CN1790060A - Hard-coated film and method of manufacturing the same - Google Patents

Abstract

The invention is directed to a hard-coated film, comprising: a transparent film substrate; and a hard-coating layer formed on at least one side of the transparent film substrate, wherein the hard-coating layer is made from a material containing a urethane acrylate, a polyol (meth)acrylate and a (meth)acrylic polymer having an alkyl group containing at least two hydroxyl groups. There can be provided a hard-coated film that has high hardness and good flexibility and is resistant to curling due to hardening and shrinking and a method of manufacturing a hard-coated film in which a reduction in production efficiency associated with an increase in the number of manufacturing steps is prevented.

Description

Hard-coated film and manufacture method thereof

Technical field

The present invention relates at least one face of clear films base material, be provided with the hard-coated film and the manufacture method thereof of hard conating.Say in more detail, relate to compatibly to be used for the hard-coated film and the manufacture method thereof of optical element, CRT (Cathode Ray Tube), LCD (LCD), plasma scope (PDP) and electroluminescent display image display devices such as (ELD) such as polaroid.

Background technology

As one of various image display devices LCD is arranged, but be accompanied by with high visual field angling, the height of LCD become more meticulous, relevant technical renovation such as high-speed responsive, color reproduction, utilize the application of LCD also to change to TV from subnotebook PC or monitor.The basic comprising of LCD is, the flat glass substrate of transparency electrode will be possessed respectively, in the mode in the slit that becomes certain intervals by the configuration of dividing plate subtend, between this glass substrate, inject liquid crystal material, sealing, as liquid crystal cells, and then polaroid is set respectively on the lateral surface of a pair of glass substrate.Be the cover plate that glass or plastics formation are installed on the liquid crystal cells surface in the past, prevented to damage the polaroid that on the liquid crystal cells surface, attaches.But, when cover plate is installed, be disadvantageous aspect cost and the weight, then the polaroid surface is coated with processing firmly.

The transparent plastic film base material has been coated with firmly the hard-coated film of processing, usually use electric power radiation-curable resins such as heat-curing resin or uv curing resin, obtain forming the thin hard conating about 2～10 μ m on the transparent plastic film base material.When the above-mentioned resin of coating on glass is provided with hard conating, demonstrate characteristic more than the 4H in pencil hardness, but in substrate is under the situation of transparent plastic film base material, if the thickness low LCL of hard conating is abundant, usually be subjected to the influence of this transparent plastic film base material, pencil hardness is reduced to below the 3H.

Travel to home-use TV machine by application,, also carry out the same operation of televisor with the CRT that utilizes glass in the past even the user of general home-use TV machine can easily expect using the televisor of LCD with LCD.The pencil hardness of the CRT of glass is about 9H, and is apparent in view with the difference of the pencil hardness characteristic of existing hard-coated film.For this reason, even pencil hardness less than 9H, requires the further hardness of hard-coated film to improve.

In order to increase the hardness of hard-coated film, can be by increasing the bed thickness of hard conating.But, the increase of bed thickness cause splitting of hard conating or peel off, by the crimping that the cure shrinkage of hard conating causes, consequently can't actually use.Therefore, in recent years, the disadvantage that is produced is the result of realization who solves the high rigidityization of hard-coated film, it is the crimping that splits or cause by cure shrinkage of hard conating, as solution to the problems described above, finished following spy and opened flat 9-113728 communique, spy and open flat 11-300873 communique, the spy opens the 2000-52472 communique, the spy opens flat 7-287102 communique motion.

Open in the flat 9-113728 communique the spy, disclose and at least one face of transparent resin film, formed the polaroid protective film that constitutes the cured coating film layer by the composition that comprises ultra-violet solidified polyvalent alcohol (methyl) acrylic ester resin.And then also disclosing above-mentioned ultra-violet solidified polyvalent alcohol (methyl) acrylic ester resin simultaneously is the acrylic acid dipentaerythritol ester.Opening flat 9-113728 communique according to this spy, under situation about using by the cured coating film layer that constitutes as the resin of major component with the acrylic acid dipentaerythritol ester, is more than the 10 μ m by making its thickness, and can make pencil hardness is more than the 4H.In addition, also record by and be the main points that resin reduces the crimping that caused by cure shrinkage with epoxy, but, then be difficult to fully suppress crimping if the spy opens the described invention of flat 9-113728 communique.

Open in the flat 11-300873 communique the spy, disclose at least one face of plastic film substrate film that to be provided with by thickness be the hard-coated film that the cushion that constitutes of 1 layer of 3～50 μ m or multilayer and then the hard conating that forms thick 3～15 μ m on cushion form.Opening flat 11-300873 communique according to this spy, is 4H～8H as the pencil hardness of hard-coated film integral body.But,, have the problem points that operation quantity increases, production efficiency reduces because make the two-layer structure of cushion and hard conating.

Open in the 2000-52472 communique the spy, disclose and possess cured resin by the hard-coated film of rete, wherein, described cured resin is that setting contains the ultramicronized curing resin layer of internal crosslinking of inanimate matter or organic matter as the 1st hard conating on base material by rete, then, and then the film do not contain inanimate matter or the organic ultramicronized transparent cured resin of internal crosslinking is set forms.But, be the two-layer structure of the 1st hard conating and the 2nd hard conating because make cured resin by rete, to open the described invention of flat 11-300873 communique identical with above-mentioned spy, has the problem points that operation quantity increases, production efficiency reduces.

Open in the flat 7-287102 communique the spy, disclose the antireflective film that at least one face at the table back side of transparent base film, has hard conating, low-index layer at least, and then, can enumerate solvent seasoning type resin as the material that can be used for hard conating.When containing polymkeric substance with reactive group, have and suppress cure shrinkage that produces when ionizing radiation curable resin etc. comes into force and the effect that suppresses the appearance of crimping, but when adding such polymkeric substance, has the problem that can't obtain enough skin hardnesses.

Summary of the invention

The present invention puts and the invention finished just in view of the above problems, and its purpose is, the generation and the flexible outstanding hard-coated film of the crimping that inhibition causes by cure shrinkage is provided.In addition, its purpose also is, provides a kind of and suppresses that production efficiency is followed the increase of worker ordinal number and the manufacture method of the hard-coated film of the reduction that occurs.And then its purpose also is, a kind of polaroid and image display device that has possessed above-mentioned hard-coated film is provided.

The inventor etc. concentrate on studies to hard-coated film and manufacture method thereof in order to solve above-mentioned problem in the past.Found that, can reach above-mentioned purpose, so that finished the present invention by adopting following formation.

Promptly, for addressing the above problem, the invention provides a kind of hard-coated film, it is the hard-coated film that is provided with hard conating at least one face of transparent membrane base material, it is characterized in that the formation material of described hard conating comprises urethane acrylate, polyvalent alcohol (methyl) acrylate and has (methyl) acrylate copolymer of the alkyl that contains two above hydroxyls.

According to above-mentioned formation,, can give elasticity and flexible to this hard conating by containing the formation material of urethane acrylate as hard conating.In addition, by containing polyvalent alcohol (methyl) acrylate, can carry out the high rigidityization of hard conating.And then, have (methyl) acrylate copolymer that contains 2 above hydroxyls by containing, can make that cure shrinkage is relaxed and the hard conating that is suppressed of crimping.

In above-mentioned hard-coated film, above-mentioned polyvalent alcohol (methyl) acrylate preferably contains pentaerythritol triacrylate and pentaerythritol tetracrylate and constitutes.

If above-mentioned formation, can keep high rigidity and good flexible in, further suppress the generation of crimping.

In above-mentioned hard-coated film, the outside surface of above-mentioned hard conating preferably becomes concaveconvex shape.

According to above-mentioned formation, the concaveconvex structure that is positioned at the outside surface of hard conating can only prevent the light reflection and make its scattering on prescribed direction, so can prevent to mirror.Thus, can give light anti-dazzle property.

In above-mentioned hard-coated film, preferably the outside surface at above-mentioned hard conating is formed with anti-reflection layer.

When on the outside surface as above-mentioned formation anti-reflection layer being set, can be reduced in the reflection of light on the interface of hard conating and air at hard conating.Thus, when the hard-coated film with above-mentioned formation for example was applied to image display device etc., the identification that can suppress the image of display frame reduced.

In above-mentioned hard-coated film, above-mentioned anti-reflection layer preferably contains: the number-average molecular weight that converts by ethylene glycol is that 500～10000 siloxane oligomer and the number-average molecular weight by polystyrene conversion are more than 5000 and have the fluorine compounds of fluoro-alkyl structure and polysiloxane structure.

As above-mentioned formation, when anti-reflection layer is when containing siloxane oligomer and having the formation of fluorine compounds of fluoro-alkyl structure and polysiloxane structure, this anti-reflection layer solidifies because of the polysiloxane structure of siloxane oligomer and fluorine compounds reacts, so mar resistance improves.In addition, be more than 500 by the number-average molecular weight that makes siloxane oligomer, it is good to be coated with the coating and the storage stability that form material firmly, can prevent to apply liquid generation gelation.It is below 10000 by making number-average molecular weight on the other hand, can become the good layer of mar resistance of anti-reflection layer.

In above-mentioned hard-coated film, in above-mentioned anti-reflection layer, preferably contain hollow and spherical monox ultra micron.

In addition, in above-mentioned hard-coated film, the formation material of preferred above-mentioned hard conating contains levelling agent.

In addition, the manufacture method of hard-coated film of the present invention is in order to solve above-mentioned problem, on at least one face of clear films base material, form the manufacture method of the hard-coated film of hard conating, wherein, comprising: in diluting solvent, add urethane acrylate, polyvalent alcohol (methyl) acrylate at least and have (methyl) acrylate copolymer of the alkyl that contains 2 above hydroxyls and the operation of modulating the formation material of above-mentioned hard conating; Above-mentioned formation material is coated at least one face of film substrate and forms the operation of coated film; Make above-mentioned coated film solidify to form the operation of hard conating.

According to above-mentioned method,, can form elasticity and flexible outstanding hard conating by using the formation material of urethane acrylate as hard conating.In addition, by using polyvalent alcohol (methyl) acrylate,, also can form hard conating with enough hardness and mar resistance even for example be not two-layer structure.Its result can also suppress the increase of manufacturing process's quantity, and prevents the reduction of production efficiency.And then, in forming material, comprise (methyl) acrylate copolymer with the alkyl that contains 2 above hydroxyls, can relax the cure shrinkage that when above-mentioned coated film is solidified, produces, form the hard conating of the generation that has suppressed crimping.

In the manufacture method of above-mentioned hard-coated film, the preferred use contained the solvent of ethyl acetate as above-mentioned diluting solvent.Thus, can form the hard conating outstanding with the adhesiveness of film substrate.

In the manufacture method of above-mentioned hard-coated film, the content of preferred above-mentioned ethyl acetate is more than the 20 weight %.

Thus, can form the hard conating outstanding with the adhesiveness of film substrate.

In addition, optical element of the present invention is provided with foregoing hard-coated film in order to solve above-mentioned problem at least one face of optical component.

In addition, image display device of the present invention in order to solve above-mentioned problem, possesses foregoing hard-coated film or optical element.

The present invention is by method performance explained before effect as described below.

Promptly, according to the present invention, in the formation material of hard conating, contain urethane acrylate, polyvalent alcohol (methyl) acrylate and have (methyl) acrylate copolymer of the alkyl that contains 2 above hydroxyls, thus the elasticity of obtaining and flexible outstanding, than more can suppress crimping or split and hard-coated film that skin hardness is big in the past.In addition, there is no need the hard-coated film as in the past, hard conating is made two-layer structure,, prevent the reduction of production efficiency so can suppress the increase of worker ordinal number in order to increase hardness.

Description of drawings

Fig. 1 is the schematic cross-section of summary of the hard-coated film of expression an embodiment of the invention.

Fig. 2 is the schematic cross-section of summary of the antireflective hard coating film of expression other embodiments of the present invention.

Embodiment

About embodiments of the present invention, carry out following explanation with reference to accompanying drawing.Fig. 1 is the schematic cross-section of summary of the hard-coated film of expression present embodiment.

As shown in Figure 1, hard-coated film 3 is the formations that have hard conating 2 on the one side of clear films base material 1.In addition, though do not show in Fig. 1, hard conating 2 also can be arranged on the two sides of film substrate 1.In addition, in Fig. 1, illustration hard conating 2 are situations of individual layer, but so long as have the structure of hard conating of the present invention, they can also be more than 2 layers.

