CN100582818C - Hard-coated antiglare film, polarizing plate, image display, and method of manufacturing hard-coated antiglare film - Google Patents

Abstract

A hard-coated antiglare film is provided that has high hardness and excellent antiglare properties and can prevent white blur from occurring when viewed from oblique directions. The hard-coated antiglare film of the present invention includes a transparent plastic film substrate and a hard-coating antiglare layer that is formed of fine particles and a hard-coating resin on at least one surface of the transparent plastic film substrate. The hard-coating antiglare layer has a thickness of 15 to 30 mum, the fine particles have a weight average particle size of 30 to 75% of a thickness of the hard-coating antiglare layer, in the unevenness of the hard-coating antiglare layer surface that is formed by the fine particles, an average tilt angle thetaa is 1.0 DEG to 2.0 DEG , and an arithmetic average surface roughness Ra according to JIS B 0601 (1994 version) is 0.12 to 0.30 mum.

Description

Hard-coated antiglare film and manufacture method thereof, polaroid and image display device

Technical field

The present invention relates to the manufacture method of a kind of hard-coated antiglare film, polaroid, image display device and hard-coated antiglare film.

Background technology

In recent years, along with development of technology, image display device is on the basis of existing C RT (Cathode RayTube), and also exploitation has LCD (LCD), plasma display (PDP) and electroluminescent display (ELD) etc., and with its practicability.Wherein, with regard to LCD, be accompanied by with high visual field angling, height become more meticulous, relevant technical renovation such as high-speed responsive, colorrendering quality, utilize the application of LCD also to transform to TV from subnotebook PC or monitor.The basic comprising of LCD is, with the glass substrate that possesses respectively on the flat board of transparency electrode, dispose by the dividing plate subtend in the mode that becomes slit with certain intervals, between described glass substrate, inject liquid crystal material, sealing, as liquid crystal cells, and then polaroid is set respectively at the lateral surface of described a pair of glass substrate.Be that the cover plate that is made of glass or plastics is installed on described liquid crystal cells surface in the past, prevented to damage the described polaroid that on described liquid crystal cells surface, attaches.But, when described cover plate is installed, be disadvantageous aspect cost and the weight.Thereby, then described polaroid surface is coated with processing firmly.Be coated with firmly in the processing described, prevent dazzling of LCD or mirroring etc. of light source simultaneously, use hard-coated antiglare film usually.

Hard-coated antiglare film is obtained by following method, the thin antiglare hardcoat about one or both sides formation 2～10 μ m of transparent plastic film base material.Above-mentioned antiglare hardcoat uses heat-curing resin or uv curing resin etc. to resinize firmly and particulate and forming.The surface of described antiglare hardcoat becomes concaveconvex shape because of described particulate, brings into play anti-dazzle property thus.When resinizing firmly when antiglare hardcoat is set in that coating on glass is above-mentioned, demonstrate hardness more than the 4H in pencil hardness.But in substrate is under the situation of above-mentioned transparent plastic film base material, if the thickness low LCL of above-mentioned antiglare hardcoat is abundant, is subjected to the influence of above-mentioned transparent plastic film base material usually, and above-mentioned pencil hardness is reduced to below the 3H.

Travel to home-use TV machine by application,, also carry out and the same operation of televisor that utilizes glass CRT in the past even the user of general home-use TV machine can easily imagine the televisor that has used LCD with LCD.The pencil hardness of above-mentioned glass CRT is about 9H.For this reason, for the hard-coated antiglare film that uses among the LCD, require to improve hardness.

By increasing the bed thickness of antiglare hardcoat, can improve the hardness of hard-coated antiglare film.But, when increasing bed thickness, exist following problems, the particle that promptly in antiglare hardcoat, contains to be embedded to above-mentioned antiglare hardcoat inside fully, possibly can't bring into play enough anti-dazzle property (anti-dizzy property).In order to address this problem, the method for the addition that increases above-mentioned particulate is also arranged, but this moment, the amounts of particles on the layer direction increases, its result, the problem that also has turbidity value to increase.For the high rigidityization of hard-coated antiglare film and the anti-dizzy property of bringing thus or the problem of turbidity value, proposition has the spy to open that flat 11-286083 communique, spy are opened the 2000-326447 communique, the spy opens the 2001-194504 communique and the spy opens the described technology of 2001-264508 communique.In addition, for the little high meticulous image display device of Pixel Dimensions do not take place the to dazzle anti-dazzle film of fault, open in the 2003-4903 communique on the books the spy.

