity by optical interference.Refractive index lower than the low-index layer of the film base material as supporter, or combines higher than the high refractive index layer of the film base material as supporter and low-index layer and forms by anti-reflection layer preferred index.Be particularly preferably the anti-reflection layer that is made up of more than 3 layers index layers, preferably use different for refractive index from supporting side 3 layers with the stacked anti-reflection layer of the order of middle index layer (refractive index higher than supporter and refractive index lower than the layer of high refractive index layer)/high index layer/low index layer.In addition, also preferably use more than 2 layers high refractive index layers and the alternately stacked 4 layers of anti-reflection layer formed with upper strata of more than 2 layers low-index layers.
Layer as antireflection film is formed, and considers to form described as follows, but is not limited to this.
Film base material/hard conating/low-index layer
Film base material/hard conating/middle index layer/low-index layer
Film base material/hard conating/middle index layer/high index layer/low index layer
Film base material/hard conating/high refractive index layer (conductive layer)/low-index layer
Film base material/hard conating/anti-glare layer/low-index layer
< low-index layer >
Low-index layer preferably containing silica-based particulate, its refractive index preferably 23 DEG C, to measure wavelength 550nm be the scope of 1.30 ~ 1.45.
The thickness of low-index layer is preferably 5nm ~ 0.5 μm, more preferably 10nm ~ 0.3 μm, most preferably is 30nm ~ 0.2 μm.
For low-index layer formation composition, as silica-based particulate, particularly preferably at least comprise more than one and there is outer shell and the inner particle for Porous or cavity.This has outer shell and the inner particle for Porous or cavity is particularly preferably hollow silica system particulate.
Should illustrate, low-index layer the formation organo-silicon compound that also can represent containing following general formula (OSi-1) together in composition or its hydrolysate, or its condensation polymer.
General formula (OSi-1): Si (OR) 4
In formula, R represents the alkyl of carbon number 1 ~ 4.As the organo-silicon compound represented by above-mentioned general formula, specifically, tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan etc. are preferably used.
In addition, low-index layer formation composition also can contain to comprise fluorine atom in the scope of 35 ~ 80 quality % and comprise the fluorochemical of the functional group of bridging property or polymerism for the main compound with thermosetting and/or light solidity.Specifically, be fluoropolymer or fluorine-containing collosol and gel compound etc.As fluoropolymer, such as except the silane compound (such as (ten seven fluoro-1 containing perfluoroalkyl, 1,2,2-tetrahydrochysene decyl) triethoxysilane) hydrolysate or dehydration condensation beyond, can also enumerate fluorine-containing monomer unit and the cross-linking reaction unit fluorinated copolymer as Component units.In addition, solvent, silane coupler, curing agent, surfactant etc. as required also can be added in low-index layer formation composition.
< high refractive index layer >
The refractive index of high refractive index layer preferably 23 DEG C, to measure wavelength 550nm be the scope of 1.4 ~ 2.2.In addition, the thickness of high refractive index layer is preferably 5nm ~ 1 μm, more preferably 10nm ~ 0.2 μm, most preferably is 30nm ~ 0.1 μm.The method of adjustment refractive index can be reached by adding metal oxide microparticle etc. in high refractive index layer.The refractive index of metal oxide microparticle used is preferably 1.80 ~ 2.60, and more preferably 1.85 ~ 2.50.
There is no particular limitation for the kind of metal oxide microparticle, can use the metal oxide with at least one element be selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S.Can the atom of the trace such as doped with Al, In, Sn, Sb, Nb, halogens, Ta in these metal oxide microparticles, in addition, also can be their mixture.Wherein, particularly preferably use and be selected from least a kind of metal oxide microparticle in zirconia, antimony oxide, tin oxide, zinc oxide, indium oxide-Xi (ITO), the tin oxide (ATO) of antimony dopant and zinc antimonates as principal component.Particularly preferably containing zinc antimonates particle.
The average grain diameter of the primary particle of these metal oxide microparticles is 10nm ~ 200nm, is particularly preferably 10nm ~ 150nm.The average grain diameter of metal oxide microparticle can be measured from the electron micrograph that make use of SEM (SEM) etc., also can by utilizing the measurements such as the size distribution meter of dynamic light scattering method or static light scattering method etc.If particle diameter is too small, then easily condense, dispersed variation.If particle diameter is excessive, then mist degree significantly rises, not preferably.The shape of metal oxide microparticle is preferably grain of rice shape, ball shape, cubic, spindle shape, needle-like or indefinite shape.