Above-mentioned film substrate 1 so long as the outstanding base material (preferred turbidity value is below 1%) of the transmittance of visible light outstanding (preferred transmittance is more than 90%) and the transparency just be not particularly limited.Specifically, for example, can be exemplified as by polyester based polymers such as polyethylene terephthalate or PENs; Cellulose-based polymkeric substance such as diacetyl cellulose or triacetyl cellulose; The polycarbonate based polymer; The film that transparent polymers such as acrylic acid series polymeric compounds such as polymethylmethacrylate constitute.In addition, can also enumerate by polystyrene, acrylonitritrile-styrene resin styrenic, tygon, polypropylene such as (AS resins), polyolefin, olefin polymers such as ethylene-propylene copolymer with ring-type or norborene structure; Vinyl chloride-based polymer; The film that transparent polymers such as acid amides such as nylon or aromatic polyamide based polymer constitute.In addition, can also enumerate by the imide series polymkeric substance; The sulfone based polymer; The polyethersulfone based polymer; Polyethers-ether ketone based polymer; The polyphenylene sulfide based polymer; The vinyl alcohol based polymer, the vinylidene chloride based polymer; The polyvinyl butyral based polymer; The arylide based polymer; The polyoxymethylene based polymer; The epoxy based polymer; The perhaps film that constitutes of transparent polymer such as above-mentioned mixture of polymers etc.Be particularly suitable for the film that uses optic birefringence few.When the hard-coated film 3 with present embodiment is used for polaroid as protective film,, preferred triacetyl cellulose, polycarbonate, acrylic acid series polymeric compounds, has the polyolefin of ring-type or norborene structure etc. as film substrate 1.In addition, film substrate 1 can be a polariscope described later self.If such formation, the protective seam that need be made of TAC etc. and can make the structure simplification of polaroid so can reduce the worker ordinal number, does not improve production efficiency.In addition, can further make the polaroid thin layerization.In addition, be under the polariscopic situation at film substrate 1, the effect of hard conating 2 performances protective seam in the past.In addition, as hard-coated film, can have the function that is installed in the lip-deep cover plate of liquid crystal cells concurrently.

The thickness of film substrate 1 can suitably determine, considers aspects such as operations such as intensity or operability, thin layer usually, is 10～500 μ m.Be preferably 20～300 μ m especially, more preferably 30～200 μ m.And then the refractive index of film substrate 1 is not particularly limited, be generally about 1.30～1.80 preferred especially about 1.40～1.70.

Above-mentioned hard conating 2 is that urethane acrylate (A), polyvalent alcohol (methyl) acrylate (B) and (methyl) acrylate copolymer (C) with the alkyl that contains 2 above hydroxyls are constituted as forming material.

As above-mentioned urethane acrylate (A), use and to contain (methyl) acrylic acid and/or its ester, polyvalent alcohol, diisocyanate material as constituent.For example, can use the material of making as follows, promptly make hydroxyl (methyl) acrylate, make by itself and diisocyanate are reacted with at least 1 hydroxyl by (methyl) acrylic acid and/or its ester and polyvalent alcohol.(methyl) acrylic acid is acrylic acid and/or methacrylic acid, and (methyl) is the identical meaning in the present invention.These each constituents can be a kind of, can also be also with more than 2 kinds.

As (methyl) acrylic acid ester, can enumerate (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate etc. (methyl) acrylic acid cycloalkyl ester etc.

Above-mentioned polyvalent alcohol is the compound that has 2 hydroxyls at least, for example, can enumerate ethylene glycol, 1, ammediol, 1, the 2-propylene glycol, diglycol, dipropylene glycol, neopentyl glycol, 1, the 3-butylene glycol, 1, the 4-butylene glycol, 1, the 6-hexanediol, 1, the 9-nonanediol, 1, the 10-decanediol, 2,2,4-trimethyl-1, the 3-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, hydroxyl trimethylace tonitric DOPCP, the cyclohexane dihydroxymethyl, 1, the 4-cyclohexane diol, the spiroglycol, the tristane methylol, hydrogenated bisphenol A, oxirane addition bisphenol-A, epoxypropane addition bisphenol-A, trimethylolethane, trimethylolpropane, glycerine, 3-methylpentane-1,3, the 5-triol, pentaerythrite, dipentaerythritol, tripentaerythritol, carbohydrate etc.

As above-mentioned diisocyanate, can use aromatic series, aliphatics or aromatic various diisocyanates, for example, can enumerate tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluenediisocyanate, 4,4-diphenyl diisocyanate, 1,5-naphthyl diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate, Xylene Diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-methyl diphenylene diisocyanate etc., and then can also enumerate their hydride etc.

About the addition of above-mentioned urethane acrylate (A), if very few, the flexibility of the hard conating that then obtains or adhesiveness reduce; If too much, the hardness of the hard conating after the curing reduces.For this reason, with respect to being coated with the total resinous principle (total amount of A～C composition that forms material firmly, the total amount that perhaps also comprises it when adding resin material etc.), urethane acrylate (A) is preferably 15 weight %～55 weight %, more preferably 25 weight %～45 weight %.When the addition of urethane acrylate (A) and when adding, be coated with firmly sometimes that performance reduces and not preferred with respect to being coated with firmly that the total resinous principle that forms material surpasses 55 weight %.In addition, when cooperating, do not improve flexibility or adhesiveness with ratio less than 15 weight %, not preferred sometimes.

Constituent as above-mentioned polyvalent alcohol (methyl) acrylate (B), for example can enumerate two (methyl) acrylic acid pentaerythritol ester, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, (methyl) acrylic acid 1,6-hexanediol ester etc.In addition, the polymkeric substance that especially preferably contains by pentaerythritol triacrylate and pentaerythritol tetracrylate constitutes monomer component.And then, also especially preferably contain the blending constituent of pentaerythritol triacrylate and pentaerythritol tetracrylate.

The use level of polyvalent alcohol (methyl) acrylate (B) is with respect to the ratio of the preferred 70 weight % of urethane acrylate (A)～180 weight %, the more preferably ratio of 100 weight %～150 weight %.When the cooperation of polyvalent alcohol (methyl) acrylate (B) with respect to urethane acrylate (A) when surpassing the ratio of 180 weight %, the cure shrinkage of hard conating increases, its result, the crimping of hard-coated film increases, or flexibility reduces, so not preferred sometimes.In addition, when ratio during less than 70 weight %, being coated with property is that hardness or mar resistance reduce firmly, so not preferred sometimes.In addition, about mar resistance, the viewpoint from the practicality is preferably in 0～0.7 scope, more preferably in 0～0.5 scope.Use level by making polyvalent alcohol (methyl) acrylate (B) can be set in mar resistance in the above-mentioned scope in above-mentioned scope.Here, about the calculating of above-mentioned mar resistance, in embodiment described later, describe.

As above-mentioned (methyl) acrylate copolymer (C), can use (methyl) acrylate copolymer with the alkyl that contains 2 above hydroxyls.More specifically say, for example can enumerate with what following chemical formula (1) was represented and have 2, (methyl) acrylate copolymer of 3-dihydroxypropyl or in molecule, have the constitutional repeating unit in the following chemical formula (1) and have 2-hydroxyethyl and 2, (methyl) acrylate copolymer of 3-dihydroxypropyl with the structural unit of following chemical formula (2) expression.

As the addition of (methyl) acrylate copolymer (C), with respect to the ratio of the preferred 25 weight % of urethane acrylate (A)～110 weight %, the more preferably ratio of 45 weight %～85 weight % with the alkyl that contains 2 above hydroxyls.When use level surpassed 110 weight %, screening characteristics reduces, and was not preferred sometimes.In addition, when use level during less than 25 weight %, the generation of crimping significantly increases, and is not preferred sometimes.

In addition, in the present invention,, can suppress the cure shrinkage of hard conating 2, consequently prevent crimping by containing this (methyl) acrylate copolymer (C).From making the viewpoint of hard-coated film etc., preferably the generation with crimping is suppressed in the 30mm at least, by suppress the generation of crimping in this scope, can further improve operation and production efficiency.

In hard conating 2, can cooperate inorganic particles or organic fine particles.Above-mentioned inorganic particles is not particularly limited, for example, can enumerates monox, titanium dioxide, aluminium oxide, zinc paste, tin oxide, lime carbonate, barium sulphate, talcum, porcelain earth, calcium sulphate etc.In addition, organic fine particles is not particularly limited, for example, can enumerate poly-methyl methacrylate base acrylate resin powder, silicone-based toner, polystyrene resin powder, polycarbonate resin powder, propenylbenzene vinylite powder, benzoguanamine is that toner, melamine are toner, and then can also to enumerate polyolefin-based resins powder, polyester based resin powder, polyamide-based toner, polyimide be that toner, polyvinyl fluoride are toner etc.

Shape to particulate is not particularly limited, and can be the sphere of pearl, can also be indefinite forms such as powder.These particulates can suitably be selected to use more than a kind or 2 kinds.The mean grain size of particulate is 1～30 μ m, is preferably 2～20 μ m.In addition, with refractive index control, electric conductivity is given is purpose, can in particulate, disperse, the ultra micron of impregnation metal oxide etc.

Use level to inorganic particles or organic fine particles is not particularly limited, and can suitably set.For example, giving under the situation of antiglare effect, be preferably 2～60 weight portions with respect to being coated with formation material 100 weight portions firmly.In addition, under the situation of giving simple adhesion inhibiting properties, be suitably for 1～50 weight portion with respect to being coated with formation material 100 weight portions firmly.

The particle diameter of above-mentioned inorganic particles or organic fine particles is preferably below the 100nm.Particle diameter is the following ultra micron of 100nm, has the function of regulating the apparent refractive index of hard conating 2 according to its use level.The refractive index of the refractive index of film substrate 1 and hard conating 2 is preferred approximate mutually.When the difference of the refractive index of the refractive index of film substrate 1 and hard conating 2 was big, the outer reflection of light light that has incided hard-coated film 3 presented the phenomenon that is referred to as interference fringe of the form and aspect of iridescent colors, makes the display quality deterioration sometimes.Fluorescent light as the office under the environment that has used the display device that possesses hard-coated film 3, can see thing clearly is that the stronger three-wavelength fluorescent light of the luminous intensity of specific wavelength of feature increases significantly, under this three-wavelength fluorescent light, can manifest interference fringe more significantly.

When with the refringence of the refractive index of film substrate 1 and hard conating 2 during as d, d is preferably below 0.04, more preferably below 0.02.As film substrate 1, when using polyethylene terephthalate, by being to cooperate titanium dioxide about about 35% with respect to being coated with the total resinous principle that forms material firmly in the ultra micron below the 100nm at particle diameter, can d be controlled at below 0.02 with respect to the refractive index of pet film about 1.64, can suppress the generation of interference fringe.

As film substrate 1, when using triacetylcellulose film, by being to cooperate monox about about 40% with respect to being coated with the total resinous principle that forms material firmly in the ultra micron below the 100nm at particle diameter, can d be controlled at below 0.02 with above-mentioned the same refractive index about 1.48, can suppress the generation of interference fringe with respect to triacetylcellulose film.

The thickness of above-mentioned hard conating 2 is preferably 15～25 μ m, more preferably 18～23 μ m.The lower limit of thickness is made as 15 μ m,, (for example, counts more than the 4H) with pencil hardness so hardness can be maintained more than the certain value because hard conating 2 contains polyvalent alcohol (methyl) acrylate (B).In addition, in order further to increase hardness, the higher limit of thickness is made as 25 μ m, because hard conating 2 contains urethane acrylate (A) and has (methyl) acrylate copolymer (C) of the alkyl that contains 2 above hydroxyls, so the generation that crimping can fully be prevented or split etc.In addition, when thickness during less than 15 μ m, the hardness of hard conating reduces sometimes.On the other hand, when thickness surpassed 25 μ m, self crackle appearred in hard conating, and the cure shrinkage by hard conating makes hard-coated film crimping occur being coated with the face side firmly, becomes problem sometimes in practicality.

With respect to hard conating 2, can make its outside surface become the micro concavo-convex structure and give anti-dazzle property.The method that forms the micro concavo-convex structure on the surface is not particularly limited, can adopts suitable mode.For example, can enumerate disperse particles in hard conating 2 and give method of micro concavo-convex structure etc.

When the outside surface that makes above-mentioned hard conating 2 became concaveconvex shape and gives anti-dazzle property, its thickness was preferably 15～35 μ m, more preferably 20～30 μ m.The lower limit of thickness is made as 15 μ m,, (for example, counts more than the 4H) with pencil hardness so hardness can be maintained more than the certain value because hard conating 2 contains polyvalent alcohol (methyl) acrylate (B).In addition, in order further to increase hardness, the higher limit of thickness is made as 35 μ m, when hard conating 2 contains the particulate that cure shrinkage does not take place, the generation that can fully prevent crimping or split etc.In addition, when thickness during less than 15 μ m, the hardness of hard conating 2 reduces sometimes.On the other hand, when thickness surpassed 35 μ m, self crackle appearred in hard conating, and the cure shrinkage by hard conating 2 makes hard-coated film crimping occur being coated with the face side firmly, becomes problem sometimes in practicality.In addition, the thickness of the hard conating 2 when outside surface is concaveconvex shape is meant the maximum ga(u)ge that comprises up to the part that becomes convex.

Be not particularly limited being coated with the diluting solvent that forms material firmly, can use various materials.Specifically, for example can enumerate butyl oxide, dimethoxymethane, dimethoxy-ethane, diethoxyethane, epoxypropane, 1, the 4-diox, 1, the 3-dioxolane, 1,3, the 5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone, diethyl ketone, two acetone, diisobutyl acetone, cyclopentanone, cyclohexanone, methyl cyclohexanone, methyl formate, propyl formate, the formic acid n-pentyl ester, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-Amyl acetate, diacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methyl alcohol, ethanol, the 1-propyl alcohol, the 2-propyl alcohol, the 1-butanols, the 2-butanols, the 1-amylalcohol, 2-methyl-2-butanols, cyclohexanone, isobutyl acetate, hexone, methyl n-heptyl ketone, 2 pentanone, methyl-n-butyl ketone, the 2-heptanone, 3-heptanone etc.They can make up more than a kind or 2 kinds and use.The total relatively diluting solvent of ethyl acetate is preferably more than the 20 weight %, more preferably more than the 25 weight %, is preferably the scope of 30 weight %～70 weight % especially.Thus, when using triacetyl cellulose, can form the outstanding especially hard conating of adhesiveness 2 as film substrate 1.When the content of ethyl acetate surpassed 70 weight % with respect to total diluting solvent, evaporation rate was very fast, thus coating inequality or uneven drying appear easily, when less than 20 weight %,, not preferred sometimes with the adhesiveness reduction of base material.

