CN100533186C - Polarizing plate and image display including the same - Google Patents
Polarizing plate and image display including the same Download PDFInfo
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- CN100533186C CN100533186C CNB2007101041418A CN200710104141A CN100533186C CN 100533186 C CN100533186 C CN 100533186C CN B2007101041418 A CNB2007101041418 A CN B2007101041418A CN 200710104141 A CN200710104141 A CN 200710104141A CN 100533186 C CN100533186 C CN 100533186C
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Abstract
A polarizing plate is provided that has excellent polarization properties and high surface hardness and can have a reduced thickness. The polarizing plate includes a polarizer and a cured resin layer. The cured resin layer is formed directly on at least one surface of the polarizer. The cured resin layer is formed of a solventless photocurable composition containing the following components (A), (B), and (C): (A) at least one of a polyfunctional acrylic monomer and a polyfunctional methacrylic monomer; (B) a photocurable prepolymer; and (C) a photopolymerization initiator.
Description
Technical field
The present invention relates to polaroid and used the image display device of this polaroid.
Background technology
Various image display devices one of be LCD (LCD).LCD utilizes the electrooptics characteristic of liquid crystal molecule to come the device of display text or image etc.Usually, LCD possesses liquid crystal cells and at two polaroids of liquid crystal cells both sides configurations.The structure that above-mentioned polaroid normally obtains with bonding agent stickup diaphragm in the both sides of the polarizer.As said protection film, be extensive use of triacetyl cellulose (TAC) film all the time.In addition, sometimes above-mentioned polaroid being carried out hard conating (high rigidityization) handles.Above-mentioned hard conating is handled by using light-cured resin to form hard conating on the TAC film and is undertaken.Above-mentioned hard conating is handled usually the one-sided TAC film among the TAC film of the both sides of the above-mentioned polarizer is carried out (for example, referring to Patent Document 1).
On the other hand,, for example in mobile devices such as portable phone and automobile navigation instrument, use LCD, just require to improve hardness for polaroid along with the purposes expansion of LCD.In addition, for polaroid, also require to make the thickness attenuation.For this requirement, propose to have omitted the TAC film, on the surface of the polarizer, use the optical polymerism compound to form the polaroid (patent documentation 2) of protective seam.
About the raising of hardness, in pencil hardness test method, do not demonstrate the polaroid of the above hardness of 6H according to JIS K 5400 (nineteen ninety version) regulation in the past.In addition, for having omitted the TAC film in order to realize slimming, on the surface of the polarizer, having used the optical polymerism compound to form the polaroid of protective seam, aspect polarization characteristic, have problems.
Patent documentation 1: the spy opens communique 2005-No. 338550
Patent documentation 2: the spy opens communique 2005-No. 10329
Summary of the invention
Therefore, the purpose of this invention is to provide the hardness height, can slimming and the polaroid of polarization characteristic excellence and used the image display device of this polaroid.
To achieve these goals, polaroid of the present invention comprises the polarizer and curing resin layer, it is characterized in that, directly form above-mentioned curing resin layer at least one surface of the above-mentioned polarizer, above-mentioned curing resin layer is following by comprising (A) composition, (B) composition and (C) curing resin layer that forms of the no-solvent type Photocurable composition of composition.
(A) polyfunctional acrylic ester is at least a among monomer and the multifunctional methacrylate ester monomer;
(B) photo-curable prepolymer;
(C) Photoepolymerizationinitiater initiater.
Image display device of the present invention is equipped with polaroid, it is characterized in that, above-mentioned polaroid is a polaroid of the present invention.
The inventor etc. have carried out a series of research at using photocurable compound directly to form the polaroid in the past of protective seam on the polarizer repeatedly with regard to the reduction of characteristic.The result finds out, for above-mentioned polaroid in the past, because when forming protective seam, use solvent, so because the above-mentioned nip polarizer, thereby cause characteristic to reduce.Based on this opinion, the inventor finds, when directly forming curing resin layer at least one surface of no-solvent type Photocurable composition at polaroid of using above-mentioned composition, the characteristic of the polarizer does not reduce, and can form than in the past hard conating and have the more curing resin layer of high rigidity, thereby finish the present invention.Polaroid of the present invention is because the optical characteristics excellence, has more high rigidity than in the past polaroid, and can omit protective seam, so can filming.
Description of drawings
Fig. 1 (a) and (b) be the section of structure of an example of the structure of expression polaroid of the present invention.
Fig. 2 is the synoptic diagram of an example of the manufacture process of the expression polarizer.
Fig. 3 is the synoptic diagram of an example of the manufacture process of expression polaroid of the present invention.
Symbol description
1 polarizer 2 the 1st curing resin layer 3 the 2nd curing resin layer
4 bond layers, 5 protective seams
301 is the macromolecule membrane of major component with the polyvinyl alcohol resin
300 outputs, 310 swellings are bathed 320 dye baths
311,312,321,322,331,332,341,342 rollers
330 the 1st crosslinked bath 340 the 2nd crosslinked bath 350 washings are bathed
360 drying devices, 370 polarizers, 380 reel-up
401 outputs, 402 polarizers, 403 deflector rolls
404 coating machines, 405 ultraviolet lamps, 406 light sources
407 irradiators, 408 reel-up
Embodiment
In the polaroid of the present invention, the thickness (d of above-mentioned curing resin layer
1) and the thickness (d of the above-mentioned polarizer
2) ratio (d
1/ d
2) be preferably 0.3～1.2 scope.
In the polaroid of the present invention, the thickness (d of above-mentioned curing resin layer
1) and the thickness (d of the above-mentioned polarizer
2) poor (d
1-d
2) be preferably the scope of-20 μ m～+ 5 μ m.
In the polaroid of the present invention, the complex elastic-modulus of the above-mentioned polarizer is preferably more than the 6Gpa.
In the polaroid of the present invention, the thickness of above-mentioned curing resin layer is preferably the scope of 10 μ m～30 μ m.
In the polaroid of the present invention, the polyfunctional acrylic ester of above-mentioned (A) composition is that monomer or multifunctional methacrylate ester monomer preferably have 4 above acryloyl groups or methacryl in molecular structure.At this moment, the polyfunctional acrylic ester of above-mentioned (A) composition is that monomer and multifunctional methacrylate ester monomer are preferably the monomer by following general formula (I) expression.
[Chemical formula 1]
In the above-mentioned general formula (I), R
1, R
2, R
3, R
4, R
5And R
6Be respectively hydrogen atom, acryloyl group or methacryl independently; R
1, R
2, R
3, R
4, R
5And R
6In at least 4 be acryloyl group or methacryl.
In the polaroid of the present invention, the photo-curable prepolymer of above-mentioned (B) composition is preferably at least a among urethane acrylate and the urethane methacrylate.
In the polaroid of the present invention, above-mentioned no-solvent type Photocurable composition also preferably comprises following (D) composition: (D) reactive diluent.
In the polaroid of the present invention, the Photoepolymerizationinitiater initiater of above-mentioned (C) composition is preferably the acetophenone series initiators.
In the polaroid of the present invention, the above-mentioned polarizer preferably comprises iodine and polyvinyl alcohol resin.
In the polaroid of the present invention, preferred double as hard conating of above-mentioned curing resin layer and protective seam.