Open in the flat 11-286083 communique the spy, disclose and on transparent base film, formed with the particulate of the particle of weight average particle diameter 0.6～20 μ m and weight average particle diameter 1～500nm and the hard-coated antiglare film of the antiglare hardcoat that is major component of resinizing firmly.The thickness that also discloses above-mentioned antiglare hardcoat be described particle grain size following, be preferably 80% below of weight average particle diameter (being specially below the 16 μ m).

Open in the 2000-326447 communique the spy, disclose and at least one face of plastic basis material film, form the hard-coated film that the antiglare hardcoat of one deck at least forms, also disclosing the thickness that makes above-mentioned antiglare hardcoat is 3～30 μ m, and then is that inorganic particles below the 20 μ m adds in the above-mentioned antiglare hardcoat with aggregate particle size.Also disclosing the surface that makes antiglare hardcoat becomes concaveconvex shape and gives anti-dazzle property.

Open in the 2001-194504 communique the spy, disclose a kind of antireflective film, it is stackedly at least one face of plastic sheeting to be coated with by rete firmly and to be that the antireflective film layer of major component forms with metal alkoxide and hydrolysate thereof, and the elastic modulus below breaking strain of antiglare hardcoat is 0.7～5.5GPa.Its thickness that also discloses antiglare hardcoat is that the weight average particle diameter that also discloses the particulate that contains in above-mentioned antiglare hardcoat is 0.01～10 μ m below the above 20 μ m of 0.5 μ m.

Open in the 2001-264508 communique the spy, disclose a kind of anti-dazzle property antireflective film, it is that stacked above one another contains the antiglare hardcoat that weight average particle diameter is the particle of 1～10 μ m on transparent supporting body, form with low-index layer, described low-index layer is by containing the inorganic particles that weight average particle diameter is 0.001～0.2 μ m, the hydrolysate of the organosilane of photo-curable and/or its partial condensate, and the composition of fluoropolymer forms and refractive index in 1.35～1.49 scopes, the turbidity value of this anti-dazzle property antireflective film is in 3～20% scopes, and the average reflectance of 450nm～650nm is below 1.8%.Its thickness that also discloses antiglare hardcoat is 1～10 μ m.

Open in the 2003-4903 communique the spy, disclose a kind of anti-dazzle film, the anti-dazzle film of twinkling fault does not take place in it as the relative little high meticulous image display device of Pixel Dimensions, on transparent supporting body, has antiglare layer, and the surface has concavo-convex, it is characterized in that the section area of each depression is 1000 μ m ²Below.Also disclose in above-mentioned anti-dazzle film, arithmetic mean surface roughness Ra is the scope of 0.05～1.0 μ m, and the average slope angle θ a of depression is below 20 °.

But, in these existing hard-coated antiglare films, do not solve the problem of hardness and anti-dizzy property two aspects satisfactorily.Open among the 11-286083 the spy, the problem of existence is when the thickness of above-mentioned hard conating is above-mentioned degree, can't bring into play enough hardness.Open in the 2000-326447 communique the spy, the problem that exists is if be formation as described above, give no thought to the surfaceness of above-mentioned Antidazzle hard coating laminar surface, being that above-mentioned inorganic particles is embedded under the situation of the inner such formation of above-mentioned antiglare hardcoat fully, can't bring into play enough anti-dizzy property.The spy opens the antireflective film of putting down in writing in the 2001-194504 communique, although being hardness and mar resistance, the problem of its existence improves, but, for example be that to add thickness to be under the situation in the antiglare hardcoat about 20 μ m for particulate about 1.8 μ m with weight average particle diameter, particulate is embedded to above-mentioned antiglare hardcoat inside fully, can't bring into play enough anti-dizzy property.The purpose that the spy opens the anti-dazzle property antireflective film of putting down in writing in the 2001-264508 communique is to improve traumatic resistance, anti-dazzle property etc., but problem is to obtain enough hardness.Then, open flat 11-286083 communique, spy the spy and open that 2000-326447 communique, spy are opened the 2001-194504 communique, the spy opens 2001-264508 communique and special opening in the hard-coated antiglare film of 2003-4903 communique, when from oblique observation, it exists catoptrical scattering to become strong and the visible problem of the so-called oblique white stain of stain in vain.