In being coated with the formation material firmly, can add various levelling agents.As levelling agent, can suitably use the levelling agent of fluorine system or silicone-based, more preferably use the levelling agent of silicone-based.As the levelling agent of silicone-based, can enumerate reactive silicone, dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, poly-methyl alkyl siloxane etc.In the levelling agent of these silicone-based, special preferred reactive silicone.By adding reactive silicone, give lubricity and keep mar resistance to the surface.And then the layer that contains silicone component when use is during as low-index layer, if use the material with hydroxyl as reactive silicone, then adhesiveness improves.

As the levelling agent of above-mentioned reactive silicone, for example, can illustration has the material of siloxane bond, acrylate-based and hydroxyl.More specifically say, can enumerate:

(1) (dimethyl siloxane/methyl): (3-acryloyl group-2-hydroxyl propoxyl group propyl-siloxane/methyl): the multipolymer of the mol ratio of (2-acryloyl group-3-hydroxyl propoxyl group propyl-siloxane)=0.8: 0.16: 0.04;

(2) dimethyl siloxane: hydroxypropyl siloxane: 6-isocyanates hexyl cyamelide: aliphatic polyester=6.3: 1.0: 2.2: the multipolymer of 1.0 mol ratio;

(3) dimethyl siloxane: end is the methyl polyglycol propyl ether siloxane of acrylate: the multipolymer of terminal mol ratio for the methyl polyglycol propyl ether siloxane of hydroxyl=0.88: 0.07: 0.05 etc.

The use level of levelling agent is preferably below 5 weight portions with respect to being coated with total resinous principle 100 weight portions that form material firmly, more preferably the scope of 0.01～5 weight portion.

When in being coated with the curing mechanism that forms material firmly, using ultraviolet ray, form in the material if above-mentioned levelling agent is coupled to be coated with firmly, this levelling agent is exuded to air interface when preparation drying and solvent seasoning, hinder the curing of uv curing resin so can prevent block, even can obtain the hard conating 2 that also has enough hardness the most surperficial.In addition, the levelling agent of silicone-based is given lubricity by oozing out to the surface of hard conating 2,, so also can improve mar resistance.

In the formation material of above-mentioned hard conating 2, can in the scope of not damaging formation, add pigment, filling agent, spreading agent, plastifier, ultraviolet light absorber, surfactant, antioxidant, thixotropic agent etc. as required.These adjuvants can use separately, can also be also with more than 2 kinds.

Form in the material being coated with firmly of present embodiment, can use known in the past Photoepolymerizationinitiater initiater.For example, can use 2,2-dimethoxy-2-phenyl acetophenone, acetophenone, benzophenone, xanthone, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone, benzoin propyl ether, benzyl dimethyl ketal, N, N, N ', N '-tetramethyl-4,4 '-diaminobenzophenone, 1-(4-isopropyl ether)-2-hydroxy-2-methyl propane-1-ketone, other thioxanthones based compounds etc.

In order to form above-mentioned hard conating 2, on film substrate 1 coating contain urethane acrylate (A), polyvalent alcohol (methyl) acrylate (B) at least and have the alkyl that contains 2 above hydroxyls (methyl) acrylate copolymer (C) be coated with the formation material firmly, make its curing subsequently.Being coated with the formation material firmly can apply as the solution that is dissolved in solvent when coating.When being coated with firmly when forming material and applying, after drying, solidify as solution.

As the above-mentioned method that forms material that is coated with firmly of coating on film substrate 1, coating process such as can use that known injection (fountain) coating, mouthful pattern coating, spin coating, spraying, intaglio printing coating, roller coat, rod are coated with.

The above-mentioned curing mechanism that forms material that is coated with firmly is not particularly limited, but preferred ionizing radiation solidifies.Can in this mechanism, use various active-energies, but ultraviolet ray is proper.As the energy line source, line sources such as for example preferred high-pressure mercury-vapor lamp, Halogen lamp LED, xenon lamp, metal halide lamp, nitrogen laser, electron ray accelerator, radioelement.With regard to the exposure of energy line source, as the accumulated exposure amount at ultraviolet wavelength 365nm place, preferred 50～5000mJ/cm ²When exposure less than 50mJ/cm ²The time, solidify insufficient, so the hardness of hard conating reduces sometimes.In addition, when surpassing 5000mJ/cm ²The time, the painted and transparent reduction of hard conating sometimes.

As shown in Figure 2, can on above-mentioned hard conating 2, anti-reflection layer 4 be set, make antireflective hard coating film 5.Fig. 2 is the summary schematic cross-section of the antireflective hard coating film 5 of expression present embodiment.Light is when shining object, and it is so-called in the reflection at its interface, in the absorption of inside, the phenomenon of scattering to repeat, and sees through to the back side of object.When on image display device, hard-coated film being installed,, can enumerate reflection of light at air and hard conating interface as the one of the main reasons that the identification that makes image reduces.Anti-reflection layer 4 is the layers that reduce its surface reflection.In addition, though in Fig. 2, do not demonstrate, also hard conating 2 and anti-reflection layer 4 can be arranged on the two sides of film substrate 1.In addition, in Fig. 2, illustration hard conating 2 and anti-reflection layer 4 each situation of 1 layer are set, as long as but have hard conating of the present invention, anti-reflection layer 4 can be more than 2 layers.

As anti-reflection layer 4, can enumerate the layer that the stacked strict optical thin film (anti-reflection layer) of having controlled thickness and refractive index forms on hard conating 2 surfaces.This is to have utilized the phase place of the incident light of interference of light effect and catoptrical reverse to show the method for anti-reflective function by mutual elimination.

In design,, the method for the refringence that increases anti-reflection layer 4 and hard conating 2 is arranged as the mechanism that improves its interference effect based on the anti-reflection layer 4 of interference of light effect.Usually, with regard to regard to optical thin film (film of strict above-mentioned thickness of control and refractive index) the multilayer anti-reflection layer of folded 2～5 layers of layers on substrates, by only forming the different composition of multilayer refractive index with the thickness of stipulating, degree of freedom increases aspect the optical design of anti-reflection layer 4, can further improve anti-reflection effect, dividing reflective character to flatten in the visible region also becomes possibility.Because require the thickness and precision of each layer of optical thin film, usually adopt vacuum evaporation as the dry type mode, sputter, CVD etc. to carry out the formation of each layer.

Form in the material above-mentioned being coated with firmly, can use titanium dioxide, zirconia, monox, magnesium fluoride etc., but, preferably use the duplexer of titanium oxide layer and silicon oxide layer in order to demonstrate anti-reflective function biglyyer.Above-mentioned duplexer is preferred, on hard conating, form the high titanium oxide layer (refractive index: about 1.8) of refractive index, on this titanium oxide layer, form the low silicon oxide layer of refractive index (refractive index: 2 layer laminates that about 1.45) obtain, and then on this 2 layer laminates, form titanium oxide layer and silicon oxide layer in order and 4 layer laminates that form.By the anti-reflection layer of such 2 layer laminates or 4 layer laminates is set, can reduce wavelength region may (380～780nm) the reflection of luminous ray equably.

In addition, the optical thin film by stacked individual layer on film substrate 1 can demonstrate anti-reflection effect.Even anti-reflection layer 4 is being made in the design of individual layer,, be necessary to increase the refringence of anti-reflection layer 4 and hard conating 2 in order to draw anti-reflective function to greatest extent.When the thickness with above-mentioned anti-reflection layer 4 is made as d, refractive index is made as n, when the incident light wavelength is made as λ, becomes the relational expression of nd=λ/4 between the thickness of anti-reflection layer 4 and its refractive index.When anti-reflection layer 4 when being its refractive indexes less than the such low-index layer of the refractive index of film substrate 1, under the condition that the above-mentioned relation formula is set up, it is minimum that reflectivity reaches.For example, when the refractive index of anti-reflection layer 4 was 1.45, with respect to the incident light of the wavelength of the 550nm in the luminous ray, the thickness of the anti-reflection layer 4 that reflectivity becomes hour became 95nm.

The wavelength region may that demonstrates the luminous ray of anti-reflective function is that the high wavelength region may of 380～780nm, particularly visibility is the scope of 450～650nm, and what carry out usually is to be designed to minimum as the reflectivity of the 550nm of its centre wavelength.

When single layer designs anti-reflection layer 4, its thickness and precision does not have the thickness and precision of multilayer anti-reflection layer strict like that, at least with respect to design thickness in ± 10% scope, promptly design wavelength its thickness when 95nm just can use in the scope of 86nm～105nm no problemly.Thus, usually when forming the anti-reflection layer 4 of individual layer, coating process such as can adopt that injection coating, mouthful pattern coating, spin coating, spraying, intaglio printing coating, roller coat, rod as the wet type mode is coated with.

As the material that forms anti-reflection layer 4 with individual layer, for example can enumerate resin system materials such as ultraviolet curing based acrylic resin, the mixed stocker material that has disperseed inorganic particles such as colloidal silica in resin, has used the sol-gel based material of metal alkoxides such as purity titanium tetraethoxide etc. at tetraethoxysilane.In addition, each material can use fluorochemicals in order to give surface soiling.From the aspect of mar resistance, the low-refraction layer material that inorganic constituents content is many compares look, special preferred sols-gel based material.The sol-gel based material can use in the part condensation.

Contain fluorine-based sol-gel based material as above-mentioned, can illustration perfluoroalkyl alkoxy silane.As the perfluoroalkyl alkoxy silane, for example can enumerate and use general formula: CF ₃(CF ₂) _nCH ₂CH ₂Si (OR) ₃The compound of (in the formula, R represents that carbon number is 1～5 alkyl, and n represents 0～12 integer) expression.Specifically, for example can enumerate trifluoro propyl trimethoxy silane, trifluoro propyl triethoxysilane, ten trifluoro octyl group trimethoxy silanes, ten trifluoro octyltri-ethoxysilane, 17 fluorine decyl trimethoxy silanes, 17 fluorine decyl triethoxysilanes etc.Wherein, preferred said n is 2～6 compound.

As low-index layer (anti-reflection layer), can use preferably that to open the described number-average molecular weight that converts by ethylene glycol of 2004-167827 communique be that 500～10000 siloxane oligomer and the number-average molecular weight by polystyrene conversion are more than 5000 and being coated with firmly of fluorine compounds with fluoro-alkyl structure and polysiloxane structure forms the material that material constitutes by containing the spy.

In low-index layer (anti-reflection layer), can add inorganic colloidal sol in order to improve film strength.Inorganic colloidal sol is not particularly limited, for example can enumerates monox, aluminium oxide, magnesium fluoride etc., but preferred especially silica sol.The addition of inorganic colloidal sol can suitably be set in the scope of 10～80 weight portions with respect to total solid composition 100 weight portions that low-refraction forms material.As the particle diameter of inorganic colloidal sol, preferably in the scope of 2～50nm, more preferably in the scope of 5～30nm.

In the formation material of above-mentioned anti-reflection layer 4, preferably contain hollow and spherical monox ultra micron.Hollow and the spherical preferred mean grain size of monox ultra micron are about 5～300nm, and this ultra micron is to form the hollow spheres that the cavity forms in the enclosure with pore, and solvent and/or gas when including this particulate of modulation in this cavity form.The presoma material that is preferred for forming above-mentioned cavity remains in this cavity.The thickness of above-mentioned shell is preferably in the scope about 1～50nm, and in about 1/50～1/5 scope of mean grain size.The overlayer of the preferred multilayer of above-mentioned shell constitutes.Preferred above-mentioned pore is sealed, and above-mentioned cavity is by above-mentioned body seal.In anti-reflection layer 4, keep porous matter or cavity, can reduce the refractive index of anti-reflection layer 4, so can preferably use.

Hollow and the spherical ultramicronized mean grain size of monox are about 5～300nm.This be because, when mean grain size during less than 5nm, the trend that have the volume ratio of the shell in the spheroidal particle to increase, the ratio of the volume in cavity reduces, on the other hand, when mean grain size surpasses 300nm, be difficult to obtain stable dispersion liquid, in addition, the transparency that contains this ultramicronized anti-reflection layer reduces easily.The scope that hollow and the spherical ultramicronized preferred mean grain size of monox are 10～200nm.In addition, above-mentioned mean grain size can be obtained by dynamic light scattering method.