The manufacture method of polaroid of the present invention for example is to comprise following (A) and (B) manufacture method of operation.In above-mentioned manufacture method, can also comprise following (C) operation.The preferred form of manufacture method of the present invention is identical with polaroid of the present invention with condition.But polaroid of the present invention also can be with the method manufacturing beyond the above-mentioned manufacture method.
(A) the above-mentioned Photocurable composition of coating and form the operation of coated film at least one surface of the polarizer;
(B) above-mentioned coated film is carried out photo-irradiation treatment and it is solidified to form the operation of curing resin layer;
(C) operation by bond layer or the stacked protective seam of bonding agent on the surface that does not form above-mentioned curing resin layer of above-mentioned polaroid.
The present invention is described in detail below by enumerating example.
[A, polaroid of the present invention]
As mentioned above, polaroid of the present invention is to use the direct structure that forms above-mentioned curing resin layer and obtain of Photocurable composition at least one surface of the polarizer.Among the present invention, above-mentioned curing resin layer can form on a surface of the above-mentioned polarizer, also can form on two surfaces of the above-mentioned polarizer.Among the present invention, above-mentioned " directly forming " is meant, do not carry out stacked by other layer such as bond layer, adhesive phase or parts etc. with the above-mentioned polarizer and the direct state of contact of above-mentioned curing resin layer.Among the present invention, the flat shape of above-mentioned polaroid for example is a rectangle, can be square, can be rectangle also, is preferably rectangle.Therefore, among the present invention, the shape of each structure member such as the above-mentioned polarizer and above-mentioned curing resin layer is preferably rectangle, can be square, also can be rectangle, preferably consistent with the flat shape of polaroid rectangle.As mentioned above, preferred double as protective seam of above-mentioned curing resin layer and hard conating, if this mode, polaroid just can slimming.
From preventing that above-mentioned curing resin layer from producing the reason consideration of be full of cracks, as mentioned above, the thickness (d of curing resin layer
1) and the thickness (d of the above-mentioned polarizer
2) ratio (d
1/ d
2) be preferably 0.3～1.2 scope, more preferably 0.4～1.0 scope is preferably 0.5～0.8 scope especially.
From preventing that above-mentioned curing resin layer from producing the reason consideration of be full of cracks, as mentioned above, the thickness (d of above-mentioned curing resin layer
1) and the thickness (d of the above-mentioned polarizer
2) poor (d
1-d
2) being preferably the scope of-20 μ m～+ 5 μ m, the scope of μ m～0 μ m more preferably-16 is preferably the scope of-12 μ m～-4 μ m especially.
In the polaroid of the present invention, the pencil hardness of above-mentioned cured resin laminar surface is preferably more than the 6H, and more preferably the scope of 7～9H is preferably 9H especially.In addition, above-mentioned pencil hardness is the pencil cut value of measuring according to JIS K 5400 (nineteen ninety version).The polaroid through after the hard conating processing does not in the past show the above hardness of 6H.Its reason is presumed as follows.By inference, the hard conating of polaroid in the past can not realize that the above high rigidity of 6H is because disposed protective seams such as TAC film in the both sides of the polarizer, and formed hard conating on the surface of above-mentioned protective seam.Relative therewith, by inference, in polaroid of the present invention,, on the surface of the polarizer, directly form curing resin layer by using the no-solvent type Photocurable composition, be the above high surface hardness of 6H thereby obtain pencil hardness.That is, by inference, in polaroid in the past; on the protective seam of softness, form hard conating, in contrast, in polaroid of the present invention; owing on the polarizer harder, directly form curing resin layer, so can realize the high rigidity that 6H is above than protective seam.Thus, the inventor at first finds, by directly form curing resin layer on the surface of the polarizer, can realize the high rigidity that 6H is above, and this can be described as the not effect of the excellence of expectability of those skilled in the art.In addition, above-mentioned supposition to the present invention without any limiting or restriction.
There is shown the structure of an example of polaroid of the present invention at the section of Fig. 1 (a).In addition, in Fig. 1 (a), for the structure of easy to understand polaroid of the present invention, the size of each structure member is different with reality with ratio, and other structural drawing (1 (b)) too.Shown in Fig. 1 (a), in the polaroid 10 of this example, go up directly formation the 1st curing resin layer 2 on a surface of the polarizer 1 (being upper surface in the figure), go up on another surface of the polarizer 1 (being lower surface in the figure) and directly form the 2nd curing resin layer 3.In the polaroid 10 of this example, above-mentioned the 1st curing resin layer 2 and the 2nd curing resin layer 3 double as protective seam and hard conatings.Consequently, polaroid 10 is able to slimming.Among the present invention, above-mentioned curing resin layer can be a single layer structure, also can be the stepped construction more than two layers.
There is shown the structure of another example of polaroid of the present invention at the section of Fig. 1 (b).In addition, in Fig. 1 (b), to the part mark identical symbol identical with Fig. 1 (a).As shown in the figure, in the polaroid 10 of this example, go up directly formation curing resin layer 2, on another surface of the polarizer 1, form protective seams 5 by bond layer 4 on a surface of the polarizer 1 (being the surface of upside in the figure).In the polaroid 10 of this example, above-mentioned curing resin layer 2 double as protective seam and hard conatings, consequently, polaroid 10 is able to slimming.In addition, also can on above-mentioned protective seam 5, form hard conating.Among the present invention, bond layer and protective seam can be single layer structures, also can be the stepped constructions more than two layers.
On at least one surface of polaroid of the present invention, can also have the bonding coat that is used for other parts stickup.In addition, in the polaroid of the present invention, the surface structure of above-mentioned curing resin layer also can be a concaveconvex structure.When if the surface of curing resin layer is concaveconvex structure, then has the function of anti-dazzle property.In addition, in the polaroid of the present invention, can also form anti-reflection layer (low-index layer) on the surface of above-mentioned curing resin layer.
The thickness of polaroid of the present invention is the scope of 20～250 μ m for example, is preferably the scope of 40～200 μ m, more preferably the scope of 60～180 μ m.
In the polaroid of the present invention, its whole transmissivity (T) is preferably 38～45% scope, and its degree of polarization (P) is preferably more than 98%.By above-mentioned whole transmissivity (T) and above-mentioned degree of polarization (P) are set at above-mentioned scope, in the liquid crystal indicator that has used polaroid of the present invention, can obtain the higher display image of contrast ratio of frontal.Above-mentioned whole transmissivity (T) is 39～44% scope more preferably, and above-mentioned degree of polarization (P) is more preferably more than 99%.
Degree of polarization can be by measuring the parallel transmissivity (H of polaroid
0) with vertical transmissivity (H
90), by formula: degree of polarization (%)={ (H
0-H
90)/(H
0+ H
90)
1/2* 100 obtain.Above-mentioned parallel transmissivity (H
0) be that two identical polaroids are overlapping according to the parallel mode of absorption axes each other and the value of the transmissivity of the parallel type laminated polarizing sheet made.In addition, above-mentioned vertical transmissivity (H
90) be that two identical polaroids are overlapping according to the vertical mode of each other absorption axes and the value of the transmissivity of the vertical-type laminated polarizing sheet made.In addition, these transmissivities are the Y values of having carried out the visibility revisal by the 2 degree visuals field (illuminant-C) of JIS Z 8701-1982.
