CN110382648A - Adhesive phase, unilateral protection polarizing coating, image display device and its method for continuous production with adhesive phase - Google Patents

Adhesive phase, unilateral protection polarizing coating, image display device and its method for continuous production with adhesive phase Download PDF

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Publication number
CN110382648A
CN110382648A CN201880015688.7A CN201880015688A CN110382648A CN 110382648 A CN110382648 A CN 110382648A CN 201880015688 A CN201880015688 A CN 201880015688A CN 110382648 A CN110382648 A CN 110382648A
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China
Prior art keywords
adhesive phase
methyl
polarizing coating
mentioned
polarizer
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CN201880015688.7A
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Chinese (zh)
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CN110382648B (en
Inventor
森本有
外山雄祐
藤田雅人
江原卓
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Nittosan Engineering Co Ltd
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Nittosan Engineering Co Ltd
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Priority claimed from JP2018049340A external-priority patent/JP6688822B2/en
Priority claimed from JP2018049345A external-priority patent/JP6730348B2/en
Priority claimed from JP2018063036A external-priority patent/JP7153459B2/en
Application filed by Nittosan Engineering Co Ltd filed Critical Nittosan Engineering Co Ltd
Publication of CN110382648A publication Critical patent/CN110382648A/en
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    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Polarising Elements (AREA)

Abstract

The purpose of the present invention is to provide provide to can inhibit the defect as caused by nano slit and anti-static function and operational excellent adhesive phase and the unilateral protection polarizing coating with adhesive phase with the adhesive phase again.Adhesive phase of the invention contains (methyl) acrylic polymer as basic polymer, above-mentioned (methyl) acrylic polymer contains (methyl) alkyl acrylate that the carbon atom number of (methyl) methyl acrylate and alkyl is 2~12 as monomeric unit, above-mentioned adhesive phase meets following formula (1), wherein, Abs (a): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, the peak absorbance of the antisymmetric stretching vibration of the C-O-C key of (methyl) methyl acrylate is belonged to；Abs (b): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, the peak absorbance of the antisymmetric stretching vibration of the C-O-C key of above-mentioned (methyl) alkyl acrylate is belonged to；Abs (c): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, in 800~900cm‑1Minimum absorbance in range.

Description

Adhesive phase, the unilateral protection polarizing coating with adhesive phase, image display device and its Method for continuous production
Technical field
The unilateral protection polarizing coating with adhesive phase the present invention relates to adhesive phase and with the adhesive phase.It is above-mentioned Unilateral protection polarizing coating with adhesive phase can be individually or to form liquid crystal display device in the form of its optical film has been laminated (LCD), the image display devices such as organic EL display device.
Background technique
For liquid crystal display device, from the point of view of its image forming mode, in the glass base for forming liquid crystal panel surface The two sides configuration polarizing coating of plate is essential.For polarizing coating, usually used is by polyvinyl alcohol film and iodine Etc. the one or two sides of polarizer that is formed of dichroic materials be bonded made of protective film partially using polyvinyl alcohol bonding agent etc. Vibrating diaphragm.
When above-mentioned polarizing coating is fitted in liquid crystal cells etc., adhesive is usually used.In addition, being capable of wink due to having When fixed polarizing coating, without carrying out the drying process for making polarizing coating cementation the advantages that, therefore adhesive can be in advance with viscous The form of mixture layer is arranged at the single side of polarizing coating.That is, in the fitting of polarizing coating, the usually usable list with adhesive phase Protect polarizing coating in side
In addition, polarizing coating, the unilateral protection polarizing coating with adhesive phase are in thermal shock (for example, repeating -30 DEG C and 80 DEG C The thermal shock test of temperature condition is tested at a high temperature of 100 DEG C) harsh environment in, exist and be easy because the contraction of polarizer is answered The variation of power and the problem of the entire absorption axis direction of polarizer cracks (through-wall crack).That is, the list with adhesive phase Protect durability relative to thermal shock of the polarizing coating in above-mentioned harsh environment insufficient in side.In particular, for from slimming Viewpoint is set out and has been used only in the unilateral side with adhesive phase of the unilateral protection polarizing coating of the single side setting protective film of polarizer For protecting polarizing coating, the above-mentioned durability relative to thermal shock is insufficient.In addition, being existed by the through-wall crack that above-mentioned thermal shock causes It is more prone to produce in the case where the becoming large-sized of polarizing coating.
For example, in order to assign the high-durability in hot environment, it has been proposed that using the storage modulus at 23 DEG C be 0.2~ 10MPa and the bonding for protecting polarizing coating as the unilateral side with adhesive phase with a thickness of 2 μm of adhesive phases more than and less than 25 μm Oxidant layer (patent document 1).In addition, in order to also assign good durability in the high temperature environment, it has been proposed that the one of polarizer Face be arranged pressure-sensitive adhesive layer and the another side of polarizer setting the protective layer made of transparent resin film polarizing film in, Use the adhesive layer for the storage modulus for showing 0.15~1MPa within the temperature range of 23~80 DEG C as above-mentioned pressure-sensitive adhesive Oxidant layer (patent document 2).In addition, the generation in order to inhibit above-mentioned through-wall crack, it has been proposed that use the absorption with polarizer The convergent force in the orthogonal direction of axis controls smaller and storage modulus of the adhesive phase at 23 DEG C is the viscous of 0.20MPa or more Adhesive phase (patent document 3) of the mixture layer as the unilateral protection polarizing coating with adhesive phase.In addition, for polarizer also into Go slimming, such as, it has been proposed that optical characteristics as monomer transmissivity, degree of polarization has been carried out to control and show that height takes The slim polarizer (patent document 4) of tropism.
However, in patent document 1, even if meeting durability, also due to the thickness of polarizer is up to 25 μm and can not Prevent the generation of the through-wall crack as caused by the shrinkage stress of polarizer.In addition, Patent Documents 1 to 3 are to improve band adhesive phase The durability of unilateral protection polarizing coating be project, therefore, the boric acid used in polarizer is relatively more.It it is known that: polarizer Contained in boric acid more than in the case where special value, when heating, can promote to be crosslinked because of boric acid, and the shrinkage stress of polarizer becomes Greatly, therefore, not preferred from the viewpoint of the generation for inhibiting through-wall crack.That is, in Patent Documents 1 to 3, although can pass through It controls the storage modulus of adhesive phase and prevents through-wall crack to a certain extent, but cannot say and can sufficiently inhibit through-wall crack It generates.
On the other hand, polarizer is also thinned.It is being thinned the unilateral protection polarizing coating with adhesive phase Used in the case where polarizer, the variation of the shrinkage stress of polarizer becomes smaller.It follows that if be made have passed through it is slim The polarizer of change is then able to suppress the generation of above-mentioned through-wall crack.
It is well known, however, that in the unilateral protection polarizing coating with adhesive phase that is inhibited of generation of above-mentioned through-wall crack, In the case where controlling optical characteristics as described in Patent Document 4 and being thinned polarizer (for example, thickness is made to reach 12 μm or less In the case where), when being impacted to the unilateral protection polarizing coating load machinery with adhesive phase (including polarizer side is applied and is based on The case where load of convex folding), superfine gap (hereinafter also referred to nanometer can be locally generated in the absorption axis direction of polarizer Slit).It is also known that the generation of above-mentioned nano slit and the size of polarizing coating and irrelevant.It is further known that using in polarizer Two sides have protective film two sides protection polarizing coating in the case where, above-mentioned nano slit will not be generated.In addition, being produced in polarizer In the case where having given birth to through-wall crack, the stress on through-wall crack periphery will be released, therefore through-wall crack will not be generated adjacently, but For nano slit, it is known that not only can individually generate, but also can adjacently generate.It is also known that through-wall crack has Along the progressivity that the absorption axis direction for the polarizer for producing crackle extends, but nano slit does not have above-mentioned progressivity.By This is it is found that above-mentioned nano slit is being thinned in the unilateral protection polarizing coating that is inhibited of generation of through-wall crack Polariscope and the new project generated in the case that optical characteristics is controlled in given range, be by with it is conventionally known above-mentioned The project that the different phenomenon of through-wall crack causes.
In addition, above-mentioned nano slit is superfine, therefore can not detected in common environment.Therefore, though Nano slit is produced on polarizer, it is also difficult to the unilateral side with adhesive phase is only confirmed according to light leakage and simply observing Protect the defect of polarizing coating.That is, be usually by unilateral side protection polarizing coating production strip it is membranaceous and using automatic visual inspection and Defect inspection is carried out, but is difficult to detected nano slit as defect by the defect inspection.It is also known that above-mentioned The defect as caused by nano slit can be by fitting in image display panel for the unilateral protection polarizing coating with adhesive phase Glass substrate etc. be placed in heating environment in the case where, nano slit occurs the extension to width direction and detects (example Such as, the presence or absence of above-mentioned light leakage).
Therefore, for having used the unilateral side with adhesive phase of slim polarizer to protect polarizing coating, expect not only to inhibit to pass through Through cracks line also inhibits the defect as caused by nano slit.Further, for the unilateral protection polarizing coating with adhesive phase, Due to have with two sides the polarizing coating of the two sides protection structure of protective film compared to be it is relatively thin, be easy to cause in operation inclined Warpage, fracture occur for vibrating diaphragm.
In order to inhibit the defect as caused by above-mentioned nano slit, it has been proposed that in the unilateral protection polarizing coating with adhesive phase Polarizer and adhesive phase between be arranged hyaline layer (overlay) technology (patent document 5).By the way that hyaline layer is arranged, right Above-mentioned polarizing coating becomes to be not susceptible to bend when above-mentioned polarizing coating application external stress, therefore can inhibit the generation of nano slit.
In addition, the unilateral protection polarizing coating with adhesive phase is pasted on liquid crystal cells when manufacturing liquid crystal display device When, mold release film is removed from the adhesive phase of the unilateral protection polarizing coating with adhesive phase, but remove the mold release film to generate Electrostatic.So, the electrostatic of generation will affect the orientation of the liquid crystal inside liquid crystal display device, cause bad.In addition, sometimes It can occur to show unevenness as caused by electrostatic when using liquid crystal display device.The generation of electrostatic for example can be by polarizing coating Outer surface forms antistatic layer and inhibits, but its effect is small, there are problems that fundamentally preventing electrostatic from generating.Therefore, In order to inhibit its generation in the underlying position that electrostatic generates, it is desirable that assign anti-static function to adhesive phase.As to bonding The method of oxidant layer imparting anti-static function, it has been proposed that for example cooperate ionic compound in the adhesive for forming adhesive phase Scheme (patent document 6~8).Specifically, propose in patent document 6 be combined with alkali metal salt and/or it is organic sun from Son-anion salt pressure-sensitive adhesive for optical films composition.In patent document 7, the bonding as the polarizing coating with adhesive phase The raw material of oxidant layer, propose containingThe adhesive composition of anion salt and alkali metal salt.In patent document 8, as The raw material of the adhesive phase of adhesion type polarizing film proposes the adhesive composition containing alkali metal salt.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-44211 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2008-197309 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2013-72951 bulletin
Patent document 4: No. 4751481 specifications of Japanese Patent No.
Patent document 5: No. 6077618 specifications of Japanese Patent No.
Patent document 6: Japanese Unexamined Patent Publication 2015-199942 bulletin
Patent document 7: Japanese Unexamined Patent Publication 2014-48497 bulletin
Patent document 8: Japanese Unexamined Patent Publication 2012-247574 bulletin
Summary of the invention
Problems to be solved by the invention
However, the case where being combined with ionic compound in the adhesive phase of the unilateral protection polarizing coating with adhesive phase Under, if the unilateral protection polarizing coating with adhesive phase is exposed in humidified ambient, existing causes resisting for adhesive phase quiet The problems such as Electricity Functional reduction or polarizer deteriorate and so-called decoloration occur, degree of polarization reduces.