Hollow and the spherical ultramicronized manufacture method of monox for example have following operation (a)～operation (c).Hollow and spherical monox ultra micron obtain as dispersion liquid.As such hollow and the spherical ultramicronized manufacture method of monox, for example, can compatibly adopt the spy to open that disclosed monox is the manufacture method of particulate in the 2000-233611 communique.That is,

(a) operation of modulation nuclear particle dispersion liquid as follows, described nuclear particle dispersion liquid is to be that aqueous alkali more than 10 or the pH that has been dispersed with kind of particle as required add the aqueous solution of silicate and/or acidic silicic acid liquid, the soluble inorganic compound aqueous solution of alkali simultaneously in the aqueous alkali more than 10 at pH, uses SiO ₂Represent monox, use MO _XMol ratio (the MO during mineral compound of expression beyond the monox _X/ SiO ₂) in 0.3～1.0 scope;

(b) form the tectal operation of the 1st monox, promptly in described nuclear particle dispersion liquid, add silica source and on nuclear particle, form the 1st monox overlayer;

(c) remove part or all operation of the element that constitutes above-mentioned nuclear particle, promptly in above-mentioned dispersion liquid, add the element that constitutes above-mentioned nuclear particle is removed in acid part or all.

Hollow of the present invention and the spherical ultramicronized mean grain size of monox are in the scope of 5～300nm.This is because when mean grain size during less than 5nm, the volume ratio of the shell in the spheroidal particle increases, the ratio of the volume in cavity reduces, on the other hand, and when mean grain size surpasses 300nm, be difficult to obtain stable dispersion liquid, in addition, the transparency that contains this ultramicronized anti-reflection layer reduces easily.The scope that hollow and the spherical ultramicronized preferred mean grain size of monox are 10～200nm.In addition, above-mentioned mean grain size can be obtained by dynamic light scattering method.

Above-mentioned hollow and spherical monox ultra micron dispersion liquid can make antireflection formation with applying liquid by mixing with various matrix components.Various matrix components are meant the composition that can form tunicle on the surface of hard conating, can be from being suitable for adhesiveness or the hardness with base material, select in the resin of conditions such as screening characteristics etc. to use, for example, can enumerate the vibrin that all the time uses, acryl resin, carbamate resins, vestolit, epoxy resin, melamine resin, fluororesin, silicone resin, butyral resin, phenolics, the vinyl acetate resin, ultraviolet curable resin, the electron ray curing resin, emulsion resin, water soluble resin, hydrophilic resin, the potpourri of these resins, and then can also enumerate organic resins such as the multipolymer of these resins or modification body.In addition, form the material of anti-reflection layer 4, illustrative water-disintegrable organo-silicon compound etc. can be used as matrix components as above-mentioned individual layer.

When organic resin is used as matrix components, for example, use suitable organic solvent, dilute to the dispersion in organic solvent that utilizes organic solvents such as alcohol to replace the water as above-mentioned hollow and the spherical ultramicronized dispersion medium of monox to form, as required above-mentioned ultra micron being carried out dispersion in organic solvent and matrix that known coupling agent is scattered in the organic solvent after handling, can make antireflection and form with applying liquid.

On the other hand, when using water-disintegrable organo-silicon compound as matrix components, for example, by in the mixed liquor of alkoxy silane and alcohol, adding water and as the acid or the alkali of catalyzer, obtain the partial hydrolysate of alkoxy silane, mix above-mentioned dispersion liquid therein, dilute with organic solvent as required, can make coating fluid.

Coating in the liquid above-mentioned monox ultra micron and the part by weight of matrix components preferably at the monox ultra micron: the scope of matrix=1: 99～9: 1.When above-mentioned part by weight surpasses 9: 1, the undercapacity of anti-reflection layer and lack practicality sometimes.On the other hand, when above-mentioned part by weight during less than 1: 99, the ultramicronized additive effect of above-mentioned monox is difficult to manifest.

Forming the refractive index of anti-reflection layer 4 on the surface of above-mentioned hard conating 2, because of the refractive index of the matrix of the mixture ratio of monox ultra micron and matrix components etc. and use is different, but is 1.2～1.42, becomes low-refraction.In addition, the refractive index of monox ultra micron of the present invention self is 1.2～1.38.

On the hard conating 2 of hard-coated film, be provided with the antireflective hard coating film of anti-reflection layer 4, preferred on the pencil hardness this point.It is small uneven to contain ultramicronized hard conating 2 surface formation, and this has influence on the slip (pencil tangles easily, and power is transmitted easily) of pencil.When anti-reflection layer 4 is set, unevenly become smooth, usually, the pencil hardness of hard conating is the pencil hardness that the layer about 3H can become 4H.

As such hollow and the spherical ultramicronized manufacture method of monox, for example, can compatibly adopt and open the spy that disclosed monox is the manufacture method of particulate in the 2000-233611 communique.

The drying when forming low-index layer and the temperature of curing are not particularly limited, and are generally 60～150 ℃, carry out usually 1 minute～30 minutes under preferred 70～130 ℃, under the situation of considering throughput rate, about more preferably 1 minute～10 minutes.In addition, after dry and curing,, obtain the more antireflective hard coating film of high rigidity by further carrying out heat treated.Temperature to heat treated is not particularly limited, and is generally 40～130 ℃, carries out usually 1 minute～100 hours under preferred 50～100 ℃, in order further to improve mar resistance, more preferably carries out more than 10 hours.In addition, temperature, time are not limited to above-mentioned scope, can suitably adjust.The method by heating plate, baker, band oven etc. can be suitably adopted in heating.

Because it is higher that anti-reflection layer 4 is installed in the most surperficial frequency of image display device, be subjected to pollution easily from external environment condition.Particularly adhere to pollutants such as fingerprint or hand dirt, sweat or haircut material at one's side easily, because of adhering to, this surface reflectivity is changed or attachment turns white and floats, seem that displaying contents is unclear or the like, compare, pollute more obvious with the situation of simple transparent panel etc.Under these circumstances, in order to give and above-mentioned anti-adhesion property, easy removing property function associated, can be on anti-reflection layer 4 stacked fluorine-containing silane based compound or fluorine-containing organic compound etc.

By to film substrate 1 or the hard conating 2 that on film substrate 1, has carried out coating carry out various surface treatments, can improve the cementability of film substrate 1 and hard conating 2, film substrate 1 and polariscope or hard conating 2 and anti-reflection layer 4.As its surface treatment, can use low pressure plasma processing, ultraviolet treatment with irradiation, corona treatment, flame treatment, acid or alkali treatment.In addition, specify as with triacetyl cellulose when the film substrate surface treatment and the preferred alkali soap processing of using.Preferably to carry out with washing also dry circulation after the cellulose ester film surface impregnation is in aqueous slkali.As aqueous slkali, can enumerate potassium hydroxide solution, sodium hydroxide solution, the normal concentration of hydroxide ion is 0.1N～3.0N, more preferably 0.5N～2.0N.The aqueous slkali temperature in 25 ℃～90 ℃ scope, more preferably 40 ℃～70 ℃.Subsequently, wash processing, dried, can be implemented the surface-treated triacetyl cellulose.

In addition, in order to prevent crimping, can carry out solvent processing as described below to the back side (face opposite) of film substrate 1 with the formation face of hard conating 2.Solvent processing is, adopts known method in the past, coating comprise the solvent that can make film substrate 1 dissolving maybe can make its swelling solvent composition and carry out.By being coated with such solvent, give the character that makes its change circle to the rear side of film substrate 1, thus, possessed the film substrate 1 of hard conating 2, offset the formation face side that makes hard conating 2 and produce the power of crimping, and prevent the generation of crimping.

As above-mentioned solvent, except the potpourri of the solvent that makes its dissolving and/or the solvent that makes its swelling, also further contain the solvent that does not make its dissolving sometimes.Composition and coating weight that use has mixed above-mentioned solvent according to the kind of the crimping degree of film substrate 1 or resin with suitable ratio are carried out.

When further when improving the Edge curl preventing function, with regard to the solvent composition that uses, increase can make the solvent of its dissolving and/or can make the mixture ratio of the solvent of its swelling, reduce not make the ratio of the solvent of its dissolving is effective.Its mixture ratio is preferably use (can make the solvent of its dissolving and/or can make the solvent of its swelling): (not making the solvent of its dissolving)=10: 0～1: 9.As the solvent that makes transparent resin film dissolving or swelling that in such blend compositions, contains, for example can enumerate benzene,toluene,xylene, diox, acetone, methyl ethyl ketone, N, dinethylformamide, methyl acetate, ethyl acetate, triclene, methylene chloride, ethlyene dichloride, tetrachloromethane, trichloroethanes, chloroform etc.As the solvent that does not make its dissolving, for example, can enumerate methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol etc.

Use intaglio printing coating machine, dip coater, oppositely coating machine or extrusion coating machine etc., these solvent compositions are coated on the surface of film substrate 1, and to make wet coating thickness (thickness before dry) be 1～100 μ m, 5～30 μ m more preferably.

So each solvent of coating can disperse after drying, and is in addition can also trace remaining, but the state that preferred solvent does not remain in coated face is for well.

In addition, in order to prevent the generation of crimping, can on the back side of film substrate 1 (face opposite), transparent resin layer as described below be set with the formation face of hard conating 2.As above-mentioned transparent resin layer, for example can enumerate with thermoplastic resin, radiation-curable resin, heat-curing resin, other reactive resins is the layer of major component.Wherein, especially preferably with the layer of thermoplastic resin as major component.

As above-mentioned thermoplastic resin, for example can enumerate vinyl chloride-vinyl acetate copolymer, vestolit, the vinyl acetate resin, the multipolymer of vinyl acetate and vinyl alcohol, the vinyl chloride-vinyl acetate copolymer of partial hydrolysis, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, vinyl based polymer or multipolymers such as ethylene-vinyl acetate copolymer, nitrocellulose, cellulose-acetate propionate, cellulose derivatives such as cellulose acetate-butyrate resin, maleic acid and/or acrylic acid multipolymer, acrylate copolymer, acrylonitritrile-styrene resin, haloflex, acrylonitrile-chlorianted polyethylene-styrene terpolymer, MBS, acryl resin, polyvinyl acetal resin, polyvinyl butyral resin, the polyester polyurethane resin, the polyethers polyurethane resin, the polycarbonate polyurethane resin, vibrin, polyether resin, polyamide, amino resins, the styrene-butadiene resin, rubber such as butadiene-acrylonitrile resin are resin, the silicone-based resin, fluorine resin etc.In these thermoplastic resins, for example having used the cellulose-based resin bed of diacetyl cellulose etc. is particularly preferred as transparent resin layer.

In addition, hard-coated film 3, antireflective hard coating film 5 can be fitted in the optical component that is used for LCD or ELD with its film substrate 1 side by bonding agent or tackifier usually.When fitting, can implement and above-mentioned same surface treatment film substrate 1.

As optical component, for example can enumerate polariscope or polaroid.Polaroid uses the polaroid that has transparent protective film in polariscopic one or both sides usually.When on polariscopic two sides transparent protective film being set, inside and outside transparent protective film can be an identical materials, can also be different materials.Polaroid is configured in the both sides of liquid crystal cells usually.In addition, polaroid is so that the roughly mutually orthogonal mode of the absorption axes of two polaroids disposes.

Then, in the optical element of stacked hard-coated film of the present invention or antireflective hard coating film, be that example describes with the polaroid.Hard-coated film 3 of the present invention or antireflective hard coating film 5 are by using laminated polarizing mirror or polaroids such as tackifier or bonding agent, the polaroid that can obtain having function of the present invention.

Above-mentioned polariscope is not particularly limited, can uses various polariscopes.As polariscope, for example can enumerate, divide on the hydrophilic macromolecule film such as saponification film the material of unilateral stretching after the dichroic substance such as absorption iodine or dichroic dye at polyvinyl alcohol film, part dimethoxym ethane polyvinyl alcohol film, ethylene-vinyl acetate copolymer pastern; Polyenes such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol (PVA) or Polyvinylchloride are oriented film etc.Wherein, higher by the polariscopic polarization dichroic ratio that dichroic substance such as polyvinyl alcohol film and iodine are formed, so preferred especially.These polariscopic thickness are not particularly limited, but are about 5～80 μ m usually.

With polyvinyl alcohol film with iodine staining after the polariscope that unilateral stretching forms for example, after can dyeing by the aqueous solution that polyvinyl alcohol (PVA) be impregnated in iodine, make for 3～7 times that are stretched to raw footage.As required, but also can impregnated in the aqueous solution of potassium iodide etc. of boronic acid containing or zinc sulfate, zinc chloride etc.In addition, as required, also can be before dyeing polyvinyl alcohol film be impregnated in the water and wash.

By the washing polyvinyl alcohol film, except can the lip-deep dirt of flush away polyvinyl alcohol film and anti blocking agent, also can prevent non-uniform phenomenons such as stain by making the polyvinyl alcohol film swelling.Stretch and both can after with iodine staining, carry out,, perhaps also can after stretching, dye with iodine on one side also can stretch by an Edge Coloring.Also can or stretch in the water-bath in the aqueous solution of boric acid or potassium iodide etc.