In the polaroid of the present invention, its colourity a value (whole a value) is preferably-and more than 2.0, its colourity b value (whole b value) is preferably below 4.2.In addition, the optimal value of above-mentioned colourity a value (whole a value) and above-mentioned colourity b value (whole b value) is 0.Approach 0 numerical value by above-mentioned colourity a value (whole a value) and above-mentioned colourity b value (whole b value) are set at, can obtain the more bright-coloured display image of color.
[the B. polarizer]
The polarizer that uses among the present invention just can be selected any suitable polarizer so long as can realize the object of the invention.As the above-mentioned polarizer, for example can list: make dichroic substance such as hydrophilic macromolecule thin film adsorbs iodine or dichroic dye and carry out the film that uniaxial tension forms, polyenes such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol (PVA) and Polyvinylchloride are oriented film etc.As above-mentioned hydrophilic macromolecule film, for example can list: polyvinyl alcohol film, part formolation polyvinyl alcohol film, ethylene-vinyl acetate copolymer pastern divide saponification film etc.Among the present invention, preferably make polyvinyl alcohol film absorption iodine and the polarizer that forms.
The thickness of the above-mentioned polarizer is the scope of 5～50 μ m for example, is preferably the scope of 10～40 μ m, more preferably the scope of 20～40 μ m.
The complex elastic-modulus of the above-mentioned polarizer (Er) is preferably more than the 6Gpa.By using the polarizer of the complex elastic-modulus more than the 6Gpa, further can obtain the polaroid of high rigidity.Above-mentioned complex elastic-modulus is the scope of 8～15Gpa more preferably, is preferably the scope of 9～14Gpa especially.The complex elastic-modulus of the polarizer (Er) for example can wait suitably and adjust by moisture, the cross-linking density of adjusting the polarizer.
Under the situation of the polarizer that forms making polyvinyl alcohol film absorption iodine, if the optical characteristics of considering, then above-mentioned content of iodine for example is the scope of 2.0～5.0 weight %, is preferably the scope of 2.0～4.0 weight %.
The above-mentioned polarizer preferably also comprises at least a among potassium and the boron.The potassium content of the above-mentioned polarizer is preferably the scope of 0.2～1.0 weight %, more preferably the scope of 0.3～0.9 weight %.The boron content of the above-mentioned polarizer is preferably the scope of 0.5～3.0 weight %, more preferably the scope of 1.0～2.8 weight %.The above-mentioned polarizer is by containing potassium and boron, the polarizer (polaroid) that can obtain having preferred complex elastic-modulus (Er), degree of polarization is high.The Production Example that comprises at least a polarizer among potassium and the boron will get final product in the thin film dipped at least a solution among potassium and boron as the formation material of the polarizer in this way.Above-mentioned solution also can double as contains the solution of iodine.
Above-mentioned polyvinyl alcohol resin can be that the vinyl esters based polymer saponification that monomer polymerization obtains obtains by for example making vinyl esters.If consider the permanance of the polarizer, then the saponification degree of above-mentioned polyvinyl alcohol resin is preferably 95～99.9 moles of %.The average degree of polymerization of above-mentioned polyvinyl alcohol resin can be selected suitable value as required and aptly, is preferably 1200～3600 scope.In addition, above-mentioned average degree of polymerization can be obtained according to for example JIS K 6274 (version in 1994).
Above-mentioned polyvinyl alcohol film preferably contains at least a among plastifier and the surfactant.As above-mentioned plastifier, for example can list: polyvalent alcohols such as ethylene glycol and glycerine.As above-mentioned surfactant, for example can list non-ionic surfactant.By using above-mentioned polyvalent alcohol, above-mentioned surfactant, can further improve the dyeability and the stretchability of the polarizer.
As the method that obtains above-mentioned polyvinyl alcohol film, can adopt any suitable shaping processing method.As above-mentioned shaping processing method, can suitably use known method in the past.
As above-mentioned polyvinyl alcohol film, also can directly use commercially available film.As commercially available polyvinyl alcohol film, for example can list: the trade name " Tohcello VinylonFilm " of the trade name of the Kuraray of Co., Ltd. system " Kuraray Vinylon Film ", Tohcello Co., Ltd. system, the trade name of The Nippon Synthetic Chemical Industry Co., Ltd's system " day is closed Vinylon Film " etc.
An example with reference to the manufacture method of 2 pairs of polarizers of figure describes.As shown in the figure, for example, macromolecule membrane (material film) 301 that with the polyvinyl alcohol resin is major component is by output 300 outputs, be immersed in the swelling that comprises pure water and bathe 310 and comprise in the dye bath 320 of iodine aqueous solution, the limit vertically applies tension force than different roller 311,312,321 and 322 to film with speed, and swelling treatment is carried out on the limit and dyeing is handled.Then, thin film dipped in the 1st crosslinked bath 330 neutralizations the 2nd crosslinked bath 340 that comprises potassium iodide after will handling through swelling treatment and dyeing, the limit vertically applies tension force than different roller 331,332,341 and 342 to film with speed, and crosslinking Treatment and final stretch processing are carried out in the limit.To impregnated in the washing that comprises pure water and bathe in 350 through the film after the crosslinking Treatment by roller 351 and 352, wash processing.Carry out drying by the film after will handling through washing with drying device 360, thereby moisture for example will be adjusted to 10～30%, batch with reel-up 380.Thus, the polarizer 370 can be in these a series of operations obtains by material film being stretched as 5～7 times of raw footage for example.
In order to improve the adhesiveness with curing resin layer etc., the above-mentioned polarizer also can carry out surface modification treatment arbitrarily.As above-mentioned surface modification treatment, for example can list: corona treatment, Cement Composite Treated by Plasma, glow discharge processing, flame treatment, ozone treatment, UV ozone treatment, UV treatment etc.These processing can be used separately or be used in combination more than two kinds.
[C. curing resin layer]
Above-mentioned curing resin layer of the present invention above-mentioned by comprising (A) composition, (B) composition and (C) Photocurable composition of composition form.Among the present invention, the polyfunctional acrylic ester of above-mentioned (A) composition is that monomer or multifunctional methacrylate ester monomer are meant, has the acrylic ester monomer or the methacrylate ester monomer of two above acryloyl groups or methacryl in molecular structure.In addition, among the present invention, the photo-curable prepolymer of above-mentioned (B) composition is meant to have photoreactive functional group in molecular structure, and the repeat number of structural unit is the polymkeric substance more than 2.The repeat number of said structure unit is 2～20 a scope for example.
Above-mentioned curing resin layer can comprise above-mentioned (A) composition, (B) composition and (C) composition unreacted and residual unreacted reactant also can not comprise such unreacted reactant.But in order to obtain high skin hardness, preferably the unreacted reactant that comprises in above-mentioned curing resin layer is less, does not preferably contain unreacted reactant.
Consider that from the viewpoint of hardness the thickness of above-mentioned curing resin layer is thick more, hardness is high more.But,, also in above-mentioned curing resin layer, produce be full of cracks sometimes if blocked up.Consider the preferred thickness of suitably setting above-mentioned curing resin layer from high rigidity and the viewpoint that prevents to chap.The thickness of above-mentioned curing resin layer is the scope of 5～30 μ m for example, is preferably the scope of 7～23 μ m, more preferably the scope of 10～23 μ m.
The complex elastic-modulus of above-mentioned curing resin layer (Er) is preferably more than the 4Gpa, more preferably the scope of 4～8Gpa, the more preferably scope of 5～7Gpa.The hardness of above-mentioned curing resin layer (H) is preferably more than the 400MPa, more preferably the scope of 400～800Mpa, the more preferably scope of 500～700Mpa.Demonstrate the Er of above-mentioned scope and the solidification compound of H by use, can form the high curing resin layers of scratch hardness such as pencil hardness.