Metal oxide microparticle also can utilize organic compound to carry out surface treatment.By carrying out finishing with organic compound to the surface of metal oxide microparticle, the dispersion stabilization in organic solvent can be improved, dispersion particle diameter control become easy, and suppress through time cohesion, precipitation.Therefore, the finishing amount in preferred organic compound is 0.1 quality % ~ 5 quality % relative to metal oxide microparticle, is more preferably 0.5 quality % ~ 3 quality %.The example of the organic compound that surface treatment uses comprises polyalcohol, alkanolamine, stearic acid, silane coupler and titanate coupling agent.Wherein be preferably silane coupler.In addition, more than two kinds surface treatments can also be combined.
In addition, high refractive index layer also can contain pi-conjugated system electric conductive polymer.As long as the organic polymer that pi-conjugated system electric conductive polymer main chain is made up of pi-conjugated system then can use.Such as, polythiophene class, multi-metal polypyrrole, polyaniline compound, poly-sub-benzene class, polyacetylene class, poly-sub-phenylethylene class, polyacene class, the sub-vinyl of polythiophene and their copolymer can be enumerated.From the aspect of the easiness of being polymerized, stability, preferred polythiophene class, polyaniline compound, polyacetylene class.
Pi-conjugated system electric conductive polymer just illustrates sufficient electric conductivity, dissolubility to resin glue under without the state replaced, but in order to improve electric conductivity, dissolubility further, also the functional groups such as alkyl, carboxyl, sulfo group, alkoxyl, hydroxyl, cyano group can be imported.The ratio of this polymer and binding agent is preferably 10 ~ 400 mass parts relative to polymer 100 mass parts binding agent, is particularly preferably 100 ~ 200 mass parts relative to polymer 100 mass parts binding agent.
In addition, high refractive index layer also can contain ionic compound.As ionic compound, can enumerate by imidazoles system, pyridine system, ester ring type amine system, aliphatic amine system, aliphatic the cation of system and BF 4 -, PF 6 -deng inorganic ions system, CF 3sO 2 -, (CF 3sO 2) 2n -, CF 3cO 2 -deng the compound etc. that the anion of fluorine system is formed.
(polarizer)
Next, the polarizer of the blooming using present embodiment is described.Polarizer can make with general method.Preferably saponification process is carried out to the rear side of the blooming of present embodiment, use fully saponified type polyvinyl alcohol water solution the blooming of process to be fitted in iodine solution dipping and to stretch and on the face of at least side of polarizing coating that makes.Should illustrate, the blooming of present embodiment of also can fitting on the face of the opposite side of polarizing coating, above-mentioned film base material of also can fitting.
In addition, be used in the dephased optical compensation films of tool (phase retardation film) that length of delay Ro in wavelength 590nm face is 20 ~ 70nm, the length of delay Rt of film thickness direction is 70 ~ 400nm in addition, also can make the polarizer that can amplify the angle of visual field.This polarizer can such as make with the method recorded in Japanese Unexamined Patent Publication 2002-71957 publication.In addition, use further preferably and there is liquid-crystal compounds orientations such as making discotic mesogenic and the optical compensation films of optical anisotropic layer that formed.Such as, optical anisotropic layer can be formed with the method recorded in Japanese Unexamined Patent Publication 2003-98348 publication.
In addition, as the commercially available polarizer membrane base material preferably used, KC8UX2MW, KC4UX, KC5UX can be enumerated, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR-2, KC8UE, KC4UE (Konica Minolta Opto Co., Ltd. system) etc.
Polarizing coating as the main composition element of polarizer is the element of the light of plane of polarization by means of only certain orientation.Now known representational polarizing coating is polyethenol series polarizing coating, wherein has and makes the polarizing coating of iodine staining and the polarizing coating that dichroic dye is dyeed to polyvinyl alcohol mesentery, but deflection film is not limited to them.
Polarizing coating uses polyvinyl alcohol water solution masking, is dyeed by its uniaxial tension, or after dyeing after uniaxial tension, preferably carries out durability process with boron compound and the film that obtains.Polarizing coating preferably uses thickness to be 5 ~ 30 μm, is preferably the polarizing coating of 8 ~ 15 μm.
The one side of the blooming of present embodiment of fitting in the face of this polarizing coating and form polarizer.Preferred utilization with fully saponified polyvinyl alcohol etc. for the bonding agent of the water system of principal component is fitted.
(adhesive layer)
The adhesive layer used at the one side of film base material in order to the baseplate-laminating with liquid crystal cells is preferably optically transparent and the viscoplasticity of display appropriateness, the layer of adhesion properties.
Specifically, as adhesive layer, such as, can use the polymer such as bonding agent or adhesive such as acrylic acid series copolymer, epoxy system resin, polyurethane, silicon-type polymer, polyethers, butyral system resin, polyamide series resin, polyvinyl alcohol resin, synthetic rubber.These materials can be used to form film by seasoning, chemical curing method, thermal curing method, heat melting method, photocuring processes etc., be solidified to form adhesive layer by making it.Wherein, the bonding physical property of acrylic acid series copolymer the most easily controls, and the excellences such as the transparency, weatherability, durability, can preferably use.