Summary of the invention

The aspect that the present invention proposes just in view of the above problems, its purpose is, the manufacture method of hard-coated antiglare film, the polaroid that uses it, image display device and the hard-coated antiglare film of the outstanding and then white stain can prevent from oblique the observation time of a kind of hardness and anti-dizzy property is provided.

In order to achieve the above object, hard-coated antiglare film of the present invention, it comprises the transparent plastic film base material, at least one face of above-mentioned transparent plastic film base material by particulate with resinize firmly and form antiglare hardcoat.Described antiglare hardcoat has the thickness of the scope of 15～30 μ m.The weight average particle diameter of described particulate is 30～75% a scope of the thickness of above-mentioned antiglare hardcoat.In the concaveconvex shape of the described Antidazzle hard coating laminar surface that is formed by described particulate, average slope angle θ a is the scope of 1.0～2.0 degree, and the arithmetic mean surface roughness Ra of JIS B 0601 (version in 1994) is the scope of 0.12～0.30 μ m.

Polaroid of the present invention comprises the hard-coated antiglare film of polariscope and the invention described above.

Image display device of the present invention comprises at least one of polaroid of the hard-coated antiglare film of the invention described above and the invention described above.

The manufacture method of hard-coated antiglare film of the present invention, be the manufacture method that is formed with the hard-coated antiglare film of antiglare hardcoat at least one face of transparent plastic film base material, it comprises: prepare to comprise particulate, resinize firmly and the antiglare hardcoat of solvent forms the operation of material; At least one face at described transparent plastic film base material applies described antiglare hardcoat formation material and forms the operation of filming; Form the operation of antiglare hardcoat with making described curing of coating.Described antiglare hardcoat has the thickness of the scope of 15～30 μ m.The weight average particle diameter of described particulate is 30～75% a scope of the thickness of described antiglare hardcoat.Described solvent contains ethyl acetate with the ratio that accounts for more than the whole 50 weight %.In the concaveconvex shape on the surface that is formed by described particulate, average slope angle θ a is the scope of 1.0～2.0 degree, and the arithmetic mean surface roughness Ra of JIS B 0601 (version in 1994) is the scope of 0.12～0.30 μ m.

In hard-coated antiglare film of the present invention, by with the thickness setting of above-mentioned antiglare hardcoat in the afore mentioned rules scope, can realize high rigidityization.In hard-coated antiglare film of the present invention, the weight average particle diameter of above-mentioned particulate is set in the afore mentioned rules scope, and in the concaveconvex shape of above-mentioned Antidazzle hard coating laminar surface, above-mentioned average slope angle θ a and above-mentioned arithmetic mean surface roughness Ra are set in the afore mentioned rules scope, anti-thus dizzy property is good, the white stain in the time of can also preventing from oblique the observation effectively.Thereby, possessing hard-coated antiglare film of the present invention and the image display device of having used its polaroid, its picture obtains due care; operability is good; anti-dizzy property is good, and the white stain in the time of can preventing from oblique the observation has been brought into play effects such as display characteristic is good.Can utilize the manufacture method of the invention described above to make this high performance hard-coated antiglare film of the present invention.But also can utilize other manufacture methods to make hard-coated antiglare film of the present invention.In manufacture method of the present invention,, use to account for the solvent that ratio more than the whole 50 weight % contains ethyl acetate, so antiglare hardcoat that forms and the adhesiveness between the transparent plastic film base material uprise as solvent.

Description of drawings

Fig. 1 is the profile schema diagram of formation of an example of expression hard-coated antiglare film of the present invention.

Fig. 2 is the profile schema diagram of formation of other example of expression hard-coated antiglare film of the present invention.

Fig. 3 is the mode chart of an example of the relation of expression roughness curve, height h and standard length L.

Fig. 4 is the mode chart of expression from an example of the method for the white stain of oblique evaluation.