The Photocurable composition that uses among the present invention is the no-solvent type that does not contain solvent.When using the no-solvent type Photocurable composition,,, also can use the material of the weak material of solvent resistance as the polarizer so can not make applied polarizer deterioration owing to do not comprise solvent.In addition, when forming curing resin layer, do not need the solvent seasoning operation, can not produce variety of issue (whiting, be full of cracks, curing deficiency etc.) because of solvent produces.In addition, owing to do not have solvent evaporates in atmosphere when forming curing resin layer, thereby can not produce the environmental pollution that causes by solvent and to operator's Health cost.
The polyfunctional acrylic ester of above-mentioned (A) composition that uses among the present invention is that monomer or methacrylate ester monomer use for the cross-linking density that improves above-mentioned curing resin layer.Above-mentioned polyfunctional acrylic ester is that monomer or methacrylate ester monomer preferably have 4～6 acryloyl groups or methacryl in molecular structure, more preferably is the acrylic ester monomer or the methacrylate ester monomer of above-mentioned general formula (I).As the preferred example of above-mentioned general formula (I), the compound by following general formula (II) expression is arranged.
[Chemical formula 2]
Above-mentioned polyfunctional acrylic ester is that the weight-average molecular weight (Mw) of monomer or multifunctional methacrylate ester monomer is preferably 250～800 scope.By weight-average molecular weight (Mw) is set at above-mentioned scope, can obtain skin hardness excellence, curing resin layer that cure shrinkage is little.Above-mentioned weight-average molecular weight (Mw) is preferably 320～700 scope, more preferably 400～650 scope.
In above-mentioned (A) composition, as the above-mentioned polyfunctional acrylic ester beyond above-mentioned is monomer, for example can list: five acrylic acid dipentaerythritol ester, pentaerythritol tetracrylate, trimethyol propane triacrylate, two (trimethylolpropane) esters of tetrapropylene acid, isocyanuric acid three (acrylyl oxy-ethyl) ester etc.In addition, in above-mentioned (A) composition, above-mentioned multifunctional methacrylate ester monomer as beyond above-mentioned for example can list: pentamethyl acrylic acid dipentaerythritol ester, pentaerythritol tetramethacrylate, trihydroxy methyl propane trimethyl acrylate, two (trimethylolpropane) esters of tetramethyl acrylic acid, isocyanuric acid three (methylacryoyloxyethyl) ester etc.These polyfunctional acrylic esters are that monomer or multifunctional methacrylate ester monomer can be used alone, and also can more than two kinds and use.
Above-mentioned polyfunctional acrylic ester is that monomer or multifunctional methacrylate ester monomer also can use commercially available product.Commercially available product can be used a kind separately, also can the commercially available product more than two kinds be used in combination.Polyfunctional acrylic ester as above-mentioned commercially available product is monomer or multifunctional methacrylate ester monomer, for example can list: Toagosei Co., Ltd's system trade name " Aronix " series, Toagosei Co., Ltd's system trade name " ARON OXETANE " series, Nippon Kayaku K. K's system trade name " KAYARAD " series etc.
Among the present invention, be that fundamental purpose is used with the film rerum natura of improving curing resin layer as the photo-curable prepolymer (being also referred to as the photo-curable oligomer) of above-mentioned (B) composition.By and with above-mentioned (A) composition and above-mentioned (B) composition, can make above-mentioned curing resin layer have the flexibility of appropriateness, can obtain skin hardness firmly and to the curing resin layer of the adhesiveness excellence of the polarizer etc.
As above-mentioned photo-curable prepolymer, be not particularly limited, for example can list: polyester acrylate, polyester methacrylate, epoxy acrylate, epoxy methacrylates, urethane acrylate, urethane methacrylate etc.These prepolymers can be used alone, and also can mix and use more than two kinds.In these prepolymers, optimization polyurethane acrylate and urethane methacrylate.Urethane acrylate and urethane methacrylate are because molecular weight is big, and the cross-linking density of the per unit area of above-mentioned curing resin layer becomes lower when therefore using it, can further suppress the cure shrinkage of above-mentioned curing resin layer.Consequently, can further reduce the be full of cracks and the warpage of the polaroid that causes by above-mentioned cure shrinkage.
Consider from skin hardness that improves curing resin layer and the viewpoint that prevents cure shrinkage, the weight-average molecular weight of above-mentioned photo-curable prepolymer (Mw) is preferably 250～5000 scope, more preferably 300～4000 scope, more preferably 400～3000 scope.
Above-mentioned urethane acrylate or urethane methacrylate in molecular structure, have urethane bond (-NHCO-) and be selected from acryloyl group and methacryl among at least a.Above-mentioned urethane acrylate or urethane methacrylate can be by for example following (a) or (b) method is synthetic.
(a) make polyisocyanate with two above isocyanate group, have the polyvalent alcohol of two above hydroxyls and be selected from least a reaction among hydroxy acrylate with an above hydroxyl and the hydroxyl-metacrylate with an above hydroxyl.
(b) make the polyisocyanate with two above isocyanate group and be selected from least a reaction among hydroxy acrylate with two above hydroxyls and the hydroxyl-metacrylate with two above hydroxyls.
As above-mentioned polyisocyanate, for example can list: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 4,4 '--diphenyl diisocyanate, 1,5-naphthalene diisocyanate, Xylene Diisocyanate etc.As above-mentioned polyvalent alcohol, for example can list: 1,3-butylene glycol, 1,4-butylene glycol, trimethylolethane, trimethylolpropane, two trimethylolethane, dipentaerythritol, two glycerine etc.As above-mentioned hydroxy acrylate, for example can list: acrylic acid 2-hydroxyl ethyl ester, acrylic acid 4-hydroxyl cyclohexyl, acrylic acid 5-hydroxyl ring monooctyl ester, pentaerythritol triacrylate etc.As above-mentioned hydroxyl-metacrylate, for example can list: methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 4-hydroxyl cyclohexyl, methacrylic acid 5-hydroxyl ring monooctyl ester, trimethyl acrylic acid pentaerythritol ester etc.
Above-mentioned urethane acrylate and urethane methacrylate also can use commercially available product.Commercially available product can be used a kind separately, also can be used in combination the commercially available product more than two kinds.Urethane acrylate or urethane methacrylate as commercially available product for example can list: The Nippon Synthetic Chemical Industry Co., Ltd's system trade name " purple light " series, DAICEL-CYTEC Co., Ltd. system aliphatic urethane acrylate etc.
Consider from viewpoints such as the skin hardness of curing resin layer and cohesives, the mass ratio (A:B) of above-mentioned (A) composition and above-mentioned (B) composition for example is the scope of A:B=98:2～50:50, the scope that is preferably A:B=98:2～60:40 (wherein, A+B=100).
Above-mentioned Photocurable composition also preferably comprises the reactive diluent as above-mentioned (D) composition.By using above-mentioned reactive diluent, the viscosity of above-mentioned Photocurable composition can be adjusted into the scope that is fit to coating, thereby obtain the above-mentioned curing resin layer of surface uniformity excellence.