In addition, the unilateral protection polarizing coating with adhesive phase to be fitted in the glass substrate etc. to form liquid crystal panel surface When there is foreign matter, bubble to be mixed into and have occurred fitting mistake in the case where, need to remove above-mentioned polarizing coating from glass substrate etc..Make Protect polarizing coating since polarizer is thin with the unilateral side with adhesive phase of slim polarizer, and only setting on one side in polarizer It is equipped with protective film, therefore, whole thickness is very thin.Therefore, the list with adhesive phase of existing slim polarizer has been used Side protection polarizing coating there are problems that being easy to happen fracture when removing from glass substrate etc..
The purpose of the present invention is to provide can inhibit the defect as caused by nano slit and anti-static function and again operate Property the excellent adhesive phase and unilateral protection polarizing coating with adhesive phase with the adhesive phase.
In addition, the purpose of the present invention is to provide the images with the above-mentioned unilateral protection polarizing coating with adhesive phase to show Device and its method for continuous production.
Solution to the problem
It is that present inventor etc. has made intensive studies as a result, it has been found that, using following adhesive phases, can solve above-mentioned Problem, so as to complete the present invention.
That is, containing (methyl) acrylic polymer the present invention relates to a kind of adhesive phase is used as basic polymer,
Wherein, it is 2 that above-mentioned (methyl) acrylic polymer, which contains (methyl) methyl acrylate and the carbon atom number of alkyl, ~12 (methyl) alkyl acrylate as monomeric unit,
Above-mentioned adhesive phase meets following formula (1).
Abs (a): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, (methyl) third is belonged to The peak absorbance of the antisymmetric stretching vibration of the C-O-C key of e pioic acid methyl ester；
Abs (b): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, above-mentioned (first is belonged to Base) alkyl acrylate C-O-C key antisymmetric stretching vibration peak absorbance；
Abs (c): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, in 800~900cm-1Model Enclose interior minimum absorbance.
The inventors of the present invention to the material of the adhesive phase for being set to polarizing coating, with the generation quantity of nano slit, antistatic Further investigation has been repeated in function and relationship operational again, as a result, it has been found that, the adhesive phase for meeting above-mentioned formula (1) can be effective Ground inhibits the defect as caused by nano slit, and anti-static function and operational excellent again.Specifically, by using (first Base) methyl acrylate as the material of adhesive phase, i.e. (methyl) acrylic polymer comonomer, it can be achieved that adhesive The high resiliency of layer.Thus, it is not easy to generate nano slit in polarizer.Moreover, the content of (methyl) methyl acrylate is more. More adhesive phase can be made to reach high resiliency, therefore be less susceptible to generate nano slit in polarizer.However, (methyl) acrylic acid first Ester can improve the cohesiveness of (methyl) acrylic polymer, and therefore, the content of (methyl) methyl acrylate is more, then adhesive The bonding force of layer is higher, then operability is poorer.In addition, the content of (methyl) methyl acrylate is more, then the movement of antistatic agent More can due to (methyl) acrylic polymer steric hindrance and be suppressed, the anti-static function of adhesive phase drop It is low.As previously mentioned, the inventors of the present invention think, (methyl) acrylic acid first of the comonomer as (methyl) acrylic polymer The content of ester can generation quantity on nano slit, the anti-static function of adhesive phase and operability is brought and significantly affected again.And And the inventors of the present invention have found, are totally reflected measuring method (Attenuated Total Reflection, ATR method) to bonding utilizing In the IR measurement that oxidant layer carries out, relative to the C-O-C for belonging to (methyl) alkyl acrylate that atomic number of alkyl carbon is 2~12 The peak absorbance of the antisymmetric stretching vibration of key belongs to the antisymmetric stretching vibration of the C-O-C key of (methyl) methyl acrylate Peak absorbance be 0.30 adhesive phase more than and less than 0.48, the defect as caused by nano slit can be effectively inhibited, into And excellent anti-static function and operational again can be had both.
It is preferred that above-mentioned adhesive phase contains alkali metal salt, also, preferably comprises and operate improver again.
Additionally, it is preferred that above-mentioned adhesive phase with a thickness of 25 μm or less.
Moreover, it relates to which a kind of unilateral protection polarizing coating with adhesive phase, has only in the single side of polarizer Protect polarizing coating and in the polarizer side of above-mentioned unilateral protection polarizing coating directly or across overlay in unilateral side with protective film With above-mentioned adhesive phase.
It is preferred that above-mentioned polarizer with a thickness of 12 μm or less.
Additionally, it is preferred that above-mentioned polarizer contains polyvinyl alcohol resin, and by monomer transmissivity T and degree of polarization P table The mode that the optical characteristics shown meets the condition of following formula is constituted:
P >-(100.929T-42.4- 1) × 100 (wherein, T < 42.3) or
P >=99.9 (wherein, T >=42.3).
Additionally, it is preferred that it is 25 weight % boric acid below that above-mentioned polarizer, which contains relative to polarizer total amount,.
Diaphragm can be set on the adhesive phase of the above-mentioned unilateral protection polarizing coating with adhesive phase.It is arranged septate Unilateral protection polarizing coating with adhesive phase can be used in the form of coiling body.
Moreover, it relates to the image display device with the above-mentioned unilateral protection polarizing coating with adhesive phase.
Moreover, it relates to which a kind of method for continuous production of image display device, this method include following processes: will be from The coiling body of the above-mentioned unilateral protection polarizing coating with adhesive phase is continuously sent out and is bonded by the above-mentioned band that above-mentioned diaphragm transports The unilateral protection polarizing coating of oxidant layer continuously fits in the surface of image display panel via above-mentioned adhesive phase.
The effect of invention
The unilateral protection polarizing coating with adhesive phase of the invention due to above-mentioned adhesive phase, even if not setting The generation of nano slit can also be effectively inhibited by setting overlay.In addition, the unilateral protection polarization of the invention with adhesive phase Process of the film since setting overlay can be omitted, compared with the traditional method for being provided with overlay, production can be improved Property.In addition, the anti-static function of the unilateral protection polarizing coating of the invention with adhesive phase is excellent, therefore, it is not susceptible to decolourize. In addition, the unilateral protection polarizing coating of the invention with adhesive phase is operational again excellent, therefore, even if having used slim In the case where polariscope, above-mentioned polarizing coating can also be removed, from glass substrate etc. without being broken.
Detailed description of the invention
Fig. 1 is an example of the diagrammatic cross-section of the unilateral protection polarizing coating of the invention with adhesive phase.
Fig. 2 is an example of the schematic diagram compared to nano slit caused by polarizer and through-wall crack.
Fig. 3 is the schematic diagram that the assessment item being related to the nano slit of Examples and Comparative Examples is illustrated.
Fig. 4 be show involved in the evaluation of Examples and Comparative Examples by nano slit cause crackle photo one Example.
Fig. 5 is an example of the diagrammatic cross-section of the continuous manufacture system of image display device.
Symbol description
1 polarizer
2 protective films
3 adhesive layers etc.
4 adhesive phases
5,5a, 5b diaphragm
6,6a, 6b surface protection film
10 unilateral protection polarizing coatings
The 11 unilateral protection polarizing coatings with adhesive phase
The coiling body (volume) of the unilateral protection polarizing coating of 20a, 20b with adhesive phase
Unilateral protection polarizing coating (belt surface protective film) of 21a, 21b with adhesive phase
The continuous manufacture system of 100 image display devices
101a, 101b polarizing coating supply unit
The continuous releasing portion 151a, 151b
152a, 152b cutting part
153a, 153b stripping portion
154a, 154b reeling end
201a, 201b sticking part
300 configuration replacement portions
P image display panel
The transport portion of X image display panel
Specific embodiment
Hereinafter, the unilateral protection polarizing coating to of the invention with adhesive phase is illustrated referring to Fig.1.Band of the invention is viscous The unilateral protection polarizing coating 11 of mixture layer is for example with unilateral side protection polarizing coating 10 and adhesive phase 4.Adhesive phase 4 is the present invention Adhesive phase.As shown in Figure 1, unilateral protection polarizing coating 10 only has protective film 2 in the single side of polarizer 1.Polarizer 1 and guarantor Cuticula 2 is laminated on together across adhesive layer 3 (and adhesive phase, lower coating (priming coat) etc. press from both sides interlayer).It needs It is bright, although not shown, but for polarizing coating 10 is protected in unilateral side, adhesive layer can be set on protective film 2 or to guarantor After cuticula 2 implements activation, the adhesive layer and adhesive layer is laminated.In addition, although not shown, but multi-disc guarantor can be set Cuticula 2.Multi-disc protective film 2 can pass through adhesive layer 3 (and adhesive phase, lower coating (priming coat) etc. press from both sides interlayer) layer It is folded.
In addition, as shown in Figure 1, the adhesive phase 4 in the unilateral protection polarizing coating 11 of the invention with adhesive phase is arranged In 1 side of polarizer of unilateral protection polarizing coating 10.In addition, although not shown, but can be between polarizer 1 and adhesive phase 4 Overlay is set.Above-mentioned overlay is not particularly limited, and can be used in such as No. 6077618 specifications of Japanese Patent No. and records Well known hyaline layer etc..It should be noted that can be in the viscous of the unilateral protection polarizing coating 11 of the invention with adhesive phase Diaphragm 5 is arranged in mixture layer 4 can be set surface protection film 6 in its opposite side.The unilateral protection with adhesive phase of Fig. 1 In polarizing coating 11, thus it is shown that the case where being not only provided with diaphragm 5 but also being provided with surface protection film 6.At least the band with diaphragm 5 is viscous The unilateral protection polarizing coating 11 (further with the polarizing coating of surface protection film 6) of mixture layer can be made in the form of coiling body With as described later, for the unilateral protection with adhesive phase that for example will continuously send out from coiling body and transported using diaphragm 5 Polarizing coating 11, by it is suitable for fitting in the mode on the surface of image display panel (hereinafter also referred to via the adhesive phase 4 " volume to plate (roll-to-panel) mode ", typical situation can refer to No. 4406043 specifications of Japanese Patent No.) in be to have Benefit.The viewpoints such as the warpage of the display panel after inhibiting fitting, the generation for inhibiting nano slit are, it is preferable to use in Fig. 1 The unilateral protection polarizing coating with adhesive phase recorded.
Fig. 2 is the schematic diagram that the nano slit a that will be generated in polarizer and through-wall crack b are compared.Fig. 2 (A) is shown The nano slit a, Fig. 2 (B) generated on polarizer 1 shows the through-wall crack b generated on polarizer 1.Nano slit a It is generated because of mechanical shock, the nano slit a locally generated along the absorption axis direction of polarizer 1 can not be by initial generate It confirms, but (for example, 80 DEG C or 60 DEG C, 90%RH) can be confirmed based on extension in the direction of the width in thermal environment.Separately On the one hand, nano slit a is considered not having the progressivity extended along the absorption axis direction of polarizer.In addition, above-mentioned nanometer is narrow The generation of seam a is considered and the size of polarizing coating and irrelevant.Nano slit a not only can be generated individually, but also also can sometimes Adjacently generate.On the other hand, through-wall crack b is generated because of thermal shock (for example, thermal shock test).Through-wall crack have along Produce the progressivity that the absorption axis direction of the polarizer of crackle extends.In the case where producing through-wall crack b, periphery Stress is released, therefore through-wall crack will not be generated adjacently.