< liquid crystal indicator >
By being installed in display unit by the polarizer using the blooming of present embodiment to make, various visual excellent image display device can be made.
The blooming of present embodiment is installed on polarizer, is preferred for the liquid crystal indicator of the various type of drive such as reflection-type, transmission-type, transflective liquid crystal display device or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, OCB type.
In addition, the blooming of present embodiment also can be used with the contact panel parts of the liquid crystal indicator of contact panel.In this case, the durability (damage etc. caused by slip) visuality can be improved, pen being inputted.
< embodiment >
Below, with embodiment, concrete example of the present invention is described, but the present invention is not limited to these embodiments.
(embodiment 1)
Fig. 4 is the sectional view along broadside of the concise and to the point formation of the blooming F representing embodiment 1.Should illustrate, blooming F is that the layer of the cross section symmetry vertical with broadside at center with respect to broadside is formed, therefore in this figure, illustrate only the 1st region R1 in the 1st region R1 of blooming F and the 2nd region R2, eliminate the diagram (the following sectional view occurred too) of the 2nd region R2.
In embodiment 1, use tri cellulose acetate membrane (TAC) as film base material 1, use pentaerythritol diacrylate resin as cured film material.Then, in the broadside of film base material 1, cured film material is continued to be applied to the 2nd region R2 from the 1st region R1, make it solidify by ultraviolet irradiation, form the cured film 2 of elastic modelling quantity 4.5GPa.Should illustrate, ultraviolet irradiation condition is now illumination 100mW/cm 2, exposure 300mJ/cm 2.Thereafter, use dandy roll to carry out embossing processing to blooming F, cured film 2 is formed embossed portion 3, on film base material 1, form embossed portion 4 and make blooming F simultaneously.
Here, the position of the end of the broadside of film base material 1 is set to A.Then, the position that (with A opposition side, end) enters 50mm inside broadside from the A of position is set to D.In this case, the 1st region R1 and the 2nd region R2 is the region (50mm width) between A-D.In addition, the 1st region R1 and the 2nd region R2 separately in, cured film 2 is formed to position B2 along broadside from position B1 on film base material 1, and embossed portion entirety (embossed portion 3+ embossed portion 4) is formed to position C2 in above-mentioned broadside from position C1.Should illustrate, position B1C1 is positioned at A side, end compared with the B2C2 of position.Should illustrate, unless otherwise specified, then position C1 is consistent with position A, and position B2 is consistent with position D.
In embodiment 1, at the 1st region R1 and the 2nd region R2, the forming range of cured film 2 is the 45mm (90% between A-D) between B1-B2, and the forming range of embossed portion entirety (embossed portion 3+ embossed portion 4) is the 15mm between C1-C2.That is, at the 1st region R1 and the 2nd region R2, the forming range of the embossed portion 4 on film base material 1 is the 5mm between A (C1)-B1, and the forming range of the embossed portion 3 in cured film 2 is the 10mm between B1-C2.
In addition, the height t of embossed portion 3 is 10 μm, and the number of the protuberance 3a of embossed portion 3 is 70/cm 2.Should illustrate, the mensuration of the height t of embossed portion 3 is undertaken by contact film thickness gauge TOF-6R (Yamabun Electronics Co., Ltd.), and the mensuration of the number of protuberance 3a is undertaken by microscope VHX-2000 (Co., Ltd. KEYENCE).In addition, the thickness of the film base material 1 of use is 30 μm.
(embodiment 2)
In embodiment 2, at the 1st region R1 and the 2nd region R2, the forming range (between C1-C2) of the embossed portion entirety (embossed portion 3+ embossed portion 4) from film end is set to 8mm, the forming range (between B1-C2) of the embossed portion 3 in cured film 2 is set to 3mm, in addition, blooming F is made similarly to Example 1.
(embodiment 3)
In embodiment 3, except being set to except 1 μm by the height t of embossed portion 3, make blooming F similarly to Example 1.
(embodiment 4)
In embodiment 4, except being set to except 25 μm by the height t of embossed portion 3, make blooming F similarly to Example 1.
(embodiment 5)
In embodiment 5, except the number of the protuberance 3a by embossed portion 3 is set to 10/cm 2in addition, blooming F is made similarly to Example 1.
(embodiment 6)
In embodiment 6, except the number of the protuberance 3a by embossed portion 3 is set to 140/cm 2in addition, blooming F is made similarly to Example 1.
(embodiment 7)
In embodiment 7, the thickness except the film base material 1 by use is set to except 10 μm, makes blooming F similarly to Example 1.
(embodiment 8)
In embodiment 8, the thickness except the film base material 1 by use is set to except 40 μm, makes blooming F similarly to Example 1.
(embodiment 9)
In embodiment 9, ultraviolet irradiation condition is set to illumination 80mW/cm 2, exposure 100mJ/cm 2, by cured film material irradiation ultraviolet radiation, make the elastic modelling quantity of cured film 2 be 4.0GPa, in addition, make blooming F similarly to Example 1.
(embodiment 10)