Embodiment

In hard-coated antiglare film of the present invention and manufacture method thereof, described particulate is the different multiple particulate more than 2 kinds of weight average particle diameter, and the weight average particle diameter of at least a particulate of described multiple particulate is 30～75% a scope of the thickness of described antiglare hardcoat.

In hard-coated antiglare film of the present invention and manufacture method thereof, preferred described particulate be shaped as sphere.

In hard-coated antiglare film of the present invention, the glossiness that is preferably based on JIS K 7105 (version in 1981) is below 60.Equally, in the manufacture method of hard-coated antiglare film of the present invention, be that mode below 60 forms antiglare hardcoat preferably according to the glossiness that makes the hard-coated antiglare film that obtains according to JIS K 7105.In addition, above-mentioned " glossiness " is meant with JIS K 7105 (version in 1981) to be 60 degree mirror surface lusters of benchmark.

In hard-coated antiglare film of the present invention and manufacture method thereof, preferred described resinizing firmly comprises following (A) composition, (B) composition and (C) composition.

(A) composition: urethane acrylate and carbamate methacrylate at least a

(B) composition: polyalcohol acrylate and polyvalent alcohol methacrylate at least a

(C) composition: by at least a polymkeric substance that forms of following (C1) and following (C2) or the blended polymer of multipolymer or described polymkeric substance and multipolymer

(C1): alkyl acrylate with alkyl of at least a group in hydroxyl and the acryloyl group

(C2): alkyl methacrylate with alkyl of at least a group in hydroxyl and the acryloyl group.

Hard-coated antiglare film of the present invention preferably further is formed with anti-reflection layer on antiglare hardcoat.At this moment, preferred described anti-reflection layer contains hollow and spherical silicon oxide particle.

Below, the present invention is described in detail.But the present invention is not limited to following record.

Hard-coated antiglare film of the present invention contains the transparent plastic film base material, at the one or both sides formation antiglare hardcoat of above-mentioned transparent plastic film base material.

Above-mentioned transparent plastic film base material is not particularly limited the base material (preferred turbidity value is below 1%) that the transmittance of the preferred visible light of above-mentioned transparent plastic film base material outstanding (preferred transmittance is more than 90%) and the transparency are outstanding.The formation material of above-mentioned transparent plastic film base material for example has polyester based polymer, cellulose-based polymkeric substance, polycarbonate based polymer, acrylic acid series polymeric compounds etc.Above-mentioned polyester based polymer for example has polyethylene terephthalate, PEN etc.Above-mentioned cellulose-based polymkeric substance for example has diacetyl cellulose, triacetyl cellulose (TAC) etc.Aforesaid propylene acid based polymer for example has polymethylmethacrylate etc.The formation material of above-mentioned transparent plastic film base material also for example has styrenic, olefin polymer, vinyl chloride-based polymer, acid amides based polymer etc.Above-mentioned styrenic for example has polystyrene, acrylonitritrile-styrene resin etc.Above-mentioned olefin polymer for example has tygon, polypropylene, have the polyolefin of ring texture, have polyolefin, ethylene-propylene copolymer of norborene structure etc.Above-mentioned acid amides based polymer for example has nylon, aromatic polyamide etc.The formation material of above-mentioned transparent plastic film base material also for example has imide series polymkeric substance, sulfone based polymer, polyethersulfone based polymer, polyethers-ether ketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol based polymer, vinylidene chloride based polymer, polyvinyl butyral based polymer, arylide based polymer, polyoxymethylene based polymer, epoxy based polymer or above-mentioned mixture of polymers etc.Wherein, be particularly suitable for the film that uses optic birefringence few.Hard-coated antiglare film of the present invention for example also can be used as protective film and is used for polaroid.At this moment, as above-mentioned transparent plastic film base material, the preferred film that forms by triacetyl cellulose, polycarbonate, acrylic acid series polymeric compounds, polyolefin, polyolefin etc. with norborene structure with ring texture.In the present invention, as described later, above-mentioned transparent plastic film base material can be a polariscope self.If such formation, the protective seam that need constitute by TAC etc. not, and can make the structure simplification of polaroid.Can reduce manufacturing process's quantity of polaroid or image display device thus, improve production efficiency.And, if such formation can make the further thin layerization of polaroid.At above-mentioned transparent plastic film base material is under the polariscopic situation, the effect of above-mentioned antiglare hardcoat performance protective seam in the past.If such formation, hard-coated antiglare film can have the function that is installed in the lip-deep cover plate of liquid crystal cells concurrently.