<polarizer>
In the present invention, from the viewpoint of being thinned and inhibiting the generation of through-wall crack, the thickness of polarizer is preferably 12 μm hereinafter, more preferably 10 μm hereinafter, further preferably 8 μm hereinafter, still more preferably be 7 μm hereinafter, particularly preferably It is 6 μm or less.On the other hand, the thickness of polarizer is preferably 1 μm or more.Such slim polarizer due to uneven thickness is few, Visibility is excellent, and change in size is few, therefore the excellent in te pins of durability relative to thermal shock.
The polarizer for having used polyvinyl alcohol resin can be used in polarizer.As polarizer, it can be mentioned, for example make iodine, two Dichroic substance as color dyestuff is adsorbed in polyvinyl alcohol film, part formalizing polyvinyl alcohol film, ethylene-acetate The hydrophilic macromolecule films such as the partly-hydrolysed film of vinyl ester copolymers class and carry out film obtained from simple tension, polyvinyl alcohol it is de- Polyenoid based oriented film such as dehydrochlorinated products of water process object, polyvinyl chloride etc..In these, preferably by polyvinyl alcohol film and iodine Etc. dichroic substances formed polarizer.
Being dyed with iodine to polyvinyl alcohol film and carry out polarizer made of simple tension for example can be by by polyvinyl alcohol It is impregnated in the aqueous solution of iodine 3~7 times for dyeing and being stretched to former length and makes.As needed, also may include boric acid, Or zinc sulfate, zinc chloride etc., it can also be impregnated in the aqueous solution of potassium iodide etc..Further, it also can according to need and contaminating Polyvinyl alcohol film immersion is washed in water before color.By being washed to polyvinyl alcohol film, in addition to that can wash away Other than the dirt of polyvinyl alcohol film surface, antiblocking agent, also having makes polyvinyl alcohol membrane swelling to prevent dyeing uneven Deng uneven effect.Stretching can be carried out after being dyed using iodine, can also be stretched with Edge Coloring side, in addition it can It is dyed after being stretched using iodine.It can also be stretched in the aqueous solution of boric acid, potassium iodide etc. or water-bath.
From drawing stability, optical durability aspect, preferably polarizer contains boric acid.In addition, from inhibiting to run through The generation of crackle and nano slit inhibits from the perspective of expanding, and boric acid content contained in polarizer is total relative to polarizer Amount be preferably 25 weight % hereinafter, further preferably 20 weight % hereinafter, further preferably 18 weight % hereinafter, further Preferably 16 weight % or less.When the boric acid content contained in polarizer is more than 25 weight %, even if being thinned polarizer Thickness (such as 12 μm of thickness or less) in the case where, be also easy to cause the shrinkage stress of polarizer to increase, generate through-wall crack, Therefore not preferably.On the other hand, total relative to polarizer from the viewpoint of the drawing stability of polarizer, optical durability The boric acid content of amount is preferably 10 weight % or more, more preferably 12 weight % or more.
As representative slim polarizer, can enumerate in Japanese Patent No. No. 4751486 specifications, Japanese Patent No. No. 4751481 specifications, No. 4815544 specifications of Japanese Patent No., Japanese Patent No. No. 5048120 specifications, Japan Patents No. 2014/077636 No. 5587517 specification, No. 2014/077599 pamphlet of International Publication No., International Publication No. pamphlet The slim polarizer that the slim polarizer or the manufacturing method by recording in these documents recorded in obtain.
It is preferred that above-mentioned polarizer meets the condition of following formula with the optical characteristics that is indicated by monomer transmissivity T and degree of polarization P Mode is constituted:
P >-(100.929T-42.4- 1) × 100 (wherein, T < 42.3) or
P >=99.9 (wherein, T >=42.3).
Mainly, the polarizer constituted in a manner of meeting above-mentioned condition has as the liquid for having used large-scale display element Performance required by brilliant TV display.Specifically, contrast is 1000:1 or more and maximum brightness is 500cd/m2With On.As other purposes, such as the visible side of organic EL display device can be fitted in.
On the other hand, macromolecule (such as poly- second of the polarizer constituted in a manner of meeting above-mentioned condition due to being constituted it Enol class macromolecule) display high orientation, therefore be combined with each other with slim (such as with a thickness of 12 μm or less), it can make and be polarized The tensile break stress in the orthogonal direction of the absorption axis direction of mirror significantly becomes smaller.As a result, for example in the manufacturing process of polarizing coating In when being exposed to the mechanical shock more than the tensile break stress, generate the possibility of nano slit in the absorption axis direction of polarizer Property is high.Therefore, the present invention is particularly suitable for (or having used its band viscous using the unilateral protection polarizing coating of the polarizer The unilateral protection polarizing coating of mixture layer).
It is including the process stretched with the state of laminated body and the process dyed as above-mentioned slim polarizer Preparation method in, from the viewpoint of can be stretched to high magnification to make polarizing properties improve, preferably by such as Japanese Patent No. No. 4751481 No. 4751486 specifications, Japanese Patent No. specifications, as recording in No. 4815544 specifications of Japan Patent Include slim polarizer obtained from the preparation method of the process stretched in boric acid aqueous solution, particularly preferably pass through record Being included in boric acid aqueous solution in No. 4815544 No. 4751481 specifications of Japanese Patent No., Japan Patent specifications carries out Slim polarizer obtained from the preparation method of the process stretched in atmosphere is secondarily carried out before stretching.These are slim to be polarized Mirror can be by including by polyvinyl alcohol resin (hereinafter also referred to PVA resinoid) layer and stretching resin base material with laminated body The preparation method of process and the process dyed that state is stretched and obtain.If it is the preparation method, even if then PVA resinoid Layer it is relatively thin, also can by be stretched with resin base material it is supported and do not generating by stretch caused by be broken a problem that In the case of stretched.
<protective film>
As constitute said protection film material, preferably the transparency, mechanical strength, thermal stability, moisture barrier, respectively The material excellent to the same sex etc..It can be mentioned, for example: the polyesters such as polyethylene terephthalate, polyethylene naphthalate The acrylic polymers such as the cellulosic polymers such as polymer, cellulose diacetate, cellulose triacetate, polymethyl methacrylate Close styrenic polymers, the polycarbonate polymers such as object, polystyrene, acrylonitritrile-styrene resin (AS resin) etc.. In addition, the example as the polymer for forming said protection film, can also enumerate: polyethylene, polypropylene, ring system have norborneol Polyolefin polymers, vinyl chloride polymer, nylon, aromatic series as the polyolefin of alkene structure, ethylene-propylene copolymer The acylamide polymers such as polyamide, acid imide polymer, sulfone quasi polymer, polyether sulfone polymer, polyether-ether-ketone Type of Collective Object, polyphenylene sulfide quasi polymer, vinyl alcohol polymer, vinylidene chloride quasi polymer, vinyl butyral quasi polymer, aromatic ester Quasi polymer, polyformaldehyde quasi polymer, epoxide polymer or blend of above-mentioned polymer etc..
It should be noted that also may include a kind of any of the above additive appropriate in protective film.It, can as additive Enumerate for example: ultraviolet absorbing agent, antioxidant, lubricant, plasticizer, release agent, anti-coloring agent, fire retardant, nucleating agent, resist it is quiet Electric agent, pigment, colorant etc..The content of above-mentioned thermoplastic resin in protective film is preferably 50~100 weight %, more preferably 50~99 weight %, further preferably 60~98 weight %, particularly preferably 70~97 weight %.Above-mentioned heat in protective film The content of plastic resin be in 50 weight % situations below exist be unable to fully show thermoplastic resin intrinsic height thoroughly The hidden danger of bright property etc..
As said protection film, phase difference film, brightness enhancement film, diffusion barrier etc. also can be used.It, can as phase difference film The phase difference film for the phase difference that enumerating is 40nm or more with front phase difference and/or thickness direction phase difference is 80nm or more. Front phase difference is usually controlled in the range of 40~200nm, and thickness direction phase difference is usually controlled in the range of 80~300nm. Use phase difference film as in the case where protective film, which is also used as polarizer protective film to function, therefore can Seek to be thinned.
As phase difference film, it can enumerate and carry out thermoplastic resin film made of simple tension processing or biaxial tension processing Birefringence film.Temperature, stretching ratio of above-mentioned stretching etc. can according to phase difference value, the material of film, thickness and suitably set.
The thickness of protective film can be suitably determined, but set out in terms of strength, operability, thin layer, etc., usually It is 1~500 μm or so.Preferably 1~300 μm, more preferably 5~200 μm, further preferably 5~150 μm, particularly preferably For 5~80 μm of slim situation.
Hard conating, anti-reflection layer, anti adhering layer, expansion can be set in the not one side Nian Jie with polarizer of said protection film Dissipate the functional layers such as layer or antiglare layer.It should be noted that above-mentioned hard conating, anti-reflection layer, anti adhering layer, diffusion layer, antiglare layer Etc. functional layers other than it can be set to protective film itself, can also additionally be arranged to the layer different from protective film.
<folder interlayer>
Said protection film and polarizer can press from both sides interlayer and layer across adhesive layer, adhesive phase, lower coating (priming coat) etc. It is folded.At this point, the two is laminated in a manner of no the air gap preferably by folder interlayer.Said protection film and polarizer preferably across Adhesive layer and be laminated.
Adhesive layer can be formed using bonding agent.The type of bonding agent is not particularly limited, and various bonding agents can be used.On As long as the optically transparent layer of adhesive layer is stated then to be not particularly limited, as bonding agent, can be used aqueous, solvent borne, The bonding agent of the various forms such as hot melt, active energy ray curable, but preferably aqueous adhesive or active energy beam Curing type bonding agent.
As aqueous adhesive, can enumerate isocyanates bonding agent, polyvinyl alcohol bonding agent, gelatin class bonding agent, Ethylene base system latex class, waterborne polyester etc..Aqueous adhesive is usually used in the form of the bonding agent formed by aqueous solution, is led to Solid component often containing 0.5~60 weight %.
Active energy ray curable bonding agent is by electron beam, ultraviolet light (radical-curable, cationic curing Type) isoreactivity energy-ray carries out cured bonding agent, and it can in the form of for example electronic beam solidified, ultraviolet hardening It uses.Radical UV curing type bonding agent for example can be used in active energy ray curable bonding agent.By radical UV curing type Active energy ray curable bonding agent as ultraviolet hardening and in the case where use, which contains radical polymerization Conjunction property compound and Photoepolymerizationinitiater initiater.
The application pattern of bonding agent can suitably be selected according to viscosity, the target thickness of bonding agent.As application pattern Example, it can be mentioned, for example: reversed spreader, gravure coater (directly, reversed or hectograph), the reversed spreader of bar type, roller coating Machine, die coating machine, wire rod coating, dip coated device, bar coater etc..In addition, the modes such as impregnation method may be appropriately used in coating.
In addition, for the coating of above-mentioned bonding agent, using aqueous adhesive etc., preferably so that most end form At the thickness of adhesive layer reach the mode of 30~300nm and carry out.The thickness of above-mentioned adhesive layer is more preferably 60~ 250nm.On the other hand, in the case where using active energy ray curable bonding agent, preferably so that the thickness of above-mentioned adhesive layer The mode that degree reaches 0.1~200 μm carries out.More preferably 0.5~50 μm, further preferably 0.5~10 μm.
It should be noted that when the stacking of mirror and protective film is polarized, it can be between protective film and adhesive layer Adhesive layer is set.Adhesive layer using for example with polyester backbone, polyether skeleton, polycarbonate backbone, polyurethane skeleton, The various resins of organic silicon, polyamide backbone, polyimide backbone, polyvinyl alcohol skeleton etc. are formed.These fluoropolymer resins It can be used alone or two or more is applied in combination.In addition, can also be added other in the formation of adhesive layer Additive.Specifically, the stabilizers such as tackifier, ultraviolet absorbing agent, antioxidant, heat-resisting stabilizing agent can be further used Deng.