Fig. 5 is the sectional view along broadside of the concise and to the point formation of the blooming F representing embodiment 10.In embodiment 10, at the 1st region R1 and the 2nd region R2, the forming range (between B1-B2) of cured film 2 is set to 10mm (20% between A-D), the forming range (between C1-C2) of embossed portion entirety (embossed portion 3+ embossed portion 4) is set to 50mm.That is, in the cured film 2 of the 1st region R1 and the 2nd region R2, the forming range (between B1-C2) of embossed portion 3 is set to 10mm.In addition, blooming F is made similarly to Example 1.
(embodiment 11)
Fig. 6 is the sectional view along broadside of the concise and to the point formation of the blooming F representing embodiment 11.In embodiment 11, at the 1st region R1 and the 2nd region R2, the forming range (between B1-B2) of cured film 2 is set to 50mm (100% between A-D), the forming range (between B1-C2) of the embossed portion 3 in this cured film 2 is set to 15mm.Namely, in embodiment 11, the position B1 of the end of cured film 2 is consistent with the position A (C1) of the end of the 1st region R1 and the 2nd region R2, is therefore processed by embossing in cured film 2, only forms embossed portion 3 (film base material 1 not being formed embossed portion 4).In addition, blooming F is made similarly to Example 1.
(embodiment 12)
Fig. 7 is the sectional view along broadside of the concise and to the point formation of the blooming F representing embodiment 12.In embodiment 12, only form cured film 2 at the 1st region R1 and the 2nd region R2, and the position B2 of the end of cured film 2 moves to width end side (A side, position) relative to position D.
More specifically, at the 1st region R1 and the 2nd region R2, the forming range (between B1-B2) of cured film 2 is set to the scope (40% between A-D) from the position A of end along broadside to 20mm, the forming range (between B1-C2) of embossed portion 3 is set to 15mm.Namely, in embodiment 12, the position B1 of the end of cured film 2 is consistent with the position A (C1) of the end of the 1st region R1 and the 2nd region R2, is therefore processed by embossing in cured film 2, only forms embossed portion 3 (film base material 1 not being formed embossed portion 4).In addition, blooming F is made similarly to Example 1.
(embodiment 13)
Fig. 8 is the sectional view along broadside of the concise and to the point formation of the blooming F representing embodiment 13.Embodiment 13 also similarly to Example 12, only form cured film 2 at the 1st region R1 and the 2nd region R2, and the position B2 of the end of cured film 2 moves to width end side (A side, position) relative to position D.
More specifically, at the 1st region R1 and the 2nd region R2, be set to by the forming range of cured film 2 from apart from the position A of end to the position B1 of 10mm inside broadside to the scope (60% between A-D) apart from the 30mm of position A to the position B2 of 40mm inside broadside, the forming range (between C1-C2) of embossed portion (embossed portion 3+ embossed portion 4) is set to 20mm.In this case, in the cured film 2 of the 1st region R1 and the 2nd region R2, the forming range (between B1-C2) of embossed portion 3 is 10mm.In addition, blooming F is made similarly to Example 1.
(embodiment 14)
In embodiment 14, at the 1st region R1 and the 2nd region R2, the forming range (between C1-C2) of the embossed portion (embossed portion 3+ embossed portion 4) from film end is set to 10mm, the forming range (between B1-C2) of the embossed portion 3 in cured film 2 is set to 5mm, in addition, blooming F is made similarly to Example 1.
(embodiment 15)
In embodiment 15, except being set to except 0.5 μm by the height t of embossed portion 3, make blooming F similarly to Example 1.
(embodiment 16)
In embodiment 16, except being set to except 30 μm by the height t of embossed portion 3, make blooming F similarly to Example 1.
(embodiment 17)
In embodiment 17, except the number of the protuberance 3a by embossed portion 3 is set to 5/cm 2in addition, blooming F is made similarly to Example 1.
(embodiment 18)
In embodiment 18, except the number of the protuberance 3a by embossed portion 3 is set to 150/cm 2in addition, blooming F is made similarly to Example 1.
(embodiment 19)
In embodiment 19, ultraviolet irradiation condition is set to illumination 50mW/cm 2, exposure 50mJ/cm 2, by cured film material irradiation ultraviolet radiation, make the elastic modelling quantity of cured film 2 be 3.5GPa, in addition, make blooming F similarly to Example 1.
(comparative example 1)
In comparative example 1, at the 1st region R1 and the 2nd region R2, the forming range (between C1-C2) of the embossed portion (embossed portion 3+ embossed portion 4) from film end is set to 7mm, the forming range (between B1-C2) of the embossed portion 3 in cured film 2 is set to 2mm, in addition, blooming F is made similarly to Example 1.
(comparative example 2)
Fig. 9 is the sectional view along broadside of the concise and to the point formation of the blooming F representing comparative example 2.In comparative example 2, at the 1st region R1 and the 2nd region R2, the forming range (between B1-B2) of cured film 2 is set to 5mm (10% between A-D), the forming range (between C1-C2) of embossed portion (embossed portion 3+ embossed portion 4) is set to 45mm.That is, in comparative example 2, only on the film base material 1 of the 1st region R1 and the 2nd region R2, form embossed portion 4, cured film 2 is not formed embossed portion 3.In addition, blooming F is made similarly to Example 1.
< evaluates >