As above-mentioned reactive diluent, for example use the low monomer of 1～3 official energy.As above-mentioned low monomer; for example can list: trimethyol propane triacrylate; trihydroxy methyl propane trimethyl acrylate; diacrylate 1; 3-butanediol ester; dimethacrylate 1; 3-butanediol ester; diacrylate 1; 4-butanediol ester; dimethacrylate 1; 4-butanediol ester; diacrylate 1; 6-hexanediol ester; dimethacrylate 1,6-hexanediol ester; the diacrylate binaryglycol ester; diethyleneglycol dimethacrylate; diacrylic acid pentyl diol ester; the dimethacrylate DOPCP; acrylic acid 2-Octyl Nitrite; methacrylic acid 2-Octyl Nitrite; acrylic acid 2-hydroxyl ethyl ester; methacrylic acid 2-hydroxyl ethyl ester; acrylic acid 2-hydroxypropyl acrylate; methacrylic acid 2-hydroxypropyl acrylate; tetrahydrofurfuryl acrylate; tetrahydrofurfuryl methacrylate; acryloyl morpholine; methacryl morpholine etc.These reactive diluents can be used alone, also can be also with more than two kinds.
Consider from the viewpoint of the skin hardness of the viscosity of above-mentioned Photocurable composition and above-mentioned curing resin layer, the total amount (A+B) of above-mentioned (A) composition and above-mentioned (B) composition for example is the scope of A+B:D=95:5～50:50 with the mass ratio (A+B:D) of above-mentioned (D) composition, the scope that is preferably A+B:D=85:15～65:35 (wherein, A+B+D=100).
Photoepolymerizationinitiater initiater as above-mentioned (C) composition is not particularly limited, and for example can list: acetophenone series initiators, benzoin ether series initiators, benzophenone series initiators, thioxanthones series initiators etc.Viewpoint such as painted and curing rate considers that the Photoepolymerizationinitiater initiater of above-mentioned (C) composition is preferably the acetophenone series initiators when preventing to solidify.As above-mentioned acetophenone series initiators, for example can list: diethoxy acetophenone, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxyl-2-methyl-1-phenyl-propane-1-ketone, 2-methyl-2-morpholinyl (4-sulphomethyl phenyl) propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-phenyl-1,2-propane diketone-2-(o-ethoxy carbonyl) oxime etc.These light triggers can be used alone, also can be also with more than two kinds.
Above-mentioned Photoepolymerizationinitiater initiater can directly use commercially available product, can also be also with the commercially available product more than two kinds.As the Photoepolymerizationinitiater initiater of commercially available product, for example can list: trade name " IRGACURE " series of Ciba SpecialityChemicals company limited system etc.In addition, as above-mentioned Photoepolymerizationinitiater initiater, also can use the commercially available product of various Tokyo HuaCheng Industry Co., Ltd.
When in above-mentioned Photocurable composition, not using above-mentioned (D) composition, as the use amount of the Photoepolymerizationinitiater initiater of above-mentioned (C) composition be, total amount (A+B) 100 weight portions with respect to above-mentioned (A) composition and above-mentioned (B) composition are preferably 1～10 weight portion, more preferably 2～8 weight portions.And when stating (D) composition in the use, as the use amount of the Photoepolymerizationinitiater initiater of above-mentioned (C) composition be, total amount (A+B+D) 100 weight portions with respect to above-mentioned (A) composition, above-mentioned (B) composition and above-mentioned (D) composition are preferably 1～10 weight portion, more preferably 2～8 weight portions.
Above-mentioned Photocurable composition also can comprise the adjuvant that is fit to arbitrarily.Above-mentioned adjuvant for example can list: levelling agent, matting agent, sensitizer, antistatic agent, antioxidant, thermal polymerization inhibitor, tackifier, plastifier, non-reactive polymer etc.The use amount of above-mentioned adjuvant be, to be preferably greater than 0 and smaller or equal to the scope of 5 weight portions with respect to total amount (A+B) 100 weight portions of above-mentioned (A) composition and above-mentioned (B) composition.
Make the method for above-mentioned no-solvent type Photocurable composition generation photocuring can adopt the method that is fit to arbitrarily.For example, can be above-mentioned no-solvent type Photocurable composition directly is coated on the surface of the polarizer and forms coated film, at least a among above-mentioned coated film irradiation ultraviolet radiation and electronics line.Above-mentioned irradiation for example can be direct irradiation on above-mentioned coated film, also can be to shine from polarizer side.
An example with reference to the manufacture method of 3 pairs of above-mentioned curing resin layers of figure describes.As shown in the figure, the polarizer 402 by output 401 outputs, by deflector roll 403 conveyances, is formed the above-mentioned no-solvent type Photocurable composition of coating and forms coated film with coating part 404.Then, the polarizer that has formed above-mentioned coated film is delivered to the ultraviolet lamp 405 with light source 406 and irradiator 407,, thereby on the surface of the polarizer, form curing resin layer here to above-mentioned coated film irradiates light.The polarizer that obtains like this and the duplexer of curing resin layer batch with reel-up 408.
As the coating process of above-mentioned Photocurable composition, the coating process that has used coating machine is for example arranged.As above-mentioned coating machine, for example can list: reverse roll coater, positive transfer roller coating machine, intaglio plate coating machine, doctor knife coater, rod are coated with machine, slit die coating machine, slit aperture coating machine, episodic curtain coater, die fountain coater, Kohler coater, kiss and are coated with machine, dip coater, bead coater, knife type coater, curtain coating coating machine, flush coater, spin coater, extrusion coating machine, heat fusing coating machine etc.Above-mentioned coating machine preferably reverse roll coater, positive transfer roller coating machine, intaglio plate coating machine, rod is coated with machine, slit die coating machine, slit aperture coating machine, episodic curtain coater and die fountain coater.Above-mentioned coating machine preferably uses the coating machine of the dispense tip that has utilized the cruciform coating device, so that prevent the concentration change of coating fluid.If use the coating process of above-mentioned coating machine, it is little just can to obtain thickness deviation, i.e. the curing resin layer of uniform thickness is so be preferred.
Above-mentioned ultraviolet lamp comprises for example light source, irradiator, cooling device and supply unit.As above-mentioned light source, for example can list: high-pressure sodium lamp, ozone free mercury lamp, xenon lamp, fusing lamp, metal halide lamp etc.The wavelength of above-mentioned light source can be considered that set time and ultraviolet penetration depth wait suitably and select.The wavelength of above-mentioned light source is the scope of 100～400nm for example, is preferably the scope of 210～380nm.The accumulation light quantity of irradiates light is preferably 50～1000mJ/cm
2Scope.
In order to reduce heat to the damage of the polarizer, above-mentioned irradiator preferably has the wave filter (for example, heat ray blocking wave filter) of the wavelength that is used to interdict infrared ray and luminous ray.Above-mentioned cooling device and supply unit are for the temperature that makes light source and irradiator integral body keeps constant, make the illumination of light stability ground and use.As above-mentioned cooling device, for example can list: cooling devices such as air cooling (air draft or supply and exhaust) mode and water-cooling pattern.