In general, adhesive layer is pre-set on protective film, and make the adhesive layer of the protective film via adhesive layer Side and polarizer are laminated.Being formed for adhesive layer can be protected by the way that the forming material of adhesive layer to be coated on using well known technology On cuticula and it is dried to carry out.Thickness, coating for the forming material of adhesive layer, after being usually considered that drying Smoothness etc. and be prepared into being diluted to the solution of debita spissitudo.Thickness after the drying of adhesive layer is preferably 0.01~ 5 μm, more preferably 0.02~2 μm, further preferably 0.05~1 μm.It should be noted that adhesive layer can be set it is more Layer, but in this case it is also preferred that the overall thickness of adhesive layer is made to fall in above range.
Adhesive phase is formed by adhesive.As adhesive, various adhesives can be used, it can be mentioned, for example: rubber is viscous Mixture, silicone adhesive category, carbamates adhesive, vinyl alkyl ethers adhesive, gathers acrylic adhesives Vinyl pyrrolidone class adhesive, polyacrylamide adhesive, cellulose family adhesive etc..It can correspond to above-mentioned adhesive Type and select the base polymer of adhesiveness.It is excellent from optical transparence, show suitable profit in above-mentioned adhesive The excellent aspect such as adhesion characteristic as moist, coherency and cementability and weatherability, heat resistance is set out, it is preferable to use propylene Acrylic binder.
Lower coating (priming coat) is formed to improve the adaptation of polarizer and protective film.As composition primary coat The material of layer, as long as playing base material film and polyvinyl alcohol resin layer both of which the material of a degree of strong closing force Material is then not particularly limited.For example, the excellent thermoplastic resins etc. such as the transparency, thermal stability, draftability can be used.As heat Plastic resin, it can be mentioned, for example: acrylic resin, polyolefin resin, polyester resin, polyvinyl alcohol resin or it Mixture.
<adhesive phase>
The adhesive phase of the invention for being set to above-mentioned unilateral protection polarizing coating contains (methyl) acrylic polymer work For basic polymer.Above-mentioned (methyl) acrylic polymer contains (methyl) acrylic acid that the carbon atom number of alkyl is 2~12 Arrcostab and (methyl) methyl acrylate are as monomeric unit.Moreover, adhesive phase of the invention meets following formula (1).It needs Illustrate, the alkyl of above-mentioned (methyl) alkyl acrylate optionally has various substituent groups.In this case, the carbon of abovementioned alkyl Atomicity does not include the carbon atom number of above-mentioned substituent group.
Abs (a): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, (methyl) third is belonged to The peak absorbance of the antisymmetric stretching vibration of the C-O-C key of e pioic acid methyl ester
Abs (b): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, above-mentioned (first is belonged to Base) alkyl acrylate C-O-C key antisymmetric stretching vibration peak absorbance
Abs (c): in the IR measurement carried out using total reflection measuring method to above-mentioned adhesive phase, in 800~900cm-1Model Enclose interior minimum absorbance.
The peak of the antisymmetric stretching vibration of the C-O-C key of (methyl) methyl acrylate is belonged in 1100~1130cm-1's Range occurs.In addition, belonging to the peak of the antisymmetric stretching vibration of the C-O-C key of above-mentioned (methyl) alkyl acrylate 1150 ~1260cm-1Range occur.
Abs (c) is in 800~900cm-1The absorbance of minimum absorbance, i.e. baseline in range.
Above-mentioned formula (1) IR parameter ((Abs (a)-Abs (c))/(Abs (b)-Abs (c))) not in above-mentioned numberical range In the case where interior, the crackle that will lead to adhesive phase inhibits function, again operability or any characteristic of anti-static function to be deteriorated.
When forming adhesive phase of the invention, acrylic adhesives are used.The optical transparence of acrylic adhesives It is excellent, the adhesion characteristic of suitable wetability, coherency and cementability is shown, weatherability, heat resistance etc. are excellent, therefore, fit In the forming material as adhesive phase.
As above-mentioned acrylic adhesives, the acrylic acid with (methyl) acrylic polymer for basic polymer is used Class adhesive, and it is somebody's turn to do (methyl) alkyl acrylate that (methyl) acrylic polymer is 2~12 with the carbon atom number of alkyl Monomeric unit be main framing and include (methyl) methyl acrylate monomeric unit.In the model for not damaging effect of the invention In enclosing, above-mentioned (methyl) acrylic polymer can also contain the monomeric unit of (methyl) acrylate other than the above.It needs It is noted that (methyl) acrylate refers to acrylate and/or methacrylate, the meaning with (methyl) of the invention It is identical.
(methyl) alkyl acrylate that carbon atom number as abovementioned alkyl is 2~12, it is specific enumerable: (methyl) third Olefin(e) acid ethyl ester, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) acrylic acid Monooctyl ester, (methyl) Isooctyl acrylate monomer, (methyl) nonyl acrylate, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, And (methyl) dodecylacrylate.In addition, aftermentioned (methyl) acrylic acid carboxyalkyl ester, (methyl) propylene can be enumerated The carbon atom of the alkyl such as sour hydroxyalkyl acrylate, (methyl) acrylate and (methyl) alkoxyalkyl acrylate Number replaces Arrcostab for 2~12 (methyl) acrylic acid.They may be used alone or in combination use., it is preferable to use choosing in these From ethyl acrylate, propyl acrylate, n-butyl acrylate, n-amylmethacrylate, the just own ester of acrylic acid and acrylic acid 2- At least one of ethylhexyl more preferably uses n-butyl acrylate.It should be noted that using two or more above-mentioned (first Base) in the case where alkyl acrylate, the Abs (b) in above-mentioned formula (1) is the aggregate value of each peak absorbance (but sometimes also with 1 Peak occurs.).
Meet the adhesive phase of above-mentioned formula (1) in order to obtain, in above-mentioned (methyl) acrylic polymer, as monomer list Member, preferably comprise abovementioned alkyl carbon atom number be 2~12 70~99 weight % of (methyl) alkyl acrylate, more preferably 75~98 weight %, further preferably 80~96 weight % are as monomeric unit.In addition, above-mentioned (methyl) acrylic Object preferably comprises 1~15 weight % of (methyl) methyl acrylate, more preferably 2~12 weight %, further preferably 4~10 weights Measure %.
For the purpose of improving cementability, heat resistance, one or more of various monomers can be imported by copolymerization In above-mentioned (methyl) acrylic polymer.As the concrete example of such comonomer, carboxyl group-containing monomer, hydroxyl can be enumerated Monomer, nitrogen containing monomer and monomer containing aromatic group etc..
It as carboxyl group-containing monomer, can illustrate for example: acrylic acid, methacrylic acid, (methyl) carboxy ethyl acrylate, (methyl) Carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid etc..They may be used alone or in combination use.
As hydroxyl monomer, can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) third Olefin(e) acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxy dodecyl acrylate, acrylic acid (4- Hydroxymethyl-cyclo-hexyl) methyl esters etc.. They may be used alone or in combination use.
As nitrogen containing monomer, it can be mentioned, for example: vinyl monomer with lactam nucleus (such as N- vinyl pyrrole The vinyl pyrrolidones class monomers such as alkanone, methyl ethylene pyrrolidones and have beta-lactam nucleus, δ-lactam nucleus and ε- Vinyl lactam class monomer of the lactam nucleus such as lactam nucleus etc.)；Maleimide, N- N-cyclohexylmaleimide, N- benzene The maleimides monomer such as base maleimide；(methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- bis- Ethyl (methyl) acrylamide, N- hexyl (methyl) acrylamide, N- methyl (methyl) acrylamide, N- butyl (methyl) propylene Amide, N- methylol (methyl) acrylamide, N- hydroxymethyl-propane (methyl) acrylamide etc. (N- substitution) amides monomer； (methyl) acrylate, (methyl) acrylic-amino propyl ester, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (first Base) (methyl) acrylate such as tbutylaminoethylacrylate, (methyl) acrylic acid 3- (3- pyridyl group) propyl ester Class monomer；N- (methyl) acryloyl-oxy methylene succinimide, N- (methyl) acryloyl group -6- oxygroup hexa-methylene amber The succinimides class monomers such as acid imide, eight methylene succinimide of N- (methyl) acryloyl group -8- oxygroup；Acrylonitrile, first The cyano such as base acrylonitrile (methyl) acrylic ester monomer；Vinylpyridine, vinylpiperidone, vinyl pyrimidine, vinyl Piperazine, vinylpyrazine, vinyl pyrrole, vinyl imidazole, vinylAzoles, polyvinyl morpholinone, N- Vinylcarboxylic acid amide Class etc..They may be used alone or in combination use.
As monomer containing aromatic group, it can be mentioned, for example: (methyl) benzyl acrylate, (methyl) phenyl acrylate, (first Base) phenoxyethyl acrylate etc..They may be used alone or in combination use.
In addition to above-mentioned monomer, the monomers containing anhydride group such as maleic anhydride, itaconic anhydride can also be enumerated；Acrylic acid oneself in Ester addition product；Styrene sulfonic acid, allyl sulphonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide third The monomers containing sulfonic group such as sulfonic acid, (methyl) sulfopropyl acrylate, (methyl) propane sulfonic acid；2- hydroxyethyl propylene Phosphorous acid-based monomers such as acyl phosphate etc..They may be used alone or in combination use.
It can also use: vinyl acetate, vinyl propionate, styrene, α-methylstyrene, N- caprolactam Equal vinyl monomers；The acrylic monomers containing epoxy group such as (methyl) glycidyl acrylate；(methyl) acrylic acid is poly- Glycol ester, (methyl) acrylic acid polypropylene glycol ester, (methyl) acrylic methoxy glycol ester, (methyl) methoxyethyl The polyethylene glycols acrylate monomer such as polypropylene glycol ester；(methyl) tetrahydrofurfuryl acrylate, has fluorine-containing (methyl) acrylate Acrylic ester monomers such as machine silicon (methyl) acrylate, acrylic acid 2- methoxy acrylate etc..They may be used alone or in combination It uses.
From improving the cohesiveness of above-mentioned (methyl) acrylic polymer, more effectively inhibit the generation of above-mentioned nano slit From the perspective of, it preferably will be in above-mentioned carboxyl group-containing monomer, above-mentioned hydroxyl monomer and above-mentioned nitrogen containing monomer by copolymerization At least one polar monomer imports above-mentioned (methyl) acrylic polymer, more preferably by copolymerization by above-mentioned carboxyl group-containing monomer, Above-mentioned hydroxyl monomer and above-mentioned nitrogen containing monomer import above-mentioned (methyl) acrylic polymer.As above-mentioned carboxyl group-containing monomer, It is preferred that (methyl) acrylic acid.As above-mentioned hydroxyl monomer, it is preferably selected from (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) third One or more of olefin(e) acid 2- hydroxy propyl ester and (methyl) acrylic acid 4- hydroxybutyl.Above-mentioned nitrogen containing monomer preferably has interior acyl The vinyl monomer of amine ring, more preferably above-mentioned vinyl pyrrolidone class monomer, further preferably N- vinyl pyrrole Alkanone.By the way that above-mentioned nitrogen containing monomer is imported above-mentioned (methyl) acrylic polymer by copolymerization, can more effectively inhibit The generation of nano slit, and the durability (peel resistance) of adhesive phase when can be improved high temperature and/or high humidity.
Above-mentioned (methyl) acrylic polymer preferably comprise above-mentioned 0.01~2 weight % of carboxyl group-containing monomer, more preferably 0.05~1 weight %, further preferred 0.1~0.3 weight % are as monomeric unit.