The blooming F made in above-described embodiment 1 ~ 19, comparative example 1 ~ 2 being wound around, wrapping offset, wrinkling (ゲ ー ジ バ Application De to core direction) (attach, adhesion), volume appearance, film rupture and evaluate, and result is shown in table 1.
[table 1]
Here, the metewand of wrapping offset is as described below.
◎: do not produce wrapping offset completely, well.
Zero: produce wrapping offset a little, but be no problem level.
△: produce wrapping offset further, but be level no problem in practical.
×: in-problem degree ground produces wrapping offset, bad.
Wrinkling metewand is as described below.
◎: do not produce wrinkling completely, well.
Zero: produce wrinkling a little, but be no problem level.
△: produce wrinkling further, but be level no problem in practical.
×: in-problem degree ground produces wrinkling, bad.
The metewand of volume appearance is as described below.
◎: volume is not out of shape, volume appearance is good.
Zero: volume produces warpage a little, but is no problem level.
△: volume produces warpage further, but is level no problem in practical.
×: in-problem degree ground produces the warpage of volume, bad.
The metewand of film fracture is as described below.
◎: the fracture not producing film completely, well.
Zero: the fracture producing film a little, but be no problem level.
△: the fracture producing film further, but be level no problem in practical.
×: in-problem degree ground produces the fracture of film, bad.
As shown in Table 1, in embodiment 1 ~ 19, embossed portion 3 in cured film 2 forms more than 3mm in broadside, for wrapping offset and wrinkling, be good (◎) or no problem level (zero) or level no problem in actual use (△).On the other hand, in comparative example 1 ~ 2, the embossed portion 3 in cured film 2 is less than 3mm in broadside, wrapping offset and wrinklingly all to produce, and is bad (×).Therefore, can saying by continuing to form the embossed portion 3 of more than 3mm in broadside in cured film 2, wrapping offset and wrinkling can be suppressed.
In addition, in embodiment 15, even if embossed portion 3 continued to form more than 3mm in broadside in cured film 2, compared with embodiment 1, also wrapping offset and wrinkling is produced further.Think this is because, the height of embossed portion 3 is little of 0.5 μm, and embossed portion 3 therefore cannot be utilized to suppress wrapping offset and wrinkling fully.
In addition, in embodiment 16, be wound around volume distortion, volume appearance and embodiment 1 are in a ratio of bad result.Think this is because, height greatly to 30 μm of embossed portion 3, therefore when being wound around, protuberance 3a easily swings to inside broadside, and its result, the volume of winding produces warpage further.
On the other hand, in embodiment 1 ~ 14, the height of embossed portion 3 is the scope of 1 ~ 25 μm, wrapping offset, wrinkling, volume appearance be well (◎) or no problem level (zero).Therefore, can say to suppress wrapping offset and adhesion, suppress the distortion of volume simultaneously and make volume appearance good, the height of preferred embossed portion 3 is 1 ~ 25 μm.
In addition, in embodiment 17, even if embossed portion 3 continued to form more than 3mm in broadside in cured film 2, compared with embodiment 1, also wrapping offset and wrinkling is produced further.Think this is because, the number of the protuberance 3a of embossed portion 3 is 5/cm 2, the quantity of protuberance 3a is very few, therefore cannot play the function utilizing embossed portion 3 to suppress wrapping offset and adhesion efficiently.
In addition, in embodiment 18, compared with embodiment 1, the fracture of film in winding, is produced further.Think this is because, the number of carrying out the protuberance 3a of embossed portion 3 is 150/cm 2embossing add man-hour, give grievous injury to film base material 1, thus the broadside of film intensity decline.
On the other hand, in embodiment 1 ~ 14, the number of the protuberance 3a of embossed portion 3 is 10 ~ 140/cm 2, the fracture of wrapping offset, wrinkling, film is good (◎) or no problem level (zero).Therefore, can say that the number of the protuberance 3a of preferred embossed portion 3 is 10 ~ 140/cm in order to suppress wrapping offset, adhesion and film fracture 2.
In addition, in embodiment 19, even if embossed portion 3 continued to form more than 3mm in broadside in cured film 2, compared with embodiment 1, also wrapping offset and wrinkling is produced further.Think this is because, the elastic modelling quantity of cured film 2 is low to moderate 3.5GPa, therefore cannot give required hardness to the embossed portion 3 on the surface being formed at cured film 2, and produces wrapping offset, wrinkling further.
On the other hand, in embodiment 1 ~ 14, the elastic modelling quantity of cured film 2 is more than 4.0GPa, does not see wrapping offset, wrinkling generation.Think this is because, by forming hard embossed portion 3 on the surface of cured film 2, embossed portion 3 reliably play suppress wrapping offset, wrinkling generation function.Therefore, can say the function in order to reliably play the embossed portion 3 suppressing wrapping offset etc., the elastic modelling quantity of preferred consolidation film 2 is more than 4.0GPa.
Utilizability in industry
The present invention such as can be used for the various functional membrane such as protective film for polarizing plate, phase retardation film, angle of visual field amplification film used in liquid crystal indicator.
Symbol description
1 film base material
2 cured film
3 embossed portion
F blooming
R1 the 1st region
R2 the 2nd region