As the transparent protective film that is arranged on described polariscopic one or both sides, the preferred material that has good character in the each side such as stability of the transparency, physical strength, thermal stability, moisture shielding, phase difference value.Material as forming above-mentioned transparent protective film can be exemplified as polyester based resins such as polyethylene terephthalate or PEN; Cellulose-based resin such as diacetyl cellulose or triacetyl cellulose; Acrylic resins such as polymethylmethacrylate; Polystyrene or acrylonitritrile-styrene resin, styrene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, vinyl cyanide-ethene-styrene resin, the phenylethylene-maleic anhydride phenylethylene resin series such as imine copolymer, styrene-maleic anhydride copolymer that contract; Polycarbonate-based resin etc.In addition, by polyolefin-based resins such as ring system olefin resin, norbornene resin, tygon, polypropylene, ethylene-propylene copolymers; Vinyl chloride-based resin; Acid amides such as nylon or aromatic polyamide is a resin; Imide series such as aromatic polyimide or polyimide amide resin; Sulfone is a resin; Polyethersulfone is a resin; Polyetheretherketone is a resin; Polyphenylene sulfide is a resin; Vinyl alcohol is a resin, the vinylidene chloride resin; Polyvinyl butyral is a resin; The acrylic ester resin; Polyoxymethylene is a resin; Epoxy is a resin; Perhaps the macromolecule membrane of composition such as the potpourri of described resin etc. is also enumerated as the example of the resin that forms described transparent protective film.In addition, above-mentioned transparent protective film can also form the cured layer of thermosettings such as acrylic acid series, carbamate system, propenoic methyl carbamate system, epoxy system, silicone-based, uv curing resin.

In addition, can enumerate the thin polymer film of opening in the 2001-343529 communique (WO 01/37007) record the spy, for example comprise (A) side chain have replace and/or not substituted imido thermoplastic resin and (B) have the resin combination of the thermoplastic resin of replacement and/or unsubstituted phenyl and itrile group at side chain.As instantiation, can be exemplified as the film of the resin combination that contains the alternating copolymer formed by isobutylene and N-methyl maleimide and acrylonitritrile-styrene resin.The film that can use mixing extruded product by resin combination etc. to constitute as film.The phase differential of these films is little, and the photoelasticity modulus is little, so when being applied to the protective film of polaroid etc., can eliminate the bad situation such as inhomogeneous that is caused by distortion, in addition, moisture permeability is less, so the humidification permanance is outstanding.

As described transparent protective film,, preferably use cellulose-based resin and norbornene resins such as triacetyl cellulose from viewpoints such as polarization characteristic or permanance.Can enumerate ProductName " Off ジ Star Network " or the ProductName " ゼ オ ノ ア " of Japanese ゼ オ Application (strain) system, the ProductName " ア-ト Application " of JSR (strain) system etc. of Fujiphoto (strain) system particularly.

The thickness of described transparent protective film can suitably be determined, but from viewpoints such as operability, thin layer such as intensity or the property handled, generally be about 1～500 μ m.5～200 μ m more preferably.Preferred especially 10～150 μ m.If in above-mentioned scope, can mechanically protect polariscope, also do not shrink even be exposed to hot and humid polariscope down, guarantee stable optical characteristics.

In addition, transparent protective film had better not be painted.Therefore; the preferred use (wherein with Rth=(nx-nz) d; nx is the refractive index of the slow axis direction in the thin film planar, and nz is the refractive index of film thickness direction, and d is a film thickness) phase difference value of the film thickness direction of expression for-90nm～+ protective film of 75nm.Phase difference value (Rth) by using this thickness direction for-90nm～+ protective film of 75nm, can roughly eliminate painted (optical clouration) of the polaroid that causes by protective film.Thickness direction phase difference value (Rth) more preferably-80nm～+ 60nm, preferred especially-70nm～+ 45nm.

The phase difference value in the above-mentioned transparent protective film, its pellicular front and the phase difference value of thickness direction bring influence for sometimes the viewing angle characteristic of liquid crystal indicator, so preferably use the optimized transparent protective film of phase difference value.Wherein, the transparent protective film that what is called is expected to the optimization phase difference value is meant stacked transparent protective film on the polariscopic surface of liquid crystal cells nearside; and on the polariscopic surface in liquid crystal cells distally stacked transparent protective film because the optical characteristics of liquid crystal indicator is changed, so not subject to the limits.

As the phase difference value of transparent protective film stacked on the polariscopic surface of above-mentioned liquid crystal cells nearside, phase difference value (Re:(nx-ny) d in the preferred film face) be 0～5nm.0～3nm more preferably.Further preferred 0～1nm.The phase difference value of thickness direction (Rth) is preferably 0～15nm.0～12nm more preferably.Further preferred 0～10nm.Preferred especially 0～5nm.0～3nm most preferably.

The polaroid of stacked hard-coated film etc., can be on hard-coated film etc. stacked above one another transparent protective film, polariscope, transparent protective film, can also be on hard-coated film etc. stacked above one another polariscope, transparent protective film.

In addition, not having on the bonding polariscopic surface of transparent protective film, can also implement with hard conating or the antiseized processing that is linked as purpose.Implement purpose that hard conating handles and be to prevent the damage on polaroid surface etc., mode that for example can be by the outstanding curing tunicle of additional hardness that is made of suitable uv curing resin such as acrylic acid series, silicone-based or sliding properties etc. on the surface of transparent protective film etc. forms.In addition, implementing purpose that anti handles is the adhesion that prevents with adjacent layer.Wherein, above-mentioned hard conating, antiblocking layers etc. can also be arranged as other optical layers and transparent protective film branch except being arranged on transparent protective film from one's body.

In addition,, for example can insert hard conating, undercoat, adhesive layer, adhesive phase, antistatic backing, conductive layer, gas barrier layer, water vapour barrier layer, moisture barrier layer etc., perhaps it is laminated to the polaroid surface at the interlayer of polaroid.In addition, in the stage of each layer that makes polaroid, for example interpolation in the formation material of each layer, mixing etc. such as conductive particle or antistatic agent, various particulate, plastifier can be improved thus as required.

Above-mentioned transparent protective film and polariscopic laminating method are not particularly limited, for example can be undertaken by the tackifier that constitutes by acrylic acid series polymeric compounds or vinyl alcohol based polymer or the tackifier of forming by the water-soluble cross-linker of vinyl alcohol system polymers such as boric acid or borax, glutaraldehyde or melamine or oxalic acid at least etc.Thus, can become be difficult to humidity or heat influence under peel off and transmittance or the outstanding transparent protective film of degree of polarization.As described tackifier, from and as the outstanding viewpoint of the cementability between the polyvinyl alcohol (PVA) of polariscopic raw material, preferably use the polyethenol series tackifier.

The macromolecule membrane that will contain described norbornene resin is as transparent protective film, as the bonding agent when stacked with polariscope, even preferably clear is outstanding, birefringence etc. is little and also can give full play to the bonding agent of bounding force as thin layer.As such bonding agent, for example can use that to mix polycarbamate be that the dry type of resin solution and polyisocyanate resin solution is stacked sticks with glue agent, styrene butadiene rubbers is a tackifier, the two component curing type adhesives of epoxy system, the for example tackifier that forms by the two components of epoxy resin and polymercaptan, the bonding agent that forms by epoxy resin and polyamide pair components etc., special preferred solvent type tackifier, the two component curable tackifier of epoxy system, the bonding agent of preferably clear.According to tackifier, have and when using such bonding agent, preferably to use the bonding primer of using by using suitable bonding tackifier with primer raising bonding force.

As the above-mentioned bonding primer of using, so long as can improve the layer of cementability, just be not particularly limited, for example can use in same molecule, have amino, the silane of vinyl, epoxy radicals, sulfydryl, chloro isoreactivity functional group and water-disintegrable alkoxysilyl is coupling agent, the titanate esters that has the water-disintegrable hydrophilic radical that contains titanium and organic functional group in same molecule is coupling agent and has the water-disintegrable hydrophilic radical that contains aluminium and the aluminic acid ester of organic functional group is so-called coupling agents such as coupling agent in same molecule; Epoxy is a resin, and isocyanate-based resin, carbamate are resin, and the ester carbamate is the resin that resin etc. has the organic reaction group.Wherein, from industrial easy to handle viewpoint, preferably containing silane is the layer of coupling agent.

About above-mentioned polaroid, become easily in order to make to the stacked of liquid crystal cells, can on two sides or one side, adhesive layer or adhesive phase be set.

Tackifier or the bonding agent that is used for above-mentioned adhesive layer or adhesive phase is not particularly limited.Can suitably select and use polymkeric substance such as rubber system such as acrylic acid series polymeric compounds, silicone-based polymkeric substance, polyester, polycarbamate, polyamide, polyvingl ether, vinyl acetate/vinyl chloride copolymer, improved polyalkene, epoxy system, fluorine system, natural rubber, synthetic rubber for example as the tackifier or the bonding agent of base polymer.Particularly outstanding from optical transparence, show the wetting state of appropriateness and the adhesion characteristic and the outstanding viewpoints such as against weather or thermotolerance of compendency and cementability, preferably use acrylic adhesive.

The crosslinking chemical that can in described tackifier or bonding agent, contain corresponding base polymer.In addition, the filling agent or the proper additive such as pigment, colorant or antioxidant that also can in adhesive phase, cooperate resene, glass fibre or beaded glass, metal powder or other inorganic powder etc. of natural goods for example or complex to form as required.In addition, also can form and contain transparent particulate and the diffusible adhesive phase of display light.

Wherein, in described transparent particulate, for example, can use silicon dioxide, calcium oxide, aluminium oxide, titanium dioxide, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide that mean grain size is 0.5～20 μ m etc. to have the inorganic of electric conductivity is particulate, or suitable particulate such as the crosslinked or uncrosslinked organic fine particles of being made up of the suitable polymkeric substance of similar polymethylmethacrylate or polycarbamate and so on is more than a kind or 2 kinds.

Described tackifier or bonding agent be often used as with base polymer or its composition dissolves or be distributed in the solvent and solid component concentration be that adhesive solvent about 10～50 weight % uses.As above-mentioned solvent, can suitably select to use organic solvents such as toluene or ethyl acetate or water etc. and the corresponding solvent of the kind of tackifier.

Described tackifier or bonding agent also can be used as different compositions or kind the layer sandwich and be arranged on the one or both sides of polaroid or optical thin film.The thickness of above-mentioned tackifier or bonding agent can suitably be determined according to application target or bonding force etc., is generally 1～500 μ m, is preferably 5～200 μ m, is preferably 10～100 μ m especially.

For the face that exposes of described adhesive layer or adhesive phase etc., supplying before practical in order to prevent that it from polluting, and can paste peeling paper or mould release film (being also referred to as spacer) and cover temporarily.Can prevent the phenomenon that under common mode of operation, contacts thus with adhesive layer or adhesive phase.As above-mentioned spacer, for example can use as required with suitable removers such as silicone or chain alkyl class, fluorine class or molybdenum sulfides plastic sheeting, sheet rubber, paper, cloth, nonwoven fabrics, net, foam sheet or metal forming, their suitable thin slice bodies such as duplexer are applied material after the processing etc. based in the past suitable spacer.

As optical element, when practical application, can use the stacked optical thin film of other optical components (optical layers) on above-mentioned polaroid.This optical layers is not particularly limited, but can uses optical layers that reflecting plate for example, half transmitting plate, polarizer (comprise 1/2 or 1/4 etc. wavelength plate), viewing angle compensation film etc. use in the formation of liquid crystal indicator etc. more than 1 layer or 2 layers.Particularly preferred polaroid is reflection type polarizer or the semi-transmission type polaroid that further stacked reflecting plate or semi-penetration plate form on polaroid; Further laminated phase-difference plate forms on polaroid ellipsoidal polarizing plate or circular polarizing disk; The wide visual field angle polaroid that further stacked viewing angle compensation film forms on polaroid; Perhaps further stacked brightness improving film (have the polarizing separating film that polarisation is selected layer, for example the D-BEF of Sumitomo 3M (strain) system etc.) and the polaroid that forms on polaroid.In the polaroid etc. of ellipsoidal polarizing plate, band optical compensation, be to the additional hard-coated film of polaroid side.

And then, as required, the adhesiveness that also can be used to give mar resistance, permanance, against weather, humidity resistance, thermotolerance, moisture-proof, moisture-penetrability, static electricity resistance, electric conductivity, interlayer is improved, the processing of the various characteristicses such as improvement of physical strength, performance etc., the perhaps insertion of functional layer, stacked etc.

Reflection type polarizer is provided with the reflection horizon and forms on polaroid, can be used for forming the liquid crystal indicator of the type that reflection shows from the incident light of identification side (demonstration side) incident etc., and can omit the built-in of light sources such as backlight, thereby have advantages such as being easy to make the liquid crystal indicator slimming.When forming reflection type polarizer, can be undertaken by the suitable modes such as mode of on the one side of polaroid, setting up the reflection horizon of forming by metal etc. by above-mentioned transparent protective film etc. as required.

As the object lesson of reflection type polarizer, can be exemplified as by as required on the one side of the transparent protective film of handling through delustring, set up the paper tinsel formed by reflective metal such as aluminium or vapor-deposited film and form the polaroid etc. in reflection horizon.

Instead reflecting plate directly is attached to the method on the transparent protective film of above-mentioned polaroid, the reflection horizon can also be set on the suitable film that with this transparent membrane is benchmark forms reflector plate etc. and then use.Also have; because the reflection horizon is made up of metal usually; so decline from the reflectivity that prevents to cause owing to oxidation; and then keep the viewpoint of initial reflectance and the viewpoint of avoiding establishing protective seam in addition to wait for a long time, preferably cover the type of service of the state of its reflecting surface with transparent protective film or polaroid etc.