In the present invention, the thickness to above-mentioned transparent plastic film base material is not particularly limited.If for example consider aspects such as operation such as intensity or operability and thin layer, above-mentioned thickness is preferably the scope of 10～500 μ m, and the scope of 20～300 μ m more preferably most preferably is the scope of 30～200 μ m.

Above-mentioned antiglare hardcoat uses above-mentioned particulate and above-mentioned resinizing firmly and forms.

As mentioned above, above-mentioned resinize firmly for example can enumerate comprise following (A) composition, (B) composition and (C) material of composition.

(A) composition: urethane acrylate and carbamate methacrylate at least a

(B) composition: polyalcohol acrylate and polyvalent alcohol methacrylate at least a

(C) composition: by at least a polymkeric substance that forms of following (C1) and following (C2) or the blended polymer of multipolymer or above-mentioned polymkeric substance and multipolymer

(C1): the alkyl acrylate of alkyl with at least a group of hydroxyl and acryloyl group

(C2): the alkyl methacrylate of alkyl with at least a group of hydroxyl and acryloyl group

With regard to regard to the above-mentioned urethane acrylate and carbamate methacrylate of above-mentioned (A) composition, use and to contain acrylic acid, methacrylic acid, acrylate, methacrylate, polyvalent alcohol, diisocyanate material as constituent.With regard to above-mentioned urethane acrylate and above-mentioned carbamate methacrylate at least a, for example can use at least a monomer and the polyvalent alcohol of acrylic acid, methacrylic acid, acrylate and methacrylate, make hydroxy acrylate and have hydroxyl-metacrylate at least a of 1 above hydroxyl with 1 above hydroxyl, itself and diisocyanate are reacted, make therefrom.In above-mentioned (A) composition, above-mentioned urethane acrylate and above-mentioned carbamate methacrylate can be used alone.In above-mentioned (A) composition, two or more kinds may be used for above-mentioned urethane acrylate and above-mentioned carbamate methacrylate.

The aforesaid propylene acid esters for example has: alkyl acrylate, acrylic acid cycloalkyl ester etc.The aforesaid propylene acid alkyl ester for example has: methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate etc.Aforesaid propylene acid cycloalkyl ester for example has: acrylic acid cycloalkyl ester etc.Above-mentioned methacrylate for example has: alkyl methacrylate, methacrylic acid cycloalkyl ester etc.Above-mentioned alkyl methacrylate for example has: methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, butyl methacrylate etc.Above-mentioned methacrylic acid cycloalkyl ester for example has: cyclohexyl methacrylate etc.

Above-mentioned polyvalent alcohol is the compound with at least 2 hydroxyls.Above-mentioned polyvalent alcohol for example has: 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, the 3-hydroxypivalic acid 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, grape carbohydrate etc.

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

Cooperation ratio to above-mentioned (A) composition is not particularly limited.Above-mentioned by using (A) composition, can improve formation hard conating flexibility and with respect to the adhesiveness of above-mentioned transparent plastic film base material.Considerations such as viewpoint from the hardness of these aspects and above-mentioned antiglare hardcoat, with respect to the total resinous principle in the above-mentioned antiglare hardcoat formation material, the cooperation ratio of above-mentioned (A) composition is the scope of 15～55 weight % for example, is preferably the scope of 25～45 weight %.So-called above-mentioned total resinous principle is meant (A) composition, (B) composition and (C) total amount of composition, perhaps when other resinous principle of use, is meant that total amount with above-mentioned ternary total amount and above-mentioned resinous principle adds amount together, and is as follows.

Above-mentioned (B) composition for example has: diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, six acrylic acid dipentaerythritol ester, acrylic acid 1,6-hexanediol ester, dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, hexamethyl acrylic acid dipentaerythritol ester, methacrylic acid 1,6-hexanediol ester etc.These materials can use separately.They can also be also with two or more.For example, as above-mentioned polyalcohol acrylate, the preferred monomer component that constitutes by the polymkeric substance of pentaerythritol triacrylate and pentaerythritol tetracrylate and contain pentaerythritol triacrylate and the blending constituent of pentaerythritol tetracrylate.