Claims (4)

1. a blooming, is the blooming being formed with cured film on the film base material that thickness is 10 ~ 40 μm, it is characterized in that,
Each region of the both ends 50mm apart from described film base material broadside is set to the 1st region and the 2nd region,
Described cured film is that the mode of the scope of the scope of 20 ~ 100% of broadside to cover described 1st region on described film base material respectively and 20 ~ 100% of the broadside in described 2nd region is formed,
Embossing processing is carried out to the surface of the respective described cured film in described 1st region and described 2nd region being formed after described cured film, thus forms concavo-convex embossed portion,
Described embossed portion forms more than 3mm on the surface of described cured film from each end of this cured film along described broadside.
2. blooming as claimed in claim 1, it is characterized in that, the height of described embossed portion is 1 ~ 25 μm.
3. blooming as claimed in claim 1 or 2, it is characterized in that, the number of the protuberance of described embossed portion is every 1cm 2it is 10 ~ 140.
4. the blooming according to any one of claims 1 to 3, is characterized in that, the elastic modelling quantity of described cured film is more than 4.0GPa.
CN201380048580.5A 2012-09-20 2013-09-06 Optical film Pending CN104640695A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012207297 2012-09-20
JP2012-207297 2012-09-20
PCT/JP2013/074033 WO2014045898A1 (en) 2012-09-20 2013-09-06 Optical film