Above-mentioned (methyl) acrylic polymer preferably comprise above-mentioned 0.01~1 weight % of hydroxyl monomer, more preferably 0.05~1 weight %, further preferred 0.1~0.5 weight % are as monomeric unit.
Above-mentioned (methyl) acrylic polymer preferably comprises above-mentioned 0.1~5 weight % of nitrogen containing monomer, more preferable 0.5~3 Weight %, further preferred 1.5~3 weight % are as monomeric unit.
The average molecular weight of above-mentioned (methyl) acrylic polymer is not particularly limited, and weight average molecular weight is preferably 500,000 ~250 ten thousand or so.The manufacture of above-mentioned (methyl) acrylic polymer can be manufactured by various well known methods, for example, can It is suitable for selecting the radical polymerizations such as mass polymerization, solution polymerization process, suspension polymerization.As radical polymerization initiator, Various well known initiators as azo, peroxide can be used.Reaction temperature be typically set to 50~80 DEG C or so, it is anti- It is set as 1~8 hour between seasonable.In addition, in above-mentioned autofrettage, preferred solution polymerization process, as (methyl) acrylic polymer Solvent, ethyl acetate, toluene etc. usually can be used.
Crosslinking agent can be cooperated in above-mentioned adhesive.Using crosslinking agent, adaptation, durability can be improved, and can Seek the holding of the reliability and adhesive own form under high temperature.It can be suitable for using isocyanates, ring as crosslinking agent Oxygen class, peroxide, metal-chelating species,Oxazolines etc..These crosslinking agents can be used a kind or be applied in combination 2 kinds with On.
Isocyanate compound can be used in isocyanates crosslinking agent.As isocyanate compound, toluene two can be enumerated Isocyanates, chlorine phenylene vulcabond, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone two The isocyanate-monomers such as isocyanates, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate and make these Adduction system isocyanate compound obtained from the additions such as isocyanate-monomer and trimethylolpropane；Isocyanuric acid carboxylate, It is more can also to enumerate well known polyether polyol, polyester polyol, acrylic polyol, polybutadiene for biuret form compound The isocyanates through carbamate prepolymer type obtained from addition reaction such as first alcohol, polyisoprene polyol.
Above-mentioned isocyanates crosslinking agent can be used alone, and in addition can also mix two or more uses, relatively In 100 parts by weight of base polymer, the total content of above-mentioned isocyanates crosslinking agent is preferably 0.01~2 parts by weight, more preferably For 0.02~2 parts by weight, further preferably 0.05~1.5 parts by weight.It is contemplated that cohesiveness, preventing in durability test Removing etc. and suitably contain.
As peroxide crosslinking agent, various peroxide are used.As peroxide, dicetyl peroxydicarbonate can be enumerated Two (2- ethylhexyl) esters, dicetyl peroxydicarbonate two (4- tert-butylcyclohexyl) ester, peroxide-butyl carbonate, peroxidating The tertiary own ester of the neodecanoic acid tert-butyl ester, peroxidating neopentanoic acid, tert-Butyl peroxypivalate, dilauroyl peroxide, peroxidating two are just Decoyl, peroxidating isobutyric acid 1,1,3,3- tetramethyl butyl ester, peroxidating 2 ethyl hexanoic acid 1,1,3,3- tetramethyl butyl ester, two (4- Methyl benzoyl) peroxide, dibenzoyl peroxide, peroxidating tert-butyl isobutyrate etc..Wherein, particularly preferably using friendship Join that reaction efficiency is excellent, dicetyl peroxydicarbonate two (4- tert-butylcyclohexyl) ester, dilauroyl peroxide, diphenyl peroxide first Acyl.
Above-mentioned peroxide can be used alone, and in addition can also mix two or more uses, poly- relative to basis 100 parts by weight of object are closed, the total content of above-mentioned peroxide is preferably 0.01~2 parts by weight, more preferably 0.04~1.5 weight Part, further preferably 0.05~1 parts by weight.It can in the range be suitable for selection to adjust processability, again operability, crosslinking Stability, fissility etc..
Furthermore, it is possible to contain silane coupling agent in above-mentioned adhesive.By using silane coupling agent, can be improved durable Property.As silane coupling agent, the silane coupling agent with any appropriate functional group can be used.Specifically, as functional group, It can be mentioned, for example: vinyl, epoxy group, amino, sulfydryl, (methyl) acryloxy, acetoacetyl, isocyanate group, benzene Vinyl, polysulfide base etc..It is specific enumerable for example: vinyltriethoxysilane, vinyl tripropoxy silane, ethylene Three isopropoxy silane of base, vinyltributoxysilane etc. contain vinyl silicane coupling agent；γ-glycidoxypropyl group front three Oxysilane, γ-epoxy propoxy propyl triethoxysilane, 3- glycidoxypropyl diethoxy silane, 2- (3, 4- epoxycyclohexyl) ethyl trimethoxy silane etc. contains epoxy silane coupling；Gamma-amino propyl trimethoxy silicane, N- β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, N- (2- amino-ethyl) 3- amino propyl methyl dimethoxy Silane, γ-triethoxysilyl-N- (1,3- dimethyl butane) propyl amine, N- phenyl-gamma-amino propyl trimethoxy Base silane etc. contains amino silicane coupling agent；γ-mercapto propyl methyl dimethoxy silane etc. contains mercaptosilane coupling agents；To benzene second The silane coupling agents containing styryl such as alkenyl trimethoxy silane；γ-acryloyloxypropyltrimethoxysilane, γ-methyl Acryloxypropyl triethoxysilane etc. contains (methyl) acrylic silane coupling agent；3- isocyanates propyl triethoxy The coupling agents containing isocyanato silanes such as silane；The silicon of base containing polysulfide such as bis- (triethoxysilylpropyltetrasulfide) tetrasulfides Alkane coupling agent etc..
Above-mentioned silane coupling agent can be used alone, and in addition can also mix two or more uses.Relative to base polymer 100 parts by weight of object, the total content of above-mentioned silane coupling agent are preferably 0.001~5 parts by weight, more preferably 0.01~1 parts by weight, Further preferably 0.02~1 parts by weight are still more preferably 0.05~0.6 parts by weight.
Further, from the viewpoint of improving operability again, above-mentioned adhesive preferably comprises operates improver again.It is above-mentioned again Operation improver is with polar group, is easy that interaction occurs with glass interface and is easy to be segregated in glass interface Chemical substance.Operate improver again as above-mentioned, the glycol that it can be mentioned, for example: EO and PO etc. with oxyalkylene group, have it is complete The oligomer of fluoroalkyl and the polyether compound with reactive silicyl etc..Such as day can be used in above-mentioned polyether compound Polyether compound disclosed in this special open 2010-275522 bulletin.
As the above-mentioned polyether compound with reactive silicyl, it can be mentioned, for example: Kaneka Corp.'s manufacture MS polymer S203, S303, S810；SILYL EST250,EST280；SAT10,SAT200,SAT220,SAT350, The such as SAT400, EXCESTAR S2410 manufactured by Asahi Glass Co., Ltd, S2420 or S3430
Relative to 100 parts by weight of base polymer, then operating the content of improver is preferably 0.001 parts by weight or more, more More than preferably 0.01 parts by weight, more than further preferably 0.1 parts by weight, additionally, it is preferred that being 10 parts by weight hereinafter, more preferably For 5 parts by weight hereinafter, further preferably 2 parts by weight are hereinafter, be still more preferably 1 parts by weight or less.Improver is operated again Content less than 0.001 parts by weight when, it is difficult to improve the operational again of adhesive phase, when being greater than 10 parts by weight, there are adhesives The tendency that the adhesion characteristic of layer reduces.
Additionally, it is preferred that above-mentioned adhesive contains antistatic agent.When manufacturing liquid crystal display device by the list with adhesive phase When side protection polarizing coating is pasted on liquid crystal display panel, by mold release film from the adhesive phase of the unilateral protection polarizing coating with adhesive phase Removing, but can due to the mold release film removing and generate electrostatic.In addition, unilateral guarantor of the fitting with adhesive phase on liquid crystal display panel In the case where producing fitting mistake when protecting polarizing coating, need above-mentioned polarization film stripping, but can be due to the removing of the polarizing coating And generate electrostatic.The electrostatic of generation can impact the liquid crystal aligning inside liquid crystal display device, lead to unfavorable condition.Separately When outside, using liquid crystal display device, it some times happens that showing unevenness as caused by electrostatic.It is antistatic by being added in adhesive Agent can assign anti-static function to the adhesive phase of the unilateral protection polarizing coating with adhesive phase, can prevent these bad feelings Condition.
Above-mentioned antistatic agent is not particularly limited, it can be mentioned, for example:Anion salt and alkali metal salt isoiony Close object., it can be said that in the case where being added to ionic compound, it can be based on ionic compound on the surface of adhesive phase It oozes out and effectively shows anti-static function.On the other hand, it is contacted, is sometimes resulted in polarizer due to ionic compound The optical characteristics such as degree of polarization reduce.From the viewpoint of the reduction for inhibiting above-mentioned optical characteristics, alkali metal salt is particularly preferably used.
The organic salt or inorganic salts of alkali metal can be used in alkali metal salt.Alkali metal salt can be used alone a kind, or combination is more Kind uses.
As the alkali metal ion in the cationic portion for constituting alkali metal salt, each ion such as lithium, sodium, potassium can be enumerated.These alkali In metal ion, preferred lithium ion.
The anion portion of alkali metal salt can be formed by organic matter, can also be formed by inorganic matter.As composition organic salt Anion portion, can be used such as CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(CF3SO2)3C-、 C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-、(CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -、PF6 -、CO3 2-Deng.In particular, containing There is the anion portion of fluorine atom since the good ionic compound of ionic dissociation can be obtained, preferably uses.As The anion portion of inorganic salts is constituted, Cl can be used-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、 SbF6 -、NbF6 -、TaF6 -、(CN)2N-Deng.As anion portion, preferably (CF3SO2)2N-、(C2F5SO2)2N-Equal per-fluoroalkyl sulfonyls Imines, particularly preferably with (CF3SO2)2N-The trifluoromethanesulfonimide of expression.
It is specific enumerable as the organic salt of alkali metal: sodium acetate, sodium alginate, sodium lignin sulfonate, toluenesulfonic acid Sodium, LiCF3SO3、Li(CF3SO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C、KO3S (CF2)3SO3K、LiO3S(CF2)3SO3K etc., in these, preferably LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li (C4F9SO2)2N、Li(CF3SO2)3C etc., more preferable Li (CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2The fluorine-containing acyl such as N is sub- Amine lithium salts, particularly preferred per-fluoroalkyl sulfonyl imines lithium salts.
In addition, the inorganic salts as alkali metal, can enumerate lithium perchlorate, lithium bromide.
The content of alkali metal salt in adhesive is preferably 0.001~5 weight relative to 100 parts by weight of base polymer Part.When above-mentioned alkali metal salt is less than 0.001 parts by weight, the improvement effect that may cause antistatic property is insufficient.Above-mentioned alkali gold Belonging to salt is preferably 0.01 parts by weight or more, more than further preferably 0.1 parts by weight.On the other hand, above-mentioned alkali metal salt is greater than 5 When parts by weight, it may cause durability and become inadequate.Above-mentioned alkali metal salt is preferably 3 parts by weight or less.
As the method for forming adhesive phase, made using following method: for example, by above-mentioned adhesive be coated on through The diaphragm etc. for having crossed lift-off processing is drying and removing polymer solvent etc. after forming adhesive phase, is protecting polarizing coating in unilateral side Polarizer side (being in the embodiment of figure 1 polarizer) on the method that transfers；Or the above-mentioned adhesive of coating, it dries and removes Polymer solvent etc. and on polarizer formed adhesive phase method；Etc..It should be noted that in coating adhesive, More than one solvents other than polymer solvent suitably can newly be added.