Also have, in above-mentioned, the semi-transmission type polaroid can obtain the reflection horizon of the semi-transmission types such as semi-transparent semi-reflecting lens of light transmission when making with reflective layer reflects light.The semi-transmission type polaroid is located at the rear side of liquid crystal cells usually, can form the liquid crystal indicator of following type etc., promptly, in brighter environment, use under the situation of liquid crystal indicator etc., reflection comes from the incident light of identification side (demonstration side) and display image, in darker environment, use built-in built-in light sources such as backlight to come display image.That is, the semi-transmission type polaroid is very useful in the formation of the liquid crystal indicator of following type etc.,, can save the energy that uses light sources such as backlight under bright environment that is, also can use built-in light source under darker environment.

Ellipsoidal polarizing plate or circular polarizing disk that further laminated phase-difference plate on polaroid is constituted describe.Rectilinearly polarized light being changed into elliptically polarized light or circularly polarized light, elliptically polarized light or circularly polarized light being changed into rectilinearly polarized light or changed under the situation of polarization direction of rectilinearly polarized light, can use polarizer etc.Particularly, as rectilinearly polarized light being changed into circularly polarized light, circularly polarized light being changed into the polarizer of rectilinearly polarized light, can use so-called 1/4 wavelength plate (being also referred to as λ/4 plates).1/2 wavelength plate (being also referred to as λ/2 plates) is generally used for changing the situation of the polarization direction of rectilinearly polarized light.

Ellipsoidal polarizing plate can be used for following situation etc. effectively, i.e. compensation (preventing) STN (Super Twisted Nematic) type liquid crystal indicator painted (blue or yellow) that produce because of the birefringence of liquid crystal layer for example, thus carry out the above-mentioned painted white black situation that shows etc. that do not have.In addition, it is painted that the polaroid of control three-dimensional refractive index produces in the time of can also compensating (preventing) from the picture of oblique observation liquid crystal indicator, thereby preferred.Circular polarizing disk for example can be used for effectively to situation of adjusting with the tone of the image of the reflection-type liquid-crystal display device of color display image etc., but also has the function of reflecting of preventing.As the object lesson of above-mentioned polarizer, can enumerate the film that the suitable polymer blend of polycarbonate, polyvinyl alcohol (PVA), polystyrene, polymethylmethacrylate, polypropylene or other polyolefin, polyarylate (Port リ ア リ レ one ト), polyamide and so on is formed implement the oriented film of birefringent film that stretch processing forms or liquid crystal polymer, with the film of the oriented layer of film support liquid crystal polymer etc.Polarizer can be that for example various wavelength plates or the be used to material that compensates the painted or visual angle that the birefringence by liquid crystal layer causes etc. etc. has the material corresponding to the suitable phase differential of application target, also can be stacked more than 2 kinds polarizer and controlled the material etc. of optical characteristics such as phase differential.

Above-mentioned in addition ellipsoidal polarizing plate or reflection-type ellipsoidal polarizing plate are by suitably combination and laminated polarizing sheet or reflection type polarizer and polarizer form.This class ellipsoidal polarizing plate etc. also can form by stacked respectively successively (reflection-type) polaroid and polarizer in the manufacture process of liquid crystal indicator, to constitute the combination of (reflection-type) polaroid and polarizer, and as mentioned above, be pre-formed member for optical thin films such as ellipsoidal polarizing plates, because outstanding, therefore has the advantage of the manufacturing efficient that can improve liquid crystal indicator etc. at aspects such as quality of stability or lamination operation.

The viewing angle compensation film is also to make image seem more clearly, be used to enlarge the film of field angle under the situation of the direction that tilts a little observation liquid crystal display picture that is not orthogonal to picture.As this kind viewing angle compensation polarizer, by for example oriented film such as phase-contrast film, liquid crystal polymer or in the transparent base upper support material etc. of oriented layer such as liquid crystal polymer constitute.Common polarizer uses the birefringent thin polymer film that has of implementing unilateral stretching on its face direction, relative therewith, as in the polarizer of viewing angle compensation film, can use and implement having birefringent thin polymer film or on the face direction, implementing unilateral stretching and the refractive index of controlling thickness direction that on thickness direction, also is stretched and have birefringent polymkeric substance or the biaxially oriented film as the tilted alignment film etc. of two-way stretch on the face direction.As the tilted alignment film, for example can enumerate behind the bonding heat-shrinkable film on the thin polymer film under effect because of the convergent force that adds thermosetting, thin polymer film is carried out stretch processing or/and the material of shrink process, make the material of liquid crystal polymer tilted alignment etc.The raw polymer of polarizer can use with in front polarizer in the polymer phase that illustrates with polymkeric substance, can use the painted grade that variation caused at the identification angle that will prevent the phase differential that causes based on liquid crystal cells or enlarge the suitable material as purpose such as the good field angle of identification.

In addition, wait from the viewpoint that realizes the wide visual field angle that identification is good, can preferably use with triacetylcellulose film and support the optical compensation polarizer that optical anisotropic layer that the tilted alignment layer by the oriented layer of liquid crystal polymer, particularly discoid liquid crystal polymer constitutes forms.

The back side one side that polaroid and the film adhered polaroid that together forms of brightness improving is set at usually liquid crystal cells is then used.The brightness improving film is the film that shows below characteristic, promptly, when natural light incident being arranged because of the backlight of liquid crystal indicator etc. or from the reflection of rear side etc., the rectilinearly polarized light of reflection regulation polarizing axis or the circularly polarized light of prescribed direction, and make other light transmissions.Therefore brightness improving film and the stacked polaroid that forms of polaroid can be made the light incident from light sources such as backlights, and obtain the light that sees through of regulation polarized light state, simultaneously, the light beyond the described regulation polarized light state can not see through and quilt is reflected.By reflection horizon that is arranged at its rear side etc. the light that reflects on this brightness improving pellicular front is reversed once more, and make it to incide once more on the brightness improving film, make its part or all light transmission as the regulation polarized light state, thereby increase the light that sees through the brightness improving film, simultaneously provide the polarized light that is difficult to absorb to polariscope, can be thereby increase in the light quantity of utilization in the demonstration of image etc., and can improve brightness thus.Promptly, pass polariscope and make under the situation of light incident from the rear side of liquid crystal cells with backlight etc. not using the brightness improving film, have light with the inconsistent polarization direction of polariscopic polarizing axis and be polarized mirror basically and absorb, thereby can't see through polariscope.That is, though can be different because of employed polariscopic characteristic, about 50% light can be polarized mirror and sponge, and therefore, the light quantity that can utilize in liquid crystal image demonstration etc. will reduce, and cause the image deepening.Because the brightness improving film carries out following operation repeatedly, promptly, making the light with the polarization direction that can be polarized the mirror absorption is not to incide on the polariscope, but such light is reflected on the brightness improving film, and then finish counter-rotating by reflection horizon of being located at its rear side etc., light is incided on the brightness improving film once more, like this, the brightness improving film only makes in the light of the two reflection and counter-rotating, its polarization direction becomes and can see through by the polarized light of polariscopic polarization direction, provide it to polariscope simultaneously, therefore can in the demonstration of the image of liquid crystal indicator, use the light of backlight etc. effectively, thereby can make picture bright.

Also can between brightness improving film and described reflection horizon etc., diffuser plate be set.Towards described reflection horizon etc., set diffuser plate can spread the light that passes through equably by the light of the polarized light state of brightness improving film reflection, eliminates polarized light state simultaneously and becomes the nonpolarized light state.That is, diffuser plate makes polarized light return to original natural light state.Carry out following process repeatedly, that is, and with this nonpolarized light state light directive reflection horizon that is the natural light state etc., after reflections such as reflection horizon, once more by diffuser plate and incide on the brightness improving film.Make polarized light return to the diffuser plate of original natural light state by between brightness improving film and above-mentioned reflection horizon etc., being provided with, can be in the brightness of keeping display frame, reduce the brightness disproportionation of display frame, thereby even and bright picture can be provided.By this diffuser plate is set, can suitably increase the repeated reflection number of times of first incident light, and utilize the diffusion function of diffuser plate, the display frame of homogeneous and bright can be provided.

As above-mentioned brightness improving film, for example can use: the demonstration of thin-film multilayer duplexer that dielectric multilayer film or refractive index anisotropy are different and so on send as an envoy to the rectilinearly polarized light of regulation polarizing axis see through and reflect the characteristic of other light film, cholesteric liquid crystal polymer oriented film or in the film substrate upper support the demonstrating any circularly polarized light reflection that will be in left-handed or the dextrorotation of film and so on of this aligned liquid-crystal layer and film that the film etc. of the characteristic of other light transmissions is suited.

Therefore, in the brightness improving film of the type that the above-mentioned rectilinearly polarized light that makes the regulation polarizing axis sees through, directly incide on the polaroid by making this see through light, can when suppressing the absorption loss that causes by polaroid, light be seen through effectively along the direction consistent with polarizing axis.On the other hand, in the brightness improving film that makes the type that circularly polarized light sees through of cholesteric and so on, though light is incided on the polariscope, but consider from suppressing the absorption loss this point, preferably this circularly polarized light carry out rectilinearly polarized lightization, reenter afterwards and be mapped on the polaroid by polarizer.And, by using 1/4 wavelength plate, circularly polarized light can be transformed to rectilinearly polarized light as this polarizer.

About in the wide wavelength coverage in visible region, playing the polarizer of 1/4 wavelength plate effect, for example can utilize following mode to obtain, that is, the phase separation layer that will play 1/4 wavelength plate effect with respect to the light luminous energy of wavelength 550nm carries out overlapping mode etc. with the phase separation layer that the phase separation layer that shows other phase difference characteristics for example can play 1/2 wavelength plate effect.So the polarizer that is disposed between polaroid and the brightness improving film can be made of the phase separation layer more than 1 layer or 2 layers.

Also have, with regard to cholesteric, also can make up the material of different reflection wavelengths, constitute overlapping arrangement more than 2 layers or 3 layers, obtain the member of wide wavelength coverage internal reflection circularly polarized light thus, thereby can obtain the circularly polarized light that sees through of broad wavelength coverage based on this in the visible region.

In addition, polaroid is as described polarized light divergence type polaroid, can be made of the member of stacked polaroid and the optical layers more than 2 layers or 3 layers.So, also can be to have made up the reflection-type ellipsoidal polarizing plate of above-mentioned reflection type polarizer or semi-transmission type polaroid and polarizer or semi-transmission type ellipsoidal polarizing plate etc.

Hard-coated film is to stacked to polaroid of the stacked and then various optical layers of above-mentioned optical element, also can form by independent successively stacked mode in the manufacture process of liquid crystal indicator etc., and that the stacked in advance member that they form has at aspects such as quality of stability or assembly manipulations is outstanding, and improves the advantage of the manufacturing process of liquid crystal indicator etc.In stacked, can use suitable bonding agencies such as bonding coat.When bonding above-mentioned polaroid or other optical thin films, can their optic axis be adjusted into suitable arrangement angles according to purpose phase difference characteristics etc.

At above-mentioned polaroid or be laminated with at least on 1 layer the one side at least of optical component of optical thin film etc. of polaroid, be provided with above-mentioned hard-coated film, but be not provided with on the face of hard-coated film, can be provided for and the bonding bonding coats of other members such as liquid crystal cells yet.The bonding agent that forms bonding coat is not particularly limited, for example can selects aptly to use with bonding agent such as the polymkeric substance of acrylic acid series polymeric compounds, silicone-based polymkeric substance, polyester, polycarbamate, polyamide, polyethers, fluorine system or rubber system etc. as base polymer.The preferred especially optical transparence that uses similar acrylic adhesive is good and demonstrate the adhesion characteristic and the good bonding agents such as against weather or thermotolerance of wetting state, coherency and the cementability of appropriateness.

And, except above-mentioned, from prevent the foamed phenomenon that causes because of moisture absorption or peel off phenomenon, the warpage of the decline of the optical characteristics that causes because of thermal expansion difference etc. or liquid crystal cells and then from the viewpoints such as formation of the good liquid crystal indicator of high-quality and permanance, the bonding coat of the low and excellent heat resistance of preferred hydroscopicity.

In above-mentioned tackifier or bonding agent, can contain and the corresponding crosslinking chemical of base polymer.In addition, for example natural or synthetic resin, particularly tackifying resin or the filling agent that constitutes by glass fibre, beaded glass, metal powder, other inorganic powder etc., pigment, colorant, antioxidant etc. can be contained in bonding coat etc. and adjuvant in the bonding coat can be made an addition to.Also can be to contain particulate and the diffusible bonding coat of display light etc. in addition.

Bonding coat can utilize suitable mode to carry out to setting up of optical elements such as polaroid, optical thin film.As its example, for example can enumerate following mode, promptly be modulated at the binder solution of about 10～40 weight % that dissolving in the solvent that pure material or potpourri by suitable solvent such as toluene or ethyl acetates constitute or dispersion base polymer or its composition form, directly it be attached to mode on the optical element by suitable expansion mode such as curtain coating mode or application pattern then; Perhaps based on above-mentioned and after forming bonding coat on the separator with its handover and stick on mode on the optical element etc.Bonding coat also can be as forming with each layer or the overlapping layer of the layer that kind etc. is different and being provided with.The thickness of bonding coat can suitably be determined according to application target or bonding force etc., be generally 1～500 μ m, preferred 5～200 μ m, preferred especially 10～100 μ m.