Publications (1)

Publication Number Publication Date
CN104640695A true CN104640695A (en) 2015-05-20

Family

ID=50341214

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380048580.5A Pending CN104640695A (en) 2012-09-20 2013-09-06 Optical film

Country Status (4)

Country Link
JP (1) JP6048506B2 (en)
KR (1) KR20150043480A (en)
CN (1) CN104640695A (en)
WO (1) WO2014045898A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113811769A (en) * 2019-05-15 2021-12-17 电化株式会社 Membrane carrier and detection kit

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6303429B2 (en) * 2013-11-19 2018-04-04 大日本印刷株式会社 Method for producing functional film and functional film
JP6892751B2 (en) * 2016-11-28 2021-06-23 日東電工株式会社 Double-sided conductive film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002068540A (en) * 2000-08-29 2002-03-08 Toppan Printing Co Ltd Winding member
CN1558824A (en) * 2001-09-25 2004-12-29 ��ʿ��Ƭ��ʽ���� Hard coat film, base on which hard coat film is formed, image display having them
CN101475774A (en) * 2007-10-30 2009-07-08 大日本印刷株式会社 Curable resin composition for hard coat layer and hard coat film
JP2010177457A (en) * 2009-01-29 2010-08-12 Fujimori Kogyo Co Ltd Method for manufacturing rolled transfer film for imprinting and rolled transfer film for imprinting
CN102490401A (en) * 2011-10-29 2012-06-13 合肥乐凯科技产业有限公司 Hardened film for in-mold decoration and preparation method of hardened film