The thickness of adhesive phase is not particularly limited, from inhibit the defect as caused by nano slit, take into account it is excellent resist it is quiet Electricity Functional and again operability from the perspective of, preferably 25 μm or less, more preferably 23 μm or less, be more preferably 20 μm with Under, additionally, it is preferred that for 10 μm or more, more preferably 12 μm or more, further preferably 15 μm or more.
As the diaphragm that have passed through lift-off processing, organosilicon peeling liner is preferably used.It is applied by adhesive of the invention It is distributed in such liner above and makes it dry and formed in the process of adhesive phase, it, can root as the method for keeping adhesive dry According to purpose suitably using suitable method.It is preferred that using the method being thermally dried to above-mentioned coated film.Heat drying Temperature is preferably 40 DEG C~200 DEG C, further preferably 50 DEG C~180 DEG C, particularly preferably 70 DEG C~170 DEG C.By making to add Hot temperature can obtain the adhesive with excellent adhesion characteristic in above-mentioned range.
Drying time can be suitably using the suitable time.Above-mentioned drying time is preferably 5 seconds~20 minutes, further Preferably 5 seconds~10 minutes, particularly preferably 10 seconds~5 minutes.
As the forming method of adhesive phase, various methods can be used.It is specific enumerable for example: rolling method, roller lick coating Method, gravure coating process, reversed rubbing method, roller brush method, spray coating method, dipping rolling method, stick coating method, knife coating, air knife coating method, leaching Coating, utilizes the methods of extrusion coating methods of die coating machine etc. at die lip rubbing method.
In the case where above-mentioned adhesive phase exposes, piece (diaphragm) the protection adhesive that have passed through lift-off processing can use Layer is until actual use.
As the constituent material of diaphragm, it can be mentioned, for example: polyethylene, polypropylene, polyethylene terephthalate, polyester The porous materials such as the plastic foils such as film, paper, cloth, non-woven fabrics, net, foamed sheet, metal foil and their layered product etc. are suitable for thin Piece object etc., but from the excellent aspect of surface smoothness, it is preferable to use plastic foil.
As the plastic foil, as long as the film of above-mentioned adhesive phase can be protected then to be not particularly limited, it can be mentioned, for example: Polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, Polyethylene terephthalate film, polybutylene terephthalate (PBT) film, polyurethane film, vinyl-vinyl acetate copolymer Film etc..
The thickness of above-mentioned diaphragm is usually 5~200 μm, preferably 5~100 μm or so.It can also be as needed using having Machine silicon class, fluorine class, chain alkyl class or fatty acid acyl amine release agent, silicon dioxide powder etc. to above-mentioned diaphragm carry out demoulding and Antifouling process or the antistatic treatment for being coated by type, is mixed into type, vapor deposition type for above-mentioned diaphragm etc..Especially it is possible to pass through The lift-off processings such as organosilicon processing, chain alkyl processing, fluorine processing are suitably carried out to the surface of above-mentioned diaphragm and are further increased Fissility relative to above-mentioned adhesive phase.
<surface protection film>
Surface protection film can be set on the unilateral protection polarizing coating with adhesive phase.Surface protection film usually has base Material film and adhesive phase, and polarizer is protected via the adhesive phase.
As the base material film of surface protection film, from the viewpoints such as inspectability, managerial, may be selected with isotropism or Close to isotropic membrane material.As its membrane material, it can be mentioned, for example: the polyesters such as polyethylene terephthalate film Resin, cellulosic resin, acetate esters resin, polyether sulfone resin, polycarbonate resin, polyamide-based resin, polyamides Imines resinoid, polyolefin resin, polymer transparent as acrylic resin.In these materials, preferred polyesters Resin.The layered product of one kind or two or more membrane material also can be used in base material film, furthermore it is also possible to use the stretching of above-mentioned film Object.The thickness of base material film is usually 500 μm or less, preferably 10~200 μm.
As the adhesive for the adhesive phase for forming surface protection film, it can suitably select use with (methyl) acrylic polymer Closing the polymer such as object, silicone-based polymers, polyester, polyurethane, polyamide, polyethers, fluorine class, rubber is basic polymer Adhesive.It is preferably the third of basic polymer with acrylic polymer from viewpoints such as the transparency, weatherability, heat resistances Alkene acrylic binder.The thickness (dry film thickness) of adhesive phase can be determined according to required bonding force.Usually 1~ 100 μm or so, preferably 5~50 μm.
It should be noted that in surface protection film, it can be in the opposite with the face for being provided with adhesive phase of base material film On one side, lift-off processing is set using the low cementitious material that have passed through organosilicon processing, chain alkyl processing, fluorine processing etc. Layer.
<other optical layers>
Unilateral protection polarizing coating with adhesive phase of the invention can be made with other optics layer by layer in actual use Folded optical film and use.About the optical layer, be not particularly limited, can be used 1 layer or 2 layers or more such as reflecting plate, Half transmitting plate, phase plate (including 1/2 wave plate, quarter wave plate etc.), compensation film for angular field of view etc. are used for liquid crystal display device etc. sometimes Formation optical layer.In particular it is preferred that further stacking is anti-on the unilateral protection polarizing coating of the invention with adhesive phase It penetrates reflective polarizing film made of plate or Transflective plate or Semitransmissive polarizing coating, protected partially in the unilateral side with adhesive phase Elliptical polarization film made of further laminated phase-difference plate or circular polarization film on vibrating diaphragm, in the unilateral protection polarization with adhesive phase Wide visual field angle polarizing coating made of compensation film for angular field of view is further laminated on film or on the unilateral protection polarizing coating with adhesive phase Polarizing coating made of brightness enhancement film is further laminated.
The unilateral protection polarizing coating upper layer with adhesive phase it is stacked on state optical film made of optical layer can also using Optics is made in preparatory stacking to be formed in the mode being successively laminated respectively in the manufacturing process of liquid crystal display device etc. The manufacturing process that when film, stability, assembling operation etc. with quality are excellent, can make liquid crystal display device etc. improves excellent Point.The suitable bonding way such as adhesive phase can be used in stacking.Carry out the above-mentioned unilateral protection polarizing coating with adhesive phase, When the bonding of other optical films, their optic axis can be formed as suitable with angle setting according to phase difference characteristics of target etc. Degree.
The of the invention unilateral protection polarizing coating with adhesive phase or optical film are preferably used for liquid crystal display device, organic The formation etc. of the various image display devices such as EL display device.The formation of liquid crystal display device can based on existing mode come into Row.That is, liquid crystal display device usually can by by liquid crystal cells and unilateral protection polarizing coating with adhesive phase or optical film, with And as needed and the component parts such as lighting system for using are suitably assembled and import driving circuit etc. and are formed, in the present invention In, other than using this point of the unilateral protection polarizing coating with adhesive phase or optical film of the invention, there is no particular determination, It can be formed according to existing mode.For liquid crystal cells, any type of liquid crystal such as IPS type, VA type also can be used Unit, particularly preferred IPS type.
The unilateral side or two sides that liquid crystal cells can be formed in are configured with unilateral protection polarizing coating or optics with adhesive phase The suitable liquid crystal such as the liquid crystal display device of film, the liquid crystal display device for having used backlight or reflecting plate in the illumination system Showing device.At this point, the list in liquid crystal cells can be set in the unilateral protection polarizing coating of the invention with adhesive phase or optical film Side or two sides.In the case where unilateral protection polarizing coating or optical film with adhesive phase is arranged in two sides, they can be identical Material, be also possible to different materials.Further, when forming liquid crystal display device, 1 layer can be configured in position Or 2 layers or more of such as diffuser plate, antiglare layer, antireflection film, protection board, prism array, lens array sheet, light diffusing sheet, back The suitable component such as light lamp.
<method for continuous production of image display device>
Above-mentioned image display device passes through method for continuous production (volume is to plate (roll-to-panel) mode) preferably to make It makes, the method for continuous production (volume is to plate (roll-to-panel) mode) includes: will be from the list of the invention with adhesive phase The above-mentioned unilateral protection with adhesive phase that the coiling body (volume) of side protection polarizing coating is continuously sent out and transported by above-mentioned diaphragm Polarizing coating continuously fits in the surface of image display panel via above-mentioned adhesive phase.Unilateral side with adhesive phase of the invention Protecting polarizing coating is very thin film, therefore aobvious using cutting (individual cutting) slabbing and fitting in image one by one When showing mode (also referred to as " piece is to plate (sheet-to-panel) mode ") of panel, the transport of piece, to display panel be bonded when Operating difficulties, during these, unilateral protection polarizing coating (piece) with adhesive phase is impacted (example by big mechanicalness Such as, the flexure etc. based on absorption) risk increase.In order to reduce such risk, need additionally to take for example using substrate The countermeasure with a thickness of 50 μm or more thicker surface protection films etc. of film.On the other hand, if using volume to plate (roll-to- Panel) mode, then the unilateral protection polarizing coating with adhesive phase can pass through sequential like without cutting (individual cutting) slabbing Diaphragm and be steadily transported to image display panel from volume and the state kept to fit in image display panel, there is no need to Using thicker surface protection film, above-mentioned risk can be greatly reduced.As a result, with that can utilize with film thickness and storage modulus satisfaction The adhesive phase that the mode of given relational expression controls mitigates mechanical impact and complements each other, and can be realized generating for nano slit The high speed continuous production of the image display panel of effective inhibition is arrived.
Fig. 5 is the continuous manufacture system shown using volume to the liquid crystal display device of plate (roll-to-panel) mode An example schematic diagram.As shown in figure 5, the continuous manufacture system 100 of liquid crystal display device includes: transporting liquid crystal display panel P A series of transport portion X, the 1st polarizing coating supply unit 101a, the 1st sticking part 201a, the 2nd polarizing coating supply unit 101b and the 2nd patch Conjunction portion 201b.It should be noted that as coiling body (volume 1) 20a of the 1st unilateral protection polarizing coating with adhesive phase and the Coiling body (volume 2) 20b of the 2 unilateral protection polarizing coatings with adhesive phase, use along its length have absorption axiss and The coiling body of the polarizing coating for the form recorded in Fig. 1.
(transport portion)
Transport portion X transports liquid crystal display panel P.Transport portion X can have multiple transport roller and adsorption plate etc. and constitute.It transports Portion X includes to replace between the 1st sticking part 201a and the 2nd sticking part 201b relative to the carriage direction of liquid crystal display panel P The configuration replacement portion of the configuration relation of the long side and short side of liquid crystal display panel P is (for example, make liquid crystal display panel P carry out 90 ° of water Flat rotation) 300.Thus, it is possible to make the 1st unilateral guarantor of the unilateral protection polarizing coating 21a and the 2nd with adhesive phase with adhesive phase It protects polarizing coating 21b and is bonded relative to liquid crystal display panel P with the relationship of crossed Nicol.
(the 1st polarizing coating supply unit)
The 1st band adhesive that 1st polarizing coating supply unit 101a will continuously send out from the 20a of volume 1 and be transported by diaphragm 5a Unilateral protection polarizing coating (belt surface protective film) 21a of layer is continuously supplied into the 1st sticking part 201a.1st polarizing coating supply unit 101a includes the 1st continuous unloading part 151a, the 1st cutting part 152a, the 1st stripping portion 153a, the 1st reeling end 154a and multiple fortune Send energy storage parts such as roller portion, dance roller (dancer roll) etc..