Cooperation ratio to above-mentioned (B) is not particularly limited.For example, with respect to above-mentioned (A) composition, the cooperation ratio of above-mentioned (B) composition is preferably the scope of 70～180 weight %, the more preferably scope of 100～150 weight %.When the cooperation ratio of above-mentioned (B) composition is 180 weight % when following with respect to above-mentioned (A) composition, can effectively prevent the cure shrinkage of the above-mentioned antiglare hardcoat that forms.Its result can prevent the crimping of above-mentioned hard-coated antiglare film, can prevent that its flexibility from reducing.As long as the cooperation ratio of above-mentioned (B) composition is more than the 70 weight % of above-mentioned (A) composition, just can further improve the hardness of formed above-mentioned antiglare hardcoat, can improve its mar resistance.

In above-mentioned (C) composition, (C1) and alkyl (C2) are not particularly limited.Abovementioned alkyl for example is that carbon number is 1～10 alkyl.Abovementioned alkyl can be the straight chain shape, also can be a chain.As above-mentioned (C) composition, for example, can enumerate the potpourri of polymkeric substance, multipolymer or the above-mentioned polymkeric substance and the above-mentioned multipolymer of the repetitive that comprises following general formula (1).

In above-mentioned formula (1), R ¹For-H or-CH ₃, R ²For-CH ₂CH ₂OX or with the group of following general formula (2) expression, above-mentioned X be-H or the acryloyl group represented with following general formula (3).

In above-mentioned general formula (2), above-mentioned X is-H or with the acryloyl group of following general formula (3) expression, above-mentioned X can be identical, also can be different.

As above-mentioned (C) composition, for example can enumerate the polymkeric substance that forms by at least a monomer that is selected from the group that following material constitutes, the potpourri of multipolymer or above-mentioned polymkeric substance and above-mentioned multipolymer, described material for example has: acrylic acid 2,3-two hydroxypropyl acrylates, acrylic acid 2,3-two propylene acyloxy propyl ester, acrylic acid 2-hydroxyl-3-acryloxy propyl ester, acrylic acid 2-acryloxy-3-hydroxypropyl acrylate, methacrylic acid 2,3-two hydroxypropyl acrylates, methacrylic acid 2,3-two propylene acyloxy propyl ester, methacrylic acid 2-hydroxyl-3-acryloxy propyl ester, methacrylic acid 2-acryloxy-3-hydroxypropyl acrylate, acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-acryloxy ethyl ester, methacrylic acid 2-hydroxyl ethyl ester and methacrylic acid 2-acryloxy ester.

Cooperation ratio to above-mentioned (C) composition is not particularly limited.For example, with respect to above-mentioned (A) composition, the cooperation ratio of above-mentioned (C) composition is preferably the scope of 25～110 weight %, the more preferably scope of 45～85 weight %.As long as the cooperation ratio of above-mentioned (C) composition is below the 110 weight % with respect to above-mentioned (A) composition, just can make the screening characteristics of above-mentioned antiglare hardcoat formation material good.As long as the cooperation ratio of above-mentioned (C) composition is more than the 25 weight % with respect to above-mentioned (A) composition, just can prevent the cure shrinkage of formed above-mentioned antiglare hardcoat.Its result in above-mentioned hard-coated antiglare film, can prevent crimping.

The major function that is used to form the particulate of above-mentioned antiglare hardcoat is, the Antidazzle hard coating laminar surface that forms is made concaveconvex shape and gives anti-dazzle property.As above-mentioned particulate, inorganic particles and organic fine particles are for example arranged.Above-mentioned inorganic particles is not particularly limited, silicon oxide particle, titanium oxide microparticle, alumina particulate, zinc oxide fine particles, tin oxide particulate, calcium carbonate microparticle, barium sulphate particulate, talcum particulate, kaoline par-tides, calcium sulphate particulate etc. are for example arranged.Above-mentioned organic fine particles is not particularly limited, and above-mentioned organic fine particles for example has polymethylmethacrylate acrylate resin powder (PMMA particulate), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic acid styrene resin powder, benzoguanamine toner, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide powder, polyimide resin powder, polyfluoroethylene resin powder etc.These inorganic particles and organic fine particles can be used alone, and also two or more kinds may be used.