For the face that exposes of bonding coat, for before using in order to prevent its pollution etc., can paste separator to cover temporarily.Can prevent the phenomenon that under common mode of operation, contacts thus with bonding coat.As separator, on the basis of satisfying above-mentioned thickness condition, for example can use as required with suitable removers such as silicone-based or chain alkyl system, fluorine system or molybdenum sulfides plastic sheeting, sheet rubber, paper, cloth, nonwoven fabrics, net, foam sheet or metal forming, their suitable thin slice bodies such as duplexer are applied suitable separators commonly used in the past such as material after the processing.

Also have; in the present invention; also can be on each layers such as polariscope, transparent protective film, optical layers or bonding coat that form above-mentioned optical element; utilize the modes such as mode of for example using salicylate based compound or benzo phenol (benzophenol) based compound, benzotriazole based compound or ultraviolet light absorbers such as cyanoacrylate based compound, nickel coordination compound based compound to handle, make it to have ultraviolet absorption ability etc.

The optical element that hard-coated film of the present invention has been set can be preferred for formation of various devices such as liquid crystal indicator etc.Liquid crystal indicator can form according to method in the past.Promptly, in general, liquid crystal indicator can form by the component parts such as combination of liquid crystals unit and optical element aptly and the illuminator that adds as required and the driving circuit of packing into etc., in the present invention, except using optical element of the present invention, be not particularly limited, can form according to method in the past.For liquid crystal cells, also can use for example liquid crystal cells of any type such as TN type or STN type, π type.

The one or both sides that can be formed in liquid crystal cells have disposed the liquid crystal indicator of above-mentioned optical element, used the suitable liquid crystal indicators such as device of backlight or reflecting plate in illuminators.At this moment, optical element of the present invention can be arranged on the one or both sides of liquid crystal cells.When optical element was arranged on both sides, they both can be identical, also can be different.In addition, when forming liquid crystal indicator, can be on suitable position suitable parts such as for example diffuser plate of configuration more than 1 layer or 2 layers, antiglare layer, antireflection film, fender, prism array, lens arra thin slice, light diffusing sheet, backlight.

Then, Organnic electroluminescent device (organic EL display) is described.Usually, organic EL display is to stack gradually transparency electrode, organic luminous layer and metal electrode and form luminophor (organic electroluminescent body) on transparency carrier.Here, organic luminous layer is the duplexer of various organic films, and known have: for example duplexer of the duplexer of hole injection layer that is made of triphenylamine derivant etc. and the luminescent layer that is made of fluorescence organic solids such as anthracenes or this kind luminescent layer and the electron injecting layer that is made of perylene derivant etc. or the various combinations such as duplexer of these hole injection layers, luminescent layer and electron injecting layer.

Organic EL display carries out luminous according to following principle, promptly, by on transparency electrode and metal electrode, applying voltage, injected hole and electronics in organic luminous layer, the energy excitation fluorescent material that produces by the compound of these holes and electronics, when the fluorescent material that is excited is got back to ground state, will radiate bright dipping.Middle multiple mechanism is identical with general diode, also can infer thus, and electric current and luminous intensity demonstrate with respect to impressed voltage and follow the stronger non-linear of rectification.

In organic EL display, in order to take out the light that produces in the organic luminous layer, at least one side's electrode must be transparent, usually will be by tin indium oxide (ITO). the transparency electrode that waits transparent conductive body to make is used as anode.On the other hand, improve luminescence efficiency in order to carry out electronics to inject easily, it is crucial using the less material of work function on negative electrode, uses metal electrodes such as Mg-Ag, Al-Li usually.

In having the organic EL display of this formation, organic luminous layer is that film as thin as a wafer about 10nm constitutes by thickness.Therefore, organic luminous layer is also the same with transparency electrode, and light is almost completely seen through.Consequently, when not luminous from the incident of transparency carrier surface and see through transparency electrode and organic luminous layer and can be once more penetrating to the face side of transparency carrier at the light of metal electrode reflection, therefore, when carrying out identification from the outside, the display surface of organic El device is as minute surface.

In the organic EL display that comprises organic electroluminescent body as described below, can polaroid be set in the face side of transparency electrode, simultaneously between these transparency electrodes and polaroid, polarizer is set, above-mentioned organic electroluminescent body is to be provided with transparency electrode by applying the face side that voltage carries out luminous organic luminous layer, is provided with metal electrode and forms in the rear side of organic luminous layer simultaneously.

Become the effect of polarized light because polarizer and polaroid have to make from outside incident and at the light of metal electrode reflection, therefore, have the effect that can't pick out the minute surface of metal electrode by this polarized light effect from the outside.Particularly, when adopting 1/4 wavelength plate to constitute polarizer and the angle of the polarization direction of polaroid and polarizer is adjusted into π/4, can cover the minute surface of metal electrode fully.

That is, the exterior light that is incident to this organic EL display has only the rectilinearly polarized light composition because of the existence of polaroid and sees through.This rectilinearly polarized light generally can be converted to elliptically polarized light by polarizer, and when polarizer be the angle of the polarization direction of 1/4 wavelength plate and polaroid and polarizer when being π/4, become circularly polarized light.

This circularly polarized light sees through transparency carrier, transparency electrode, organic film, reflects on metal electrode, sees through organic film, transparency electrode, transparency carrier afterwards once more, converts rectilinearly polarized light once more to by polarizer.Then, because this rectilinearly polarized light is vertical with the polarization direction of polaroid, so can't see through polaroid.Its result can be covered the minute surface of metal electrode fully.

Below, describe the preferred embodiments of the present invention in detail in illustrative mode.But, Ji Zai material or use level etc. in this embodiment, short of special limited record, scope of the present invention just is not limited only to this, and only is embodiment.In addition, in each example, part and the short of special record of % all are meant weight basis.

(embodiment 1)

Blending ratio by butyl acetate and ethyl acetate is the mixed solvent of 46: 54 (the ethyl acetate ratio of relative total solvent is 54%), the material of following composition diluted to make its solid component concentration be 50%, modulate and be coated with the formation material firmly, wherein, diluted material has: as urethane acrylate (urethane acrylate, below, the A composition) be 100 parts of the urethane acrylates that constitute of acrylate and hydrogenated xylene diisocyanate by pentaerythrite, as polyvalent alcohol (methyl) acrylate (below, the six acrylic acid dipentaerythritol ester B composition) (below, B1 composition (monomer)) 49 part, pentaerythritol tetracrylate (below, B4 composition (monomer)) 41 parts and pentaerythritol triacrylate (below, B5 composition (monomer)) 24 part, as (methyl) acrylate copolymer with the alkyl that contains 2 above hydroxyls (below, the C composition) have 2-hydroxyethyl and 2, (methyl) acrylate copolymer of 3-dihydroxypropyl (big Japanese イ Application キ chemical industry Co., Ltd. system, trade name: PC1070) 59 parts, with respect to 3 parts of total resinous principle polymerization initiators (イ Application ガ キ ユ ア 184), 0.5 part of reactive levelling agent.In addition, above-mentioned reactive levelling agent is with dimethyl siloxane: the hydroxypropyl siloxane: 6-isocyanates hexyl cyamelide: aliphatic polyester=6.3: 1.0: 2.2: the multipolymer of 1.0 mol ratio generation copolymerization.

Triacetylcellulose film (refractive index: 1.48) as film substrate, use rod to be coated with machine and on above-mentioned film, apply the above-mentioned formation material that is coated with firmly,, make dried coating film with thick 80 μ m by heating 1 minute down at 100 ℃.Subsequently, with metal halide light irradiation accumulative total light quantity 300mJ/cm ²Ultraviolet ray, be cured the hard conating that handle to form thick 20 μ m, make the hard-coated film of present embodiment.

(embodiment 2)

In the present embodiment, except the thickness with hard conating changes to 15 μ m, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 3)

In the present embodiment, except the thickness with hard conating changes to 25 μ m, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 4)

In the present embodiment, except will having 2-hydroxyethyl and 2, the use level of the hard acrylate copolymer of (methyl) of 3-dihydroxypropyl is altered to outside 96 parts, adopts the method identical with embodiment 1, the making hard-coated film.

(embodiment 5)

In the present embodiment, except will having 2-hydroxyethyl and 2, the use level of the hard acrylate copolymer of (methyl) of 3-dihydroxypropyl is altered to outside 36 parts, adopts the method identical with embodiment 1, the making hard-coated film.

(embodiment 6)

In the present embodiment, except forming outside 30 parts of the crosslink propylene granulates (trade name: MX1000 combines chemistry (strain) system of grinding) that add mean grain size 10 μ m in the material being coated with firmly, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 7)

In the present embodiment, except anti-reflection layer being arranged at the hard conating of the hard-coated film that in embodiment 1, obtains, adopt the method identical, the making antireflective hard coating film with embodiment 1.

In addition, antireflection forms material and adopts method modulation as follows.Promptly, at first, as the formation material of anti-reflection layer, prepare コ Le one コ one ト N103 (コ Le one コ one ト corporate system in advance, solid constituent 2 weight %) as the mean molecular weight that converts by ethylene glycol be 500～10000 siloxane oligomer, measure its number-average molecular weight.Its result, number-average molecular weight are 950.In addition, prepare オ プ ス one JTA105 (trade name, JSR (strain) system, solid constituent 5 weight %) be more than 5000 as the number-average molecular weight by polystyrene conversion and have the fluorine compounds of fluoro-alkyl structure and polysiloxane structure, when measuring the number-average molecular weight of these fluorine compounds, the number-average molecular weight by polystyrene conversion is 8000.In addition, as hardening agent, use JTA105A (JSR corporate system, solid constituent 5 weight %).

Then, mix オ プ ス one JTA105, the JTA105A of 1 weight portion, コ Le one コ, the one ト N103 of 590 weight portions and the butyl acetate of 151.5 weight portions of 100 weight portions, the modulation anti-reflection layer forms material.The use die coater applies this anti-reflection layer and forms material on hard conating, and makes its width identical with hard conating, and by heating 3 minutes down at 120 ℃, dry, curing forms anti-reflection layer (low-index layer, thickness 0.1 μ m, refractive index 1.43)

(embodiment 8)

In the present embodiment, forms the anti-reflection layer (thickness 95nm) that material forms the method that employing and embodiment 7 are identical, making antireflective hard coating film except being provided with by antireflection as described below.

Promptly, in the mixed solvent of isopropyl alcohol/butyl acetate/hexone (54/14/32 (weight ratio)), disperse 54 parts of tetraalkoxysilanes and have that 23 parts of the silane coupling agents of fluoro-alkyl structure and polysiloxane structure, silane coupling agent with alkyl carry out surface treatment and the diameter of hydrophobization is 23 parts of the hollow of 60nm and spherical monox ultra microns, solid constituent is adjusted to 2.0%, obtains anti-reflection layer and form material.

Use this anti-reflection layer to form material, adopt method and the condition identical on hard conating, to form anti-reflection layer with embodiment 7, thus, the antireflective hard coating film of making present embodiment.

(embodiment 9)

In the present embodiment, except the thickness with hard conating is altered to 30 μ m, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 10)

In the present embodiment, except the thickness with hard conating is altered to 10 μ m, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 11)

In the present embodiment, the blending ratio of using butyl acetate and ethyl acetate is that the solvent of 79: 21 (the ethyl acetate ratio with respect to total solvent is 21%) is as mixed solvent, using this solvent to dilute and making its solid component concentration is 63%, be modulated into and be coated with the formation material firmly, use this to be coated with firmly and form material formation hard conating, in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 12)

At first, with the embodiment 1 the same hard-coated film of making present embodiment.Then, be coated with firmly on the face (with the face of the opposite side of formation face of hard conating) at the quilt of triacetylcellulose film, using wire bar that coating liquid described later is applied and make wet thickness is 20 μ m, carries out 1 minute dried under 80 ℃.In addition, as above-mentioned coating liquid, using mixed solvent acetone: ethyl acetate: IPA (isopropyl alcohol)=37: 58: 5 to cooperate diacetyl cellulose and making solid component concentration is 0.5% liquid.

(embodiment 13)

In the present embodiment, be coated with the coating liquid that applies on the face firmly, use acetone: ethyl acetate: IPA=37 as quilt at triacetylcellulose film: 58: 5 mixed solvent, in addition, adopt method similarly to Example 12, make hard-coated film.

(embodiment 14)

In the present embodiment, except not adding reactive silicone, adopt the method making hard-coated film identical with embodiment 1 as reactive levelling agent.