1st continuous unloading part 151a has the continuous submitting axis of the setting 20a of volume 1, continuously sends out and is equipped with from the 20a of volume 1 The band-like unilateral protection polarizing coating 21a with adhesive phase of diaphragm 5a.
1st cutting part 152a has cutting mechanisms and the adsorbing mechanisms such as cutter, laser aid.1st cutting part 152a is by band Unilateral protection polarizing coating 21a of the 1 of shape with adhesive phase is cut in the width direction with given length and remains diaphragm 5a. It should be noted that being formed in the width direction having used to be laminated on diaphragm 5a with given length as the 20a of volume 1 The feelings of the volume (the optics film roll for being carved into cut mark) of the band-like unilateral protection polarizing coating 21a with adhesive phase of more incision lines Under condition, the 1st cutting part 152a (also the same about the 2nd cutting part 152b described below) is not needed.
1st stripping portion 153a by using diaphragm 5a as inside is turned back and the 1st unilateral protection with adhesive phase is inclined Vibrating diaphragm 21a is removed from diaphragm 5a.As the 1st stripping portion 153a, wedge like members, roller etc. can be enumerated.
1st reeling end 154a is to 5a volumes of diaphragm after having removed the 1st unilateral protection polarizing coating 21a with adhesive phase It takes.1st reeling end 154a has the spool being arranged for batching the volume of diaphragm 5a.
(the 1st sticking part)
Polarizing coating is protected in unilateral side using the 1st after the 1st stripping portion 153a removing with adhesive phase by the 1st sticking part 201a 21a is continuously fitted in and transport portion X is utilized to transport across the 1st unilateral adhesive phase for protecting polarizing coating 21a with adhesive phase The liquid crystal display panel P (the 1st bonding process) sent.1st sticking part 81 has a pair of of doubling roller and constitutes, in doubling roller at least One is made of driven roller.
(the 2nd polarizing coating supply unit)
The 2nd band adhesive that 2nd polarizing coating supply unit 101b will continuously send out from the 20b of volume 2 and be transported by diaphragm 5b Unilateral protection polarizing coating (belt surface protective film) 21b of layer continuously fits in the 2nd sticking part 201b.2nd polarizing coating supply unit 101b includes the 2nd continuous unloading part 151b, the 2nd cutting part 152b, the 2nd stripping portion 153b, the 2nd reeling end 154b and multiple fortune Send energy storage parts such as roller portion, dance roller etc..It should be noted that the 2nd continuous unloading part 151b, the 2nd cutting part 152b, the 2nd Stripping portion 153b, the 2nd reeling end 154b are respectively provided with and the 1st continuous unloading part 151a, the 1st cutting part 152a, the 1st stripping portion 153a, the 1st reeling end 154a is similarly constituted and function.
(the 2nd sticking part)
Polarizing coating is protected in unilateral side using the 2nd after the 2nd stripping portion 153b removing with adhesive phase by the 2nd sticking part 201b 21b is continuously fitted in and transport portion X is utilized to transport across the 2nd unilateral adhesive phase for protecting polarizing coating 21b with adhesive phase The liquid crystal display panel P (the 2nd bonding process) sent.2nd sticking part 201b has a pair of of doubling roller and constitutes, in doubling roller extremely Few one is made of driven roller.
Embodiment
Hereinafter, the present invention will be described in conjunction with the embodiments, but the present invention is not limited by embodiment described below. It should be noted that part and % in each example are weight basis.Hereinafter, not special provision to be placed at room temperature for condition all 23 DEG C, 65%RH.
<production of unilateral side protection polarizing coating>
(production of polarizer)
It is 0.75% to water absorption rate, non-crystalline M-phthalic acid that Tg is 75 DEG C is copolymerized polyethylene terephthalate The single side of (IPA be copolymerized PET) film (thickness: 100 μm) substrate implements sided corona treatment, and to the sided corona treatment face in 25 DEG C of coatings with The ratio of 9:1 includes polyvinyl alcohol (99.2 moles of degree of polymerization 4200, saponification degree %) and the acetoacetyl modified PVA (degree of polymerization 1200, acetoacetyl modified rate 4.6%, 99.0 moles of % or more of saponification degree, the Nippon Synthetic Chemical Industry Co., Ltd's system, quotient The name of an article " GOHSEFIMER Z200 ") aqueous solution and be dried, form 11 μm of thickness of PVA resinoid layer, made layer Stack.
By gained laminated body in 120 DEG C of baking oven, (length side along longitudinal direction has been carried out between the different roller of peripheral speed To) it is stretched to 2.0 times of free end simple tension (assisting tension is handled in atmosphere).
Then, by laminated body 30 DEG C of liquid temperature insoluble bath (relative to 100 parts by weight of water cooperate 4 parts by weight of boric acid and Obtained boric acid aqueous solution) in impregnated of 30 seconds (insoluble processing).
Then, in 30 DEG C of liquid temperature of dyeing liquor, iodine concentration, leaching are adjusted in a manner of making polarizing film reach given transmissivity The stain time, while being impregnated.In the present embodiment, is cooperating 0.2 parts by weight of iodine relative to 100 parts by weight of water and cooperating iodine Change in iodine aqueous solution obtained from 1.0 parts by weight of potassium impregnated of 60 seconds (dyeing processing).
Then, the crosslinking bath at 30 DEG C of liquid temperature (cooperates 3 parts by weight of potassium iodide relative to 100 parts by weight of water and cooperates boric acid Boric acid aqueous solution obtained from 3 parts by weight) in impregnated of 30 seconds (crosslinking Treatment).
Then, the boric acid aqueous solution that laminated body is impregnated in 70 DEG C of liquid temperature (is cooperated into 4 weight of boric acid relative to 100 parts by weight of water Amount part simultaneously cooperate aqueous solution obtained from 5 parts by weight of potassium iodide) in while, along longitudinal direction between the different roller of peripheral speed (length direction) has carried out simple tension (stretch processing in aqueous solution) in a manner of making total stretching ratio reach 5.5 times.
Then, the cleaner bath that laminated body is impregnated in 30 DEG C of liquid temperature (is cooperated into 4 weight of potassium iodide relative to 100 parts by weight of water Part obtained from aqueous solution) in (cleaning treatment).
By operating above, the optical film laminate of the polarizer comprising 5 μm of thickness, boric acid content 16% has been obtained.It rises Boric acid content in polariscope is measured by following methods.
For obtained polarizer, Fourier transform infrared spectrophotometer (FTIR) (Perkin Elmer company is used System, trade name " SPECTRUM2000 "), it is measured and being to measure decaying total reflection light splitting (ATR) measurement of light with polarised light Boric acid peak (665cm-1) intensity and control peak (2941cm-1) intensity.By gained boric acid peak intensity and control peak intensity, Boric acid volume index is calculated using following formula, and further boric acid volume index calculated has determined boric acid content using following formula (weight %).
(boric acid volume index)=(boric acid peak 665cm-1Intensity)/(control peak 2941cm-1Intensity)
(boric acid content (weight %))=(boric acid volume index) × 5.54+4.1
(production of transparent protective film)
Transparent protective film: the easy bonding of 40 μm of thickness (methyl) acrylic resin films with lactone ring structure is handled Face uses after implementing sided corona treatment.
(production of the bonding agent suitable for transparent protective film)
By 40 parts by weight of N- hydroxyethyl acrylamide (HEAA), 60 parts by weight of acryloyl morpholine (ACMO) and light-initiated The mixing of agent " IRGACURE 819 " (BASF AG's system) 3 parts by weight, is prepared for ultraviolet hardening bonding agent.
(production of unilateral side protection polarizing coating)
On the surface of the polarizer of above-mentioned optical film laminate so that the thickness of the adhesive layer after solidifying reaches 0.5 μm Mode is coated with above-mentioned ultraviolet hardening bonding agent, while being bonded above-mentioned transparent protective film, then, as active energy beam Ultraviolet light is irradiated, so that bonding agent be made to solidify.Ultraviolet light irradiation has used the metal halide lamp for being sealed with gallium, irradiation unit: Light HAMMER10, the valve of Fusion UV Systems company manufacture: V valve, maximal illumination: 1600mW/cm2, cumulative exposure Measure 1000/mJ/cm2(380~440nm of wavelength), the Sola-Check system that the illumination of ultraviolet light is manufactured using Solatell company System is determined.Next, amorphism PET base material is removed, the unilateral protection polarization for having used slim polarizer has been made Film.The knot of the monomer transmissivity T and degree of polarization P of polarizer are measured using obtained unilateral protection polarizing coating, by following methods Fruit, the monomer transmissivity T of polarizer are 42.8%, and the degree of polarization P of polarizer is 99.99%.
Using the spectral transmission analyzer (Dot-3c of color technical research institute in village) with integrating sphere to obtained list The monomer transmissivity T and degree of polarization P of the polarizer of side protection polarizing coating are determined.
It should be noted that degree of polarization P is by protecting polarizing coatings so that the axis of homology of the two is parallel 2 identical unilateral side Mode overlap in the case where transmissivity (parallel transmission: Tp) and the feelings that are overlapped in the orthogonal mode of the axis of homology both made Transmissivity (orthogonal transmission: Tc) under condition is applied to following formula and finds out.Degree of polarization P (%)={ (Tp-Tc)/(Tp+Tc) }1/2 ×100
Each transmissivity be by when the complete polarized light obtained after Glan-Taylor prism polarizer passes through is set as 100%, with The transmissivity that the Y value as obtained from measuring 2 degree of visuals field (illuminant-C) of JIS Z8701 and have carried out visibility correction indicates.
<formation of adhesive phase>
(preparation of acrylic adhesives A)
To equipped with agitating paddle, thermometer, nitrogen ingress pipe, condenser four-neck flask in feed intake containing the positive fourth of acrylic acid 93.82 parts of ester, 4 parts of methyl methacrylate, 1.5 parts of n-vinyl pyrrolidone, 0.2 part of acrylic acid and acrylic acid 4- hydroxyl The monomer mixture that 0.48 part of butyl ester.Further, relative to 100 parts of above-mentioned monomer mixture (solid component), together with acetic acid second Ester feeds intake 0.15 part of 2, the 2 '-azodiisobutyronitrile as polymerization initiator together, import nitrogen while being slowly stirred and into It has gone nitrogen displacement, then the liquid temperature in flask is maintained near 60 DEG C, has carried out 7 hours polymerization reactions.Then, to gained Ethyl acetate is added in reaction solution, is prepared for the acrylic compounds that solid component concentration is adjusted to 20% weight average molecular weight 1,300,000 The solution of polymer.
The weight average molecular weight (Mw) of above-mentioned acrylic polymer uses TOSOH Co., Ltd GPC device (HLC- 8220GPC) it is determined.Determination condition is as described below.
Sample concentration: 0.2 mass % (THF solution)
Sample injection rate: 10 μ l
Eluent: THF
Flow velocity: 0.6ml/min
Measuring temperature: 40 DEG C
Chromatographic column: sample column；TSKguardcolumn SuperHZ-H (1)+TSKgel SuperHZM-H (2)
Reference column；TSKgel SuperH-RC (1)
Detector: differential refractometer (RI)
Weight average molecular weight is found out by polystyrene scaled value.
Relative to 100 parts of solid component of prepared acrylic polymer solution, cooperate bis- (trifluoro methylsulfonyls) sub- 1.5 parts of amine lithium (Mitsubishi Materials electronization is at Co. Ltd. system), ethyl-methyl pyrrolidinesBis- (trifluoro methylsulfonyl) imines (east Capital chemical conversion industry system) 1 part, isocyanates crosslinking agent (Mitsui Chemicals, Inc's system, trade name " Takenate D160N ") 0.17 part, 0.25 part of peroxide crosslinking agent (NOF Corp's system, trade name " NYPER BMT ") and operate again 0.1 part of improver (Kaneka Corp.'s system, trade name " SAT10 "), is prepared for acrylic adhesives A.