Above-mentioned curing resin layer is a concaveconvex structure in order to make its surface structure, also can comprise particulate.This is when being concaveconvex structure because of the surface structure that makes above-mentioned curing resin layer, can give anti-dazzle property.As above-mentioned particulate, inorganic particles and organic fine particles are for example arranged.Above-mentioned inorganic particles is not particularly limited, and for example can list: silicon oxide particle, titanium oxide microparticle, alumina particulate, zinc oxide fine particles, tin oxide particulate, calcium carbonate microparticle, barium sulphate particulate, talcum particulate, kaoline par-tides, calcium sulphate particulate etc.In addition, organic fine particles is not particularly limited, and for example can list: plexiglass powder (PMMA particulate), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic acid styrene resin powder, benzoguanamine toner, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide powder, polyimide resin powder, polyfluoroethylene resin powder etc.These inorganic particles and organic fine particles can be used alone, also can be also with more than two kinds.
The shape of above-mentioned particulate is not particularly limited, and for example can be the roughly spherical of bead, also can be that powder etc. is amorphous.The weight average particle diameter of above-mentioned particulate is the scope of 1～30 μ m for example, is preferably the scope of 2～20 μ m.As above-mentioned particulate, preferred roughly spherical particulate, more preferably length breadth ratio is the roughly spherical particulate below 1.5.
The cooperation ratio of above-mentioned particulate is not particularly limited, and can set aptly.The cooperation ratio of above-mentioned particulate is, is the scope of 2～60 weight portions for example with respect to above-mentioned no-solvent type Photocurable composition 100 weight portions, is preferably the scope of 1～50 weight portion.
Consider that from viewpoints such as the light scattering that prevents to produce and interference fringes preferably the refringence with above-mentioned particulate and above-mentioned curing resin layer reduces on the surface of above-mentioned particulate and above-mentioned curing resin layer.Specifically, the refringence of above-mentioned particulate and above-mentioned curing resin layer preferably is lower than 0.05.
In the polaroid of the present invention, can on above-mentioned curing resin layer, dispose anti-reflection layer (low-index layer).For example, when on image display device, polaroid being installed,, can list the reflection of light that on the interface of air and curing resin layer, takes place as one of key element that the image visibility is reduced.Anti-reflection layer is the layer that reduces described surface reflection.Above-mentioned anti-reflection layer can form with method in the past.In addition, also can on anti-reflection layer, form anti-contamination layer.Anti-contamination layer can form with method in the past.
[D. protective seam]
Among the present invention, " protective seam " is meant, separates the layer that forms with above-mentioned curing resin layer; for example; shown in Fig. 1 (b), be with the formation of the above-mentioned polarizer layer that forms across bond layer on the surface of above-mentioned curing resin layer side opposition side, be the textural element of choosing wantonly.As the formation material of above-mentioned protective seam, for example, consider from viewpoints such as polarization characteristic and permanance, preferably use cellulose-based resin or norbornene resins such as TAC.As the commercially available product of these resin films, for example can list: the trade name of Fuji Photo Film Co., Ltd.'s system " Fujitac ", the trade name " ZEONOA " of Japanese zeon Co., Ltd. system, trade name " ARTON " of JSR Corp.'s system etc.
The thickness of above-mentioned protective seam can determine aptly, considers from viewpoints such as operability, slimming such as intensity and the property handled, and for example be the scope of 1～500 μ m, be preferably the scope of 5～200 μ m, more preferably the scope of 10～150 μ m.Phase difference value as above-mentioned protective seam; phase difference value (Re) in the pellicular front is preferably the scope of 0～5nm; the scope of 0～3nm more preferably; the scope of 0～1nm more preferably; the phase difference value of thickness direction (Rth) is preferably the scope of 0～15nm; the scope of 0～12nm more preferably, the scope of 0～5nm more preferably most preferably is the scope of 0～3nm.
As being used for the above-mentioned polarizer and the stacked above-mentioned bonding agent of above-mentioned protection for example can be listed: bonding agent of forming by acrylic acid series polymeric compounds or vinyl alcohol system polymer etc.From considering the bonding agent that above-mentioned bonding agent preferably is made up of vinyl alcohol system polymer with the viewpoint of the bonding force of the polarizer.In addition, above-mentioned bonding agent can also comprise for example water-soluble cross-linker of vinyl alcohol system polymers such as boric acid, borax, glutaraldehyde, melamine, oxalic acid.
The macromolecule membrane that comprises norbornene resin when use is during as above-mentioned protective seam, as above-mentioned bonding agent, even preferably use the bonding agent that the transparency is excellent, the little thin layer of birefringence also can be brought into play bonding force fully.As such bonding agent, for example can use dry laminate that polyurethane series resin solution and polyisocyanate resin solution are mixed with bonding agent, styrene-butadiene rubber be bonding agent, epoxy be bi-component curing type bonding agent (for example, the bonding agent of forming by the bi-component of epoxy resin and polymercaptan, the bonding agent of forming by the bi-component of epoxy resin and polyamide) etc., special preferred solvent type bonding agent, epoxy are bi-component curing type bonding agent.According to different bonding agents, suitable bondingly can improve bonding force by using sometimes with silane coupling agent, when using such bonding agent, preferably use the above-mentioned bonding silane coupling agent of using.
[E. polaroid on liquid crystal cells stacked]
As mentioned above, when using when layer of polarizer of the present invention being stacked on the liquid crystal cells, preference is as being provided with adhesive phase on the surface of above-mentioned polaroid.Thus, be easy to layer of polarizer of the present invention is laminated on the above-mentioned liquid crystal cells.
As above-mentioned bonding agent, be not particularly limited, can suitably select to use the bonding agent that for example polymkeric substance such as rubber system such as acrylic acid series polymeric compounds, siloxane-based polymers, polyester, polyurethane, polyamide, polyvingl ether, vinyl acetate/vinyl chloride copolymer, improved polyalkene, epoxy system, fluorine-containing system, natural rubber, synthetic rubber is formed as base polymer.Particularly from the optical transparence excellence, show wellability, compendency, the cohesive of appropriateness, the viewpoint of weatherability and excellent heat resistance is considered, is preferably used acrylic adhesive.
[F. purposes]
Polaroid of the present invention can be preferred for liquid crystal indicator (LCD) and EL display various image display devices such as (ELD).Liquid crystal indicator of the present invention is the structure same with liquid crystal indicator in the past except using polaroid of the present invention.Liquid crystal indicator of the present invention for example can by with various structure members such as optics such as liquid crystal cells, polaroid of the present invention and the illuminator that adopts as required (backlight etc.) suitably assembling enroll driving circuit and wait and make.
Among the present invention, the structure of liquid crystal indicator is not particularly limited, and can list to have disposed the liquid crystal indicator of opticses such as polaroid of the present invention in the one or both sides of liquid crystal cells and used liquid crystal indicator of backlight or reflecting plate etc. in illuminator.When disposing optics such as polaroid of the present invention when the both sides at liquid crystal cells, they can be identical, also can be different.In addition, in liquid crystal indicator of the present invention, for example optics and optical components such as diffuser plate, antiglare layer, anti-reflection layer, fender, prism array, lens array sheet can be set also.
The purposes that is fit to that image display device of the present invention can be used for choosing wantonly.This purposes for example can list: OA equipment such as desktop computer, notebook computer, duplicating machine; Portable equipments such as portable phone, clock and watch, digital camera, portable information terminal (PDA), portable game; Domestic electric appliances such as video camera, TV, electronic range; Vehicle mounted equipment such as backward supervision device, auto-navigation system watch-dog, automobile audio; Commercial shop with information with presentation devices such as watch-dogs; Supervision is with guard equipment such as watch-dogs; Nurse, Medical Devices etc. such as nurse watch-dog, medical watch-dog.