(embodiment 15)

In the present embodiment, the blending ratio of using butyl acetate and MIBK (hexone) is that the solvent of 46: 54 (the MIBK ratio of relative total solvent is 54%) is as mixed solvent, and then use this solvent that solid component concentration is diluted to 63% and modulation is coated with the formation material firmly, use this to be coated with firmly and form material formation hard conating, in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 16)

In the present embodiment, the blending ratio of using butyl acetate and butanols is that the solvent of 46: 54 (the butanols ratio of relative total solvent is 54%) is as mixed solvent, and then use this solvent that solid component concentration is diluted to 63% and modulation is coated with the formation material firmly, use this to be coated with firmly and form material formation hard conating, in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 17)

In the present embodiment, use as the A composition by pentaerythrite be the urethane acrylate that constitutes of acrylate and isophorone diisocyanate (below, the A1 composition) 100 part, as 15 parts of 37 parts of 59 parts of B1 compositions, the B4 compositions of B composition and B5 compositions, have 2-hydroxyethyl and 2 as the C composition, 26 parts of (methyl) acrylate copolymers of 3-dihydroxypropyl, with respect to 2 parts of total resinous principle polymerization initiators (Irgacure 184), in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 18)

In the present embodiment, use is as 100 parts of the A1 compositions of A composition, as 16 parts of 40 parts of 38 parts of B1 compositions, the B4 compositions of B composition and B5 compositions, have 2-hydroxyethyl and 2,30 parts of (methyl) acrylate copolymers of 3-dihydroxypropyl as the C composition, (cooperated 2 parts Irgacure 184 and 2 with respect to total resinous principle polymerization initiator, 4,2.5 parts of 6-trimethylbenzene acyloin phenyl phosphine oxides) 3.5 parts, in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(embodiment 19)

In the present embodiment, except the thickness with hard conating changes to 29 μ m, adopt the method identical, the making hard-coated film with embodiment 6.

(comparative example 1)

In this comparative example, mismatch A composition and C composition, and cooperate as 100 parts of six acrylic acid dipentaerythritol ester of B composition, and then cooperate 9 parts of acrylic acid butanediol esters (below, B3 composition), in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(comparative example 2)

In this comparative example, use 5 parts of 22 parts of B4 compositions and B5 compositions as the B composition.In addition, use 133 parts of replaced C compositions of poly-methyl methacrylate base acrylate polymer, in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(comparative example 3)

In this comparative example, the potpourri that uses 5 parts of 22 parts of B4 compositions and B5 compositions is as the B composition.In addition, use 55 parts of replaced C compositions of poly-methyl methacrylate base acrylate polymer, in addition, adopt the method identical, the making hard-coated film with embodiment 1.

(thickness of hard conating)

Use the micrometer formula thickness meter of (strain) ミ Star ト ヨ system to measure.The thickness that is provided with the hard-coated film of hard conating on the clear films base material is measured, gone out the thickness of hard conating, the results are shown in table 1 by the THICKNESS CALCULATION that deducts base material.

(thickness of anti-reflection layer)

The moment MCPD2000 of many sidelights system (trade name) of Shi Yong Da mound electronics (strain) system, the waveform by interference spectrum calculates.

In addition, the hard-coated film (comprising antireflective hard coating film) that obtains is carried out following evaluation.The results are shown in table 1.

(reflectivity)

About the bonding agent that the uses thick about 20 μ m レ イ of applying Mitsubishi ヨ Application system black acrylic panel (thick 2.0mm) and make the film of the areflexia at the applying back side on the face that does not form hard conating of hard-coated film, measure the reflectivity on hard conating (or anti-reflection layer) surface.Reflectivity uses UV2400PC (the having 8 ° of inclination integrating spheres) spectrophotometer of (strain) Shimadzu Seisakusho Ltd. system, measures spectral reflectance (specular reflectance+diffuse reflectance), obtains the total reflectivity (Y value) of ° visual field, illuminant-C/2 by calculating.The results are shown in table 1.

(pencil hardness)

The face that does not form hard conating of mounting hard-coated film or antireflective hard coating film on glass plate, about hard conating (or anti-reflection layer) surface, (wherein, load 500g) implements test according to the described pencil hardness test of JIS K-5400.The results are shown in table 1.

(crimping)

It is square that hard-coated film is cut into 10cm, is placed on the glass plate and makes hard conating (or anti-reflection layer) up, measures from the lifting length (mm) of the glass plate at 4 angles, with the evaluation index of its mean value as crimping.In addition, the film that becomes circle is made as " can't measure ".In addition, indicator gauge 1 as a result.

(flexibility)

To allow film substrate become the mode of the different metallic roll of inboard and direct contact diameter, coiling hard-coated film or antireflective hard coating film have or not in the visual judgement hard conating (or anti-reflection layer) and crackle occurs.The diameter that crackle do not occur is measured as the value of flexibility.The results are shown in table 1.

(turbidity)

Turbidity (haze) with JIS-K7136 is a benchmark, uses nephelometer HR300 (color technical institute system in the village) to measure.The results are shown in table 1.

(mar resistance)

At the value of the power of the mar resistance of hard-coated film or antireflective hard coating film, obtain with following content of the test.

(1) sample is cut into wide at least 25mm, the size more than the long 100mm, it is positioned on the glass plate.Obtain the turbidity value at initial stage subsequently.

(2) on the level and smooth cross section of the cylinder of diameter 25mm, evenly be installed on the steel wool #0000,, obtain the turbidity after the test then with load 1.5kg and with the speed of the about 100mm of per second reciprocal 100 times at specimen surface.

(3) will deduct value that the initial stage turbidity value obtains index from the turbidity value after the test as mar resistance.In this is estimated, the desired value of mar resistance is big more, in the steel wool test, rise by the turbidity value after making test in the damage that produces on the surface of hard conating or anti-reflection layer, conduct is also risen with the finger target value of the mar resistance of the difference of initial stage turbidity value thus.

(adhesiveness)

Hard conating is estimated by carrying out the described grid disbonded test of JIS K5400 with respect to the adhesiveness of film substrate.That is, carry out 100 times disbonded test, the quantity that the counting hard conating is peeled off from film substrate is shown in table 1 with peeling off quantity/100.

Table 1

	The refractive index of film substrate	The refractive index of hard conating	Thickness (μ m)	Reflectivity (%)	Pencil hardness	Crimping (mm)	Flexibility (mm Φ)	Turbidity	Adhesiveness	Mar resistance
											Embodiment 1	1.48	1.51	20	4	4H	22	9.5	-	0/100	0.2
Embodiment 2	1.48	1.51	15	4	4H	15	9.5	-	0/100	0.2
											Embodiment 3	1.48	1.51	25	4	4H	30	11	-	0/100	0.2
Embodiment 4	1.48	1.51	20	4	4H	10	8	-	0/100	0.4
											Embodiment 5	1.48	1.51	20	4	5H	29	14	-	0/100	0.2
Embodiment 6	1.48	1.51	20	4	4H	20	9.5	60	0/100	0.2
											Embodiment 7	1.48	1.51	20	2.5	4H	10	9.5	-	0/100	0.3
Embodiment 8	1.48	1.51	20	1.6	4H	10	9.5	-	0/100	0.3
											Embodiment 9	1.48	1.51	30	4	5H	36	12.5	-	0/100	0.2
Embodiment 10	1.48	1.51	10	4	3H	10	8	-	0/100	0.4
											Embodiment 11	1.48	1.51	20	4	4H	24	9.5	-	10/100	0.2
Embodiment 12	1.48	1.51	20	4	4H	0	9.5	-	0/100	0.2
											Embodiment 13	1.48	1.51	20	4	4H	0	9.5	-	0/100	0.2
Embodiment 14	1.48	1.51	20	4	4H	22	9.5	-	0/100	0.5
											Embodiment 15	1.48	1.51	20	4	4H	21	9.5	-	75/100	0.2
Embodiment 16	1.48	1.51	20	4	4H	23	9.5	-	100/100	0.2
											Embodiment 17	1.48	1.53	20	4	4H	29	14	-	0/100	0
Embodiment 18	1.48	1.53	20	4	4H	27	14	-	0/100	0
											Embodiment 19	1.48	1.51	29	4	5H	28	12.5	63	0/100	0.2
Comparative example 1	1.48	1.51	20	4	5H	More than the critical value	15.5	-	10/100	1.8
											Comparative example 2	1.48	1.51	20	4	3H	0	11	-	0/100	1.4
Comparative example 3	1.48	1.51	20	4	3H	20	12.5	-	0/100	0.8

Table 2

	A composition (weight portion)	The B composition		C composition (weight portion)	Other add resin		The use level of particulate (weight portion)	The use level of polymerization initiator (weight portion)	Having or not of anti-reflection layer
										Composition	Use level (weight portion)	Resinous principle	Use level (weight portion)
		Embodiment 1	100		B1 composition/B4 composition/B5 composition	49/41/24								59	-	-	-	3	Do not have
Embodiment 2	100			B1 composition/B2 composition			49/65	59	-	-	-	3	Do not have
		Embodiment 3	100		B1 composition/B2 composition	49/65								59	-	-	-	3	Do not have
Embodiment 4	100			B1 composition/B2 composition			49/65	96	-	-	-	3	Do not have
		Embodiment 5	100		B1 composition/B2 composition	49/65								36	-	-	-	3	Do not have
Embodiment 6	100			B1 composition/B2 composition			49/65	59	-	-	30	3	Do not have
		Embodiment 7	100		B1 composition/B2 composition	49/65								59	-	-	-	3	Have
Embodiment 8	100			B1 composition/B2 composition			49/65	59	-	-	-	3	Have
		Embodiment 9	100		B1 composition/B2 composition	49/65								59	-	-	-	3	Do not have
Embodiment 10	100			B1 composition/B2 composition			49/65	59	-	-	-	3	Do not have
		Embodiment 11	100		B1 composition/B2 composition	49/65								59	-	-	-	3	Do not have
Implement	100			B1 composition/B2 composition			49/65	59	-	-	-	3	Do not have

Example 12
										Embodiment 13	100	B1 composition/B2 composition	49/65	59	-	-	-	3	Do not have
Embodiment 14	100	B1 composition/B2 composition	49/65	59	-	-	-	3	Do not have
										Embodiment 15	100	B1 composition/B2 composition	49/65	59	-	-	-	3	Do not have
Embodiment 16	100	B1 composition/B2 composition	49/65	59	-	-	-	3	Do not have
										Embodiment 17	100	B1 composition/B4 composition/B5 composition	59/37/15	26	-	-	-	2	Do not have
Embodiment 18	100	B1 composition/B4 composition/B5 composition	38/40/16	30	-	-	-	3.5	Do not have
										Embodiment 19	100	B1 composition/B2 composition	49/65	59	-	-	30	3	Do not have
Comparative example 1	-	B1 composition/B3 composition	100/9	-	The acrylic acid butanediol ester	9	-	3	Do not have
										Comparative example 2	100	B4 composition/B5 composition	22/5	-	Poly-methyl methacrylate base acrylate polymer	133	-	3	Do not have
Comparative example 3	100	B4 composition/B5 composition	22/5	-	Poly-methyl methacrylate base acrylate polymer	55	-	3	Do not have

According to the above description, by the present invention, formation material as hard conating, use contains urethane acrylate, polyvalent alcohol (methyl) acrylate and material with (methyl) acrylate copolymer of the alkyl that contains two above hydroxyls, even so forming under the situation of hard conating hard-coated film and its manufacture method that high rigidity can be provided and not have crimping or split usually on the film substrate of softness.And then hard-coated film of the present invention goes for optical elements such as polarization film, and the LCD of this polarization film has been installed, even as under the situation of home-use TV machine, also have enough hardness and mar resistance, so be fit to use.

Claims (13)

1. a hard-coated film is the hard-coated film that is provided with hard conating at least one face of transparent membrane base material, it is characterized in that,

The formation material of described hard conating comprises urethane acrylate, polyvalent alcohol (methyl) acrylate and has (methyl) acrylate copolymer of the alkyl that contains two above hydroxyls.

2. hard-coated film according to claim 1 is characterized in that,

Described polyvalent alcohol (methyl) acrylate contains pentaerythritol triacrylate, pentaerythritol tetracrylate and constitutes.

3. hard-coated film according to claim 1 and 2 is characterized in that,

The outside surface of described hard conating becomes concaveconvex shape.

4. according to any one described hard-coated film of claim 1～3, it is characterized in that,

On the outside surface of described hard conating, be formed with anti-reflection layer.

5. hard-coated film according to claim 4 is characterized in that,

Described anti-reflection layer contains:

The number-average molecular weight that converts by ethylene glycol be 500～10000 siloxane oligomer and

Number-average molecular weight by polystyrene conversion is fluorine compounds more than 5000, that have fluoro-alkyl structure and polysiloxane structure.

6. according to claim 4 or 5 described hard-coated films, it is characterized in that,

In described anti-reflection layer, contain hollow and spherical monox ultra micron.

7. hard-coated film according to claim 1 is characterized in that,

The formation material of described hard conating contains levelling agent.

8. the manufacture method of a hard-coated film is the manufacture method that forms the hard-coated film of hard conating at least one face of transparent membrane base material, it is characterized in that, comprising:

In diluting solvent, add urethane acrylate, polyvalent alcohol (methyl) acrylate at least and have (methyl) acrylate copolymer of the alkyl that contains two above hydroxyls, the operation of modulating the formation material of described hard conating;

The described formation material of coating at least one face of film substrate and form the operation of coated film; With

Make described coated film solidify and then form the operation of hard conating.

9. the manufacture method of hard-coated film according to claim 8 is characterized in that,

Use contains the material of ethyl acetate as described diluting solvent.

10. the manufacture method of hard-coated film according to claim 9 is characterized in that,

The content of described ethyl acetate is more than the 20 weight %.

11. an optical element is characterized in that,

Each described hard-coated film of claim 1～7 is arranged at least one face of optical component.

12. an image display device is characterized in that,

Possesses the described hard-coated film of claim 1.

13. an image display device is characterized in that,

Possesses the described optical element of claim 11.