(preparation of acrylic adhesives B~I)
In the preparation of above-mentioned acrylic adhesives A, the composition of monomer is changed as shown in table 1, has adjusted polymerization Condition is prepared for the solution of acrylic polymer using same method in addition to this, and is prepared for acrylic adhesives B~I.
(formation of adhesive phase)
Next, prepared acrylic adhesives A~I is utilized respectively jetting type spreader even application Yu Jingyou The surface for the polyethylene terephthalate film (diaphragm) that machine silicon class remover is handled, in 155 DEG C of air circulation It is 1 minute dry in formula constant temperature oven, adhesive phase is formd on the surface of each diaphragm respectively.
Compound in table 1 is as described below.
BA: n-butyl acrylate
MMA: methyl methacrylate
NVP:N- vinyl pyrrolidone
AA: acrylic acid
4HBA: acrylic acid 4- hydroxybutyl
LiTFSi: bis- (trifluoro methylsulfonyl) imine lithiums (Mitsubishi Materials electronization is at Co. Ltd. system)
EMPTFSi: ethyl-methyl pyrrolidinesBis- (trifluoro methylsulfonyl) imines (Tokyo chemical conversion industry system)
SAT10: improver (Kaneka Corp.'s system) is operated again
Embodiment 1~11, comparative example 1 and 2
<production of the unilateral protection polarizing coating with adhesive phase>
It is bonded made adhesive phase respectively in the polarizer side of made unilateral protection polarizing coating, makes respectively Unilateral protection polarizing coating with adhesive phase.
Unilateral protection polarizing coating for adhesive phase obtained above, with adhesive phase, has carried out following measurements and has commented Valence.Show the result in table 2.
<measurement of peak absorbance>
For the adhesive phase surface side of the obtained unilateral protection polarizing coating with adhesive phase, Fourier transform infrared is used Spectrophotometer (FTIR) (Perkin Elmer corporation, trade name " FT-IR Spectrometer Frontier "), for The stretching vibration for belonging to the ester bond in the monomer component in adhesive determines absorbance by total reflection measurement (ATR). With cumulative frequency 8 times, resolution ratio -4cm-1Condition be determined.By 1100~1130cm-1In the range of absorbance peak The peak absorbance A bs (a) of antisymmetric stretching vibration as the C-O-C key for belonging to (methyl) methyl acrylate, by 1150~ 1260cm-1In the range of absorbance peak as the C-O-C key for belonging to (methyl) alkyl acrylate antisymmetry stretch vibration Dynamic peak absorbance A bs (b), will be in 800~900cm-1Minimum absorbance (baseline) in range is used as absorbance A bs (c).Into And obtained each absorbance is substituted into following formula, calculate IR parameter.
<generation of nano slit inhibits: the test of guitar plectrum>
Unilateral protection polarizing coating obtained in Examples and Comparative Examples with adhesive phase is cut into 50mm × 150mm's Size (absorption axis direction is 50mm), as sample 11.For sample 11, in the side of protective film 2, fitting is utilized following It is used after the surface protection film 6 of method production.
(surface protection film of test)
To equipped with agitating paddle, thermometer, nitrogen ingress pipe, condenser four-neck flask in feed intake acrylic acid 2- ethyl hexyl 94 mass parts of ester (2EHA), N, 1 mass parts of N- diethyl acrylic acid amides (DEAA), ethoxydiglycol acrylate (EDE) 1 mass parts, 4 mass parts of acrylic acid 4- hydroxybutyl (HBA), the 2,2 '-azodiisobutyronitriles as polymerization initiator 0.2 mass parts, 150 mass parts of ethyl acetate, nitrogen is imported when being slowly stirred, by the liquid temperature in flask be maintained at 60 DEG C it is attached Closely, the polymerization reaction for having carried out 5 hours is prepared for acrylic polymer solution (40 mass %).Above-mentioned acrylic The weight average molecular weight of object is 570,000, and glass transition temperature (Tg) is -68 DEG C.
Above-mentioned acrylic polymer solution (40 mass %) is diluted to 20 mass % using ethyl acetate, in the solution Isocyanuric acid carboxylate (the poly- ammonia of Japan of addition hexamethylene diisocyanate in 500 mass parts (100 mass parts of solid component) Ester Industrial Co., Ltd system, CORONATE HX:C/HX) 2 mass parts (2 mass parts of solid component), as the two of crosslinking catalyst Dibutyl tin laurate (1 mass % ethyl acetate solution) 2 mass parts (0.02 mass parts of solid component), are mixed, It is prepared for acrylic adhesives solution.
By above-mentioned acrylic adhesives solution coating in 38 μm of thickness of transparent polyethylene terephthalate (PET) Film (polyester film) heats 1 minute in 130 DEG C, forms 15 μm of thickness of adhesive phase, made surface protection film.
Then, as the schematic diagram of Fig. 3 (A), Fig. 3 (B) sectional view shown in, from sample 11 remove release sheet (every Film), and be pasted on glass plate 20 across the adhesive phase of exposing 4.Then, relative to sample 11 (6 side of surface protection film) Central portion, using guitar plectrum (HISTORY corporation, model " HP2H (HARD) ") apply 200g load, in sample 11 On the direction orthogonal with the absorption axiss of polarizer 1 at a distance from 100mm in 50 round-trip loads are repeated.Above-mentioned load is negative Lotus carries out at 1 position.In addition, above-mentioned load is carried out with high speed (5m/ points).
Then, after sample 11 being placed 1 hour in 80 DEG C of environment, using following benchmark confirmed sample 11 whether there is or not The crackle of light leakage.
◎: 0~10
Zero: 11~30
×: 31 or more
Fig. 4 is the crackle for confirming the light leakage in the guitar plectrum test of the unilateral protection polarizing coating 11 with adhesive phase (following indexs of nano slit a) are an examples for polarizing the microscopical photo of film surface.In Fig. 4 (A), do not confirm by The crackle of light leakage caused by nano slit a.On the other hand, Fig. 4 (B) is to be produced due to heating along the absorption axis direction of polarizer The case where having given birth to the crackle of 3 light leakages as caused by nano slit a.In Fig. 4, using differential interference microscope to producing nanometer The sample of slit is observed.When being shot to sample, in the downside (transmitted light source for the sample for producing nano slit Side) sample for not generating nano slit is set in a manner of being orthogonal Niccol relationship, it is observed using transmitted light.
<operational evaluation again>
The made unilateral protection polarizing coating with adhesive phase is cut into 32 inches, as sample.Use layer The sample is pasted on alkali-free glass plate by press, then, 15 minutes autoclave process is carried out with 50 DEG C, 5atm, is made it completely It is closely sealed.Then, using operating device again, progress is determined under conditions of 90 ° of peel angle, peeling rate 300mm/min again Bonding force (N/25mm) when operation.Then, it is evaluated according to following benchmark.
◎: 3 (N/25mm) are below
Zero: greater than 3 (N/25mm) and for 6 (N/25mm) below
×: greater than 6 (N/25mm)
<evaluation of antistatic property>
After the diaphragm removing of the made unilateral protection polarizing coating with adhesive phase, Mitsubishi is utilized Chemical Analytech corporation MCP-HT450 determines the sheet resistance value (Ω/) of adhesive surface.In addition, will The made unilateral protection polarizing coating with adhesive phase is cut into the size of 100mm × 100mm, is pasted on liquid crystal display panel.It will The panel is placed on the backlight of the brightness with 10000cd, used as electrostatic generator ESD (ESD-8012A, SANKI corporation) generate 15kV electrostatic, thus cause the orientation disorder of liquid crystal.Use moment Multichannel photometric detector (MCPD-3000, great Zhong Electronics Co., Ltd system) measurement is by the bad caused undesirable recovery time (second) of display of the orientation.So Afterwards, it is evaluated according to following benchmark.
Within ◎: 5 seconds
Zero: greater than 5 second and be 7 seconds or less
△: greater than 7 second and be 10 seconds or less
×: greater than 10 second
As shown in Table 2, the unilateral protection polarizing coating with adhesive phase of embodiment 1~11 is not likely to produce crackle, Er Qiezai Operability and anti-static function are excellent.On the other hand, it is known that for the unilateral protection polarization with adhesive phase of comparative example 1 and 2 For film, any characteristic in the inhibition function of crackle, again operability or anti-static function is poor.
Industrial applicibility
Unilateral protection polarizing coating with adhesive phase of the invention can be individually or to use in the form of its optical film has been laminated In image display devices such as liquid crystal display device (LCD), organic EL display devices.

Claims (12)

1. a kind of adhesive phase contains (methyl) acrylic polymer and is used as basic polymer,
Wherein, it is 2~12 that described (methyl) acrylic polymer, which contains (methyl) methyl acrylate and the carbon atom number of alkyl, (methyl) alkyl acrylate as monomeric unit,
Described adhesive layer meets following formula (1),
Abs (a): in the IR measurement carried out using total reflection measuring method to described adhesive layer, (methyl) acrylic acid is belonged to The peak absorbance of the antisymmetric stretching vibration of the C-O-C key of methyl esters；
Abs (b): in the IR measurement carried out using total reflection measuring method to described adhesive layer, (methyl) third is belonged to The peak absorbance of the antisymmetric stretching vibration of the C-O-C key of olefin(e) acid Arrcostab；
Abs (c): in the IR measurement carried out using total reflection measuring method to described adhesive layer, in 800~900cm-1In range Minimum absorbance.
2. adhesive phase according to claim 1, wherein described adhesive layer contains alkali metal salt.
3. adhesive phase according to claim 1 or 2, wherein described adhesive layer contains operates improver again.
4. adhesive phase described in any one of claim 1 to 3, with a thickness of 25 μm or less.
5. a kind of unilateral protection polarizing coating with adhesive phase, with the unilateral guarantor only in the single side of polarizer with protective film Protect polarizing coating and in the polarizer side of the unilateral protection polarizing coating directly or across overlay in Claims 1 to 4 Described in any item adhesive phases.
6. the unilateral protection polarizing coating according to claim 5 with adhesive phase, wherein the polarizer with a thickness of 12 μm or less.
7. the unilateral protection polarizing coating according to claim 5 or 6 with adhesive phase, wherein the polarizer contains poly- Vinyl alcohol resin, and the structure in such a way that the optical characteristics indicated by monomer transmissivity T and degree of polarization P meets the condition of following formula At:
P >-(100.929T-42.4- 1) × 100 (wherein, T < 42.3) or
P >=99.9 (wherein, T >=42.3).
8. the unilateral protection polarizing coating according to any one of claim 5~7 with adhesive phase, wherein described to be polarized It is 25 weight % boric acid below that mirror, which contains relative to polarizer total amount,.
9. the unilateral protection polarizing coating according to any one of claim 5~8 with adhesive phase, wherein described viscous Diaphragm is provided in mixture layer.
10. the unilateral protection polarizing coating according to claim 9 with adhesive phase, is coiling body.
11. a kind of image display device, with the unilateral protection described in any one of claim 5~8 with adhesive phase Polarizing coating.
12. a kind of method for continuous production of image display device comprising following processes:
It will continuously send out and utilize from the coiling body of the unilateral protection polarizing coating with adhesive phase described in any one of claim 10 The unilateral protection polarizing coating with adhesive phase that the diaphragm transports continuously fits in image via described adhesive layer The surface of display panel.
CN201880015688.7A 2017-03-29 2018-03-29 Adhesive layer, single-sided protective polarizing film with adhesive layer, image display device, and continuous production method therefor Active CN110382648B (en)

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