The weight average particle diameter of above-mentioned particulate is 30%～75% scope of the thickness of above-mentioned antiglare hardcoat, more preferably 30～50% scope.As long as the weight average particle diameter of above-mentioned particulate is more than 30%, just can form enough concaveconvex shapes at above-mentioned Antidazzle hard coating laminar surface, can give enough anti-dazzle functions.As long as the weight average particle diameter of above-mentioned particulate is below 75%, just the concavo-convex difference on surface can be made suitable size, can make outward appearance good, catoptrical scattering suitably can be controlled in addition, can prevent white stain.In the present invention, the weight average particle diameter of above-mentioned particulate for example is 4.5～22.5 μ m, is preferably 5.4～18.8 μ m, the scope of 5.4～12.5 μ more preferably.The weight average particle diameter of above-mentioned particulate for example can utilize the Ku Erte counting method to measure.In the mensuration of the weight average particle diameter of above-mentioned particulate, for example use the particle size distribution device (trade name: Coulter multisizer of having utilized the pore electric-resistivity method, the BechmanCoulter corporate system), the resistance of electrolytic solution that is equivalent to the volume of above-mentioned particulate when measuring above-mentioned particulate by above-mentioned pore, measure the quantity and the volume of above-mentioned particulate, calculate weight average particle diameter.

Shape to above-mentioned particulate is not particularly limited, and for example can be the roughly spherical of pearl, can also be the particulate of indefinite form such as powder.As mentioned above, in the present invention, above-mentioned particulate preferred weight mean grain size is two or more multiple particulate.At this moment, above-mentioned particulate is meant that the assembly (particulate powder) that a plurality of microparticle agglutination with a kind of weight average particle diameter form has two or more.As mentioned above, above-mentioned particulate is preferably roughly spherical, and more preferably its asperratio is the roughly spherical particle below 1.5.As long as above-mentioned asperratio is below 1.5, in the concaveconvex shape of above-mentioned Antidazzle hard coating laminar surface, just can control above-mentioned arithmetic mean surface roughness Ra and above-mentioned average slope angle θ a better.Above-mentioned asperratio is more preferably less than 1.05.

Cooperation ratio to above-mentioned particulate is not particularly limited, and can suitably set the cooperation ratio of above-mentioned particulate.With respect to above-mentioned resinous principle total amount 100 weight portions, the cooperation ratio of above-mentioned particulate is the scope of 2～70 weight portions for example, is preferably the scope of 4～50 weight portions, more preferably the scope of 15～40 weight portions.

Viewpoints such as light scattering from preventing to produce at the interface of above-mentioned particulate and above-mentioned antiglare hardcoat preferably reduce the refringence between above-mentioned particulate and the above-mentioned antiglare hardcoat.By preventing that above-mentioned light scattering from also can prevent white stain.The refractive index of above-mentioned antiglare hardcoat is generally 1.4～1.6 scope, so preferred index is near the particulate of this ranges of indices of refraction.The difference of the refractive index of above-mentioned particulate and above-mentioned antiglare hardcoat is preferably less than 0.05.

In the concaveconvex shape of above-mentioned Antidazzle hard coating laminar surface, above-mentioned average slope angle θ a is the scope of 1.0～2.0 degree, and above-mentioned arithmetic mean surface roughness Ra is the scope of 0.12～0.30 μ m.If less than 0.12 μ m, then anti-dizzy property becomes insufficient to above-mentioned average slope angle θ a less than 1.0 degree or above-mentioned arithmetic mean surface roughness Ra, produce the unfavorable condition that outer light etc. is mirrored and so on.On the contrary, if above-mentioned average slope angle θ a surpasses 2.0 degree or above-mentioned arithmetic mean surface roughness Ra surpasses 0.30 μ m, can produce oblique white stain.Above-mentioned average slope angle θ a is preferably the scope of 1.1～1.8 degree, more preferably the scope of 1.2～1.6 degree.Above-mentioned arithmetic mean surface roughness Ra is preferably the scope of 0.15～0.28 μ m, more preferably the scope of 0.16～0.27 μ m.In the present invention, above-mentioned arithmetic mean surface roughness Ra and above-mentioned average slope angle θ a can adjust by the above-mentioned kind of resinizing firmly of suitable selection, the thickness of above-mentioned antiglare hardcoat, the kind of above-mentioned particulate, the weight average particle diameter of above-mentioned particulate etc., if those skilled in the art, can excessively not attempt, above-mentioned arithmetic mean surface roughness Ra and above-mentioned average slope angle θ a can be controlled in the scope of the present invention's regulation.