Embodiment
Below embodiments of the invention are described with comparative example.In addition, the present invention is not limited or restriction by embodiment and comparative example.In addition, each analytical approach in embodiment and the comparative example is as follows.
(1) Determination of thickness method:
When thickness is lower than 10 μ m, use film to make ProductName " moment many photometric systems MCPD-2000 " with spectrophotometer (Otsuka Electronics Co., Ltd.) measure.When thickness is 10 μ m when above, use Anritsu corporate system digital micrometer " KC-351C type " to measure.
(2) each element of the polarizer (I, K, B) Determination on content method:
By by the X ray intensity of x-ray fluorescence analysis, obtain each constituent content according to the lubber-line that uses standard sample to make in advance according to the circular sample of the diameter 10mm of following condition mensuration.
Analytical equipment: Liue electrical machinery Industrial Co., Ltd's system fluorescent x-ray analyzer (XRF) ProductName " ZSX100e "
Anticathode: rhodium
Analyzing crystal: lithium fluoride
Exciting light energy: 40kV-90mA
Sizing technique: FP method
(3) assay method of the transmissivity of polaroid and degree of polarization:
The transmissivity of polaroid and degree of polarization use spectrophotometer (Co., Ltd. of color technical institute system ProductName " DOT-3 " in the village) to measure by said method.
(4) assay method of hardness (H) and complex elastic-modulus (Er)
The small pieces of the polaroid that cuts out are embedded in the resin, freeze with cryoultramicrotome then, carry out ultra precision cutting and make sample.Use Hysitron corporate system ProductName " TriboIndenter ", the section of this sample is carried out single mensurations that is pressed into (be pressed into sub: Berkovich (triangular pyramidal), compression distance: 230～280nm).Each sample is carried out 3 times measure, obtain mean value.
(5) assay method of pencil hardness:
Use the pencil of different hardness, by obtaining pencil cut value according to the test method(s) of JIS K 5400 (nineteen ninety version).
(embodiment 1)
To be that (thickness is 75 μ m for the macromolecule membrane of major component with the polyvinyl alcohol resin, Kuraray Co., Ltd. system trade name " VF-PS#7500 ") impregnated in 5 baths of following (1)～(5) condition, simultaneously vertically apply tension force to film, stretching makes that final stretching ratio is 6.2 times with respect to the film raw footage.40 ℃ air circulating type drying oven inner drying 1 minute, making thickness was the polarizer A (complex elastic-modulus is 10.9GPa) of 30 μ m with this oriented film.The content of each element is among this polarizer A: content of iodine is 3.0 weight %, and potassium content is 0.6 weight %, and boron content is 2.0 weight %.
(condition)
(1) swelling is bathed: 30 ℃ pure water.
(2) dye bath: 30 ℃ aqueous solution comprises 0.03 weight portion iodine with respect to water 100 weight portions in this aqueous solution, and comprises 0.2 weight portion potassium iodide with respect to water 100 weight portions.
(3) the 1st crosslinked baths: 40 ℃ the aqueous solution that comprises the boric acid of the potassium iodide of 3 weight % and 3 weight %.
(4) the 2nd crosslinked baths: 60 ℃ the aqueous solution that comprises the boric acid of the potassium iodide of 5 weight % and 4 weight %.
(5) washing is bathed: 25 ℃ the aqueous solution that comprises the potassium iodide of 3 weight %.
Then, on the surface of above-mentioned polarizer A, use with the water soluble adhesive (The Nippon Synthetic Chemical Industry Co., Ltd system trade name " Gohsefimer Z200 ") of polyvinyl alcohol resin as major component, forming thickness is the bond layer of 0.1 μ m.By above-mentioned bond layer, on the surface of above-mentioned polarizer A, paste TAC film (thickness is 80 μ m, Fuji Photo Film Co., Ltd.'s system trade name " ZRF80S "), form protective seam.
Then, on another surface of above-mentioned polarizer A, be coated with the no-solvent type Photocurable composition of following composition and form coated film, on above-mentioned coated film, use high-pressure sodium lamp, according to being that accumulation light quantity under the 365nm is 300mJ/cm at wavelength
2The mode irradiation ultraviolet radiation, be the curing resin layer of 22 μ m thereby form thickness.
(no-solvent type Photocurable composition)
(A) composition: by acrylic ester monomer (Nippon Kayaku K. K's system trade name " KAYARAD DPHA ", Mw=578) 74 weight portions of above-mentioned general formula (II) expression
(B) composition: urethane acrylate (The Nippon Synthetic Chemical Industry Co., Ltd's trade name " purple light UV-7600B ") 5 weight portions
(C) composition: 1-hydroxycyclohexylphenylketone (Ciba Speciality Chemicals corporate system trade name " Irgacure 184 "), 5 weight portions
(D) composition: tetrahydrofurfuryl acrylate (Wako Pure Chemical Industries, Ltd.'s system) 21 weight portions
The polaroid A of the Zhi Zuoing-1 TAC film (protective seam) that has polarizer A (thickness is 30 μ m), on the curing resin layer (thickness is 22 μ m) that directly forms on the surface of the above-mentioned polarizer and another surface, paste like this by bond layer at the above-mentioned polarizer.The whole transmissivity of above-mentioned polaroid A-1 is 41.1%, and degree of polarization is 99.9%.The pencil hardness of the cured resin laminar surface of this polaroid A-1 is 9H.In addition, the complex elastic-modulus of the curing resin layer of above-mentioned polaroid A-1 (Er) is 5.5Gpa, and hardness (H) is 541MPa.With above-mentioned polaroid A-1 23 ℃ indoor preservation 24 hours, the surface state by the above-mentioned curing resin layer of visual observations then.Results verification is not be full of cracks on above-mentioned cured resin laminar surface.
(embodiment 2)
Except the thickness that makes curing resin layer is 10 μ m, similarly make polaroid A-2 with the foregoing description 1.In above-mentioned polaroid A-2, the complex elastic-modulus of whole transmissivity, degree of polarization and curing resin layer is identical with the foregoing description 1.In addition, the pencil hardness of the cured resin laminar surface of above-mentioned polaroid A-2 is 7H.With above-mentioned polaroid A-2 23 ℃ indoor preservation 24 hours, the surface state by the above-mentioned curing resin layer of visual observations then.Results verification is not be full of cracks on above-mentioned cured resin laminar surface.
(embodiment 3)
Except the thickness that makes curing resin layer is 15 μ m, similarly make polaroid A-3 with the foregoing description 1.In above-mentioned polaroid A-3, the complex elastic-modulus of whole transmissivity, degree of polarization and curing resin layer is identical with the foregoing description 1.In addition, the pencil hardness of the cured resin laminar surface of above-mentioned polaroid A-3 is 9H.With above-mentioned polaroid A-3 23 ℃ indoor preservation 24 hours, the surface state by the above-mentioned curing resin layer of visual observations then.Results verification is not be full of cracks on above-mentioned cured resin laminar surface.
(embodiment 4)
Except the thickness that makes curing resin layer is 25 μ m, similarly make polaroid A-4 with the foregoing description 1.In above-mentioned polaroid A-4, the complex elastic-modulus of whole transmissivity, degree of polarization and curing resin layer is identical with the foregoing description 1.In addition, the pencil hardness of the cured resin laminar surface of above-mentioned polaroid A-4 is 9H.With above-mentioned polaroid A-4 23 ℃ indoor preservation 24 hours, the surface state by the above-mentioned curing resin layer of visual observations then.Results verification has produced be full of cracks on above-mentioned cured resin laminar surface.