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11156289A (en) * 1997-11-27 1999-06-15 Toppan Printing Co Ltd Method for preventing deformation of taken-up and coating raw sheet
JP2000108228A (en) * 1998-10-06 2000-04-18 Dainippon Printing Co Ltd Roll film and its manufacture
JP2002211803A (en) * 2001-01-15 2002-07-31 Fuji Photo Film Co Ltd Film roll
JP2005224754A (en) * 2004-02-16 2005-08-25 Konica Minolta Opto Inc Manufacturing method of optical film having hard coat layer, hard coat film, polarizing plate, and display unit
JP2006259647A (en) * 2005-02-18 2006-09-28 Konica Minolta Opto Inc Manufacturing method of antireflection film, antireflection film, polarizing plate and liquid crystal display device
JP2008094461A (en) * 2006-10-13 2008-04-24 Fujifilm Corp Packaging method for rolled optical film and its package
JP5909925B2 (en) * 2011-08-26 2016-04-27 コニカミノルタ株式会社 Hard coat film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002068540A (en) * 2000-08-29 2002-03-08 Toppan Printing Co Ltd Winding member
CN1558824A (en) * 2001-09-25 2004-12-29 ��ʿ��Ƭ��ʽ���� Hard coat film, base on which hard coat film is formed, image display having them
CN101475774A (en) * 2007-10-30 2009-07-08 大日本印刷株式会社 Curable resin composition for hard coat layer and hard coat film
JP2010177457A (en) * 2009-01-29 2010-08-12 Fujimori Kogyo Co Ltd Method for manufacturing rolled transfer film for imprinting and rolled transfer film for imprinting
CN102490401A (en) * 2011-10-29 2012-06-13 合肥乐凯科技产业有限公司 Hardened film for in-mold decoration and preparation method of hardened film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113811769A (en) * 2019-05-15 2021-12-17 电化株式会社 Membrane carrier and detection kit

Also Published As

Publication number Publication date
JPWO2014045898A1 (en) 2016-08-18
KR20150043480A (en) 2015-04-22
WO2014045898A1 (en) 2014-03-27
JP6048506B2 (en) 2016-12-21

Similar Documents

Publication Publication Date Title
US7704570B2 (en) Polarizing plate and liquid crystal display apparatus using the same
JP5751249B2 (en) Hard coat film, method for producing the same, polarizing plate, and liquid crystal display device
JP6015469B2 (en) Optical film roll, polarizing plate, and liquid crystal display device
JP5799954B2 (en) Antiglare film, method for producing antiglare film, polarizing plate and liquid crystal display device
CN104220965A (en) Touch-panel-equipped liquid crystal display device
WO2009139284A1 (en) Polarizing plate and liquid crystal display device
WO2012164843A1 (en) Antiglare film, method for producing same, polarizing plate, image display device, member for touch panel
CN104081262A (en) Liquid crystal display device with touch screen panel
JP5971121B2 (en) Manufacturing method of optical film
KR101342183B1 (en) Polarizing plate and liquid crystal display device
CN105849600B (en) Optical film, polarizer and image display device
WO2012026192A1 (en) Hardcoat film, polarizing plate, and liquid crystal display device
JP5948750B2 (en) Antiglare film, method for producing antiglare film, polarizing plate and stereoscopic image display device
WO2014068802A1 (en) Optical film, method for producing optical film, polarizing plate and liquid crystal display device
JP5980465B2 (en) Polarizing plate and liquid crystal display device using the same
CN104640695A (en) Optical film
CN104245156A (en) Process for production of hard coat film
JP2012068562A (en) Image display apparatus
JPWO2011114764A1 (en) Retardation film and polarizing plate provided with the same
JP2013088438A (en) Optical film, production method of the same, and image display device
JP2017102368A (en) Polarizing plate protective film and polarizing plate having the same
JP5707855B2 (en) Method for producing hard coat film
US20120207976A1 (en) Polarizing plate and liquid crystal display employing the same
JP2015132661A (en) Polarizing plate protective film, manufacturing method of the same, polarizing plate, and liquid crystal display device
WO2015104940A1 (en) Cellulose ester film and cellulose ester film manufacturing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20150520

RJ01 Rejection of invention patent application after publication