(comparative example)
In the both sides of the polarizer, prepare to have the polaroid (Nitto Denko Corp's system trade name " NPF SIG1224DU ", the complex elastic-modulus of TAC film is 5.8Gpa) of TAC film.On the surface of the TAC film of a side of above-mentioned polaroid, use with the same method of the foregoing description 1 and form curing resin layer.The whole transmissivity of the polaroid B of Zhi Zuoing is 41.1% like this, and degree of polarization is 99.9%.The pencil hardness on the cured resin surface of above-mentioned polaroid B is 5H.
(reference example)
On the surface of PET film (thickness is 75 μ m, Dongli Ltd. system trade name " RumirerS27E ", complex elastic-modulus is 5.8Gpa), use with the same method of the foregoing description 1 and form curing resin layer.The pencil hardness of the cured resin laminar surface of the duplexer of Zhi Zuoing is 4H like this.
(evaluation)
The curing resin layer of the polaroid shown in the embodiment 1～4 is by the no-solvent type Photocurable composition directly being coated on the surface of the polarizer, making it that photocuring takes place then and form.These polaroids are compared with polaroid in the past, show extra high skin hardness (pencil hardness: 7～9H).On the other hand, the curing resin layer of the polaroid shown in the comparative example is to form on the surface as the TAC film of the protective seam of the polarizer.The skin hardness of the polaroid of this comparative example is compared much lower (pencil hardness: 5H) with the hardness of embodiment.The curing resin layer of the duplexer shown in the reference example is to form on the surface of the PET film that is used for touch panel etc.The skin hardness of the duplexer of reference example is also same with comparative example, compares much lower (pencil hardness: 4H) with the hardness of embodiment.
In addition, among the embodiment 1～3 below the thickness setting with curing resin layer is 23 μ m, on above-mentioned cured resin laminar surface, do not produce be full of cracks.On the other hand, be among the embodiment 4 of 25 μ m at thickness setting with curing resin layer, confirm on above-mentioned cured resin laminar surface, to have produced be full of cracks.
As mentioned above, the polarization characteristic excellence of polaroid of the present invention is compared with polaroid in the past, shows extra high skin hardness, and can slimming.Therefore, when using polaroid of the present invention, for example can prevent very effectively when liquid crystal indicator assemble and generation scar when using, and can realize the slimming of image display devices such as liquid crystal indicator.
Claims (13)
1. polaroid, it comprises the polarizer and curing resin layer, it is characterized in that, on at least one surface of the above-mentioned polarizer, directly form above-mentioned curing resin layer, above-mentioned curing resin layer is following by comprising (A) composition, (B) composition and (C) curing resin layer that forms of the no-solvent type Photocurable composition of composition
(A) polyfunctional acrylic ester is at least a among monomer and the multifunctional methacrylate ester monomer;
(B) photo-curable prepolymer;
(C) Photoepolymerizationinitiater initiater.
2. polaroid according to claim 1, the thickness d of wherein said curing resin layer
1Thickness d with the described polarizer
2Ratio d
1/ d
2It is 0.3～1.2 scope.
3. according to the polaroid of claim 1 record, the thickness d of wherein said curing resin layer
1Thickness d with the described polarizer
2Difference d
1-d
2Scope for-20～5 μ m.
4. polaroid according to claim 1, the complex elastic-modulus of the wherein said polarizer are more than the 6GPa.
5. polaroid according to claim 1, the thickness of wherein said curing resin layer are the scope of 10～30 μ m.
6. polaroid according to claim 1, the polyfunctional acrylic ester of wherein said (A) composition are that monomer or multifunctional methacrylate ester monomer have 4 above acryloyl groups or methacryl in molecular structure.
7. polaroid according to claim 6, the polyfunctional acrylic ester of wherein said (A) composition are that monomer and multifunctional methacrylate ester monomer are the monomers by following general formula (I) expression,
In the described general formula (I), R
1, R
2, R
3, R
4, R
5And R
6Be respectively hydrogen atom, acryloyl group or methacryl independently; R
1, R
2, R
3, R
4, R
5And R
6In at least 4 be acryloyl group or methacryl.
8. polaroid according to claim 1, the photo-curable prepolymer of wherein said (B) composition are at least a among urethane acrylate and the urethane methacrylate.
9. polaroid according to claim 1, wherein said no-solvent type Photocurable composition also comprise following (D) composition: (D) reactive diluent.
10. polaroid according to claim 1, the Photoepolymerizationinitiater initiater of wherein said (C) composition is the acetophenone series initiators.
11. polaroid according to claim 1, the wherein said polarizer are to make polyvinyl alcohol resin thin film adsorbs iodine and the polarizer that forms.
12. polaroid according to claim 1, wherein said curing resin layer double as hard conating and protective seam.
13. an image display device that is equipped with polaroid is characterized in that, described polaroid is the described polaroid of claim 1.
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| CN111133012A (en) * | 2017-09-22 | 2020-05-08 | 株式会社Lg化学 | Solvent-free photocurable resin composition for protective layer of polarizing plate, polarizing plate comprising cured product thereof, and image display device |
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| JP5196651B2 (en) | 2008-11-27 | 2013-05-15 | 日東電工株式会社 | Iodine polarizing film and method for producing the same |
| TW201038681A (en) * | 2009-02-17 | 2010-11-01 | Nippon Steel Chemical Co | Polarizing plate having a silicone coated hardened film and a liquid crystal display device |
| JP5788646B2 (en) * | 2009-06-25 | 2015-10-07 | 住友化学株式会社 | Polarizing plate, composite polarizing plate, and liquid crystal display device |
| CN101852943B (en) * | 2010-06-18 | 2012-05-23 | 欧浦登(福建)光学有限公司 | Polarizer of liquid crystal screen |
| JP6171276B2 (en) * | 2011-07-12 | 2017-08-02 | 住友化学株式会社 | Polarizer and manufacturing method thereof |
| TW201520043A (en) * | 2013-10-09 | 2015-06-01 | 富士軟片股份有限公司 | Polarizing plate, graphic display device |
| JP6806453B2 (en) * | 2016-03-17 | 2021-01-06 | 日東電工株式会社 | A method for manufacturing a single-protective polarizing film with a transparent resin layer, a method for manufacturing a polarizing film with an adhesive layer, and a method for manufacturing an optical laminate. |
| CN109946783A (en) * | 2019-03-26 | 2019-06-28 | 惠州市华星光电技术有限公司 | Polarizer and its manufacturing method |
| JP2020204700A (en) * | 2019-06-17 | 2020-12-24 | 日東電工株式会社 | Method for manufacturing laminated polarization film and device for manufacturing laminated polarization film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111133012A (en) * | 2017-09-22 | 2020-05-08 | 株式会社Lg化学 | Solvent-free photocurable resin composition for protective layer of polarizing plate, polarizing plate comprising cured product thereof, and image display device |
| CN111133012B (en) * | 2017-09-22 | 2022-01-28 | 杉金光电(苏州)有限公司 | Solvent-free photocurable resin composition for protective layer of polarizing plate, polarizing plate comprising cured product thereof, and image display device |
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| CN101075000A (en) | 2007-11-21 |
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