In the present invention, above-mentioned average slope angle θ a is the value with following mathematical expression [1] definition.Above-mentioned average slope angle θ a for example is a value of utilizing the described method of aftermentioned embodiment to measure.

Average slope angle θ a=tan ^-1Δ a [1]

In above-mentioned mathematical expression [1], Δ a is shown in following mathematical expression [2], be in the standard length L of the roughness curve of JIS B 0601 (1994 year version) regulation, with the total (h1+h2+h3 of poor (the height h) of the minimum point of adjacent peak maximum and paddy ... + the value that hn) obtains divided by above-mentioned standard length L.Above-mentioned roughness curve is by phasic difference compensation form height bandpass filter, removes the curve that the waviness of the surface composition longer than provision wavelengths forms from section curve.Above-mentioned section curve is meant when cutting off the object face with the rectangular plane of object face, the profile that its otch manifests.Fig. 3 represents the example of above-mentioned roughness curve, height h and standard length L.

Δa＝(h1+h2+h3…+hn)/L [2]

Above-mentioned arithmetic mean surface roughness Ra is also referred to as arithmetic average roughness Ra.It is one of index of expression body surface roughness, is prescribed in JIS B 0601 (version in 1994).Above-mentioned arithmetic mean surface roughness Ra can utilize for example method mensuration of aftermentioned embodiment.

The poor d of the refractive index of above-mentioned transparent plastic film base material and the refractive index of above-mentioned antiglare hardcoat is preferably below 0.04.As long as the poor d of above-mentioned refractive index is below 0.04, just can suppress the generation of interference fringe.Above-mentioned d is more preferably below 0.02.

The thickness of above-mentioned antiglare hardcoat is the scope of 15～30 μ m.As long as above-mentioned thickness is in the scope of afore mentioned rules, above-mentioned antiglare hardcoat just can become the also sufficient hard conating (for example, counting more than the 4H with pencil hardness) of hardness, in addition, it is appropriate that the concave-convex surface shape also becomes, and anti-dizzy property is good, and can prevent oblique white stain.The thickness of above-mentioned antiglare hardcoat is preferably the scope of 18～25 μ m.

Hard-coated antiglare film of the present invention can utilize following method to make, for example, preparation comprises and contains above-mentioned particulate, above-mentioned resinize firmly and the antiglare hardcoat of solvent forms material, at least one face at described transparent plastic film base material applies described antiglare hardcoat formation material, formation is filmed, and makes described curing of coating and forms described antiglare hardcoat.

Above-mentioned solvent is not particularly limited, above-mentioned solvent for example has: 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 ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone, ethyl 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, cyclohexanol, isobutyl acetate, hexone (MIBK), methyl n-heptyl ketone, 2 pentanone, methyl-n-butyl ketone, the 2-heptanone, the 3-heptanone, ethoxyethyl acetate(EA), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (EGMBE), glycol monomethyl ether, propylene glycol monomethyl ether acetic acid esters, propylene glycol monomethyl ether etc.These materials can be used alone, and also two or more kinds may be used.Consider from the adhesiveness aspect that improves described transparent plastic film base material and described antiglare hardcoat, preferred above-mentioned solvent contains ethyl acetate with the ratio that accounts for more than the whole 20 weight %, more preferably contain ethyl acetate, most preferably contain ethyl acetate with the ratio that accounts for whole 70 weight % with the ratio that accounts for more than the whole 60 weight %.Solvent types with ethyl acetate and usefulness is not particularly limited, and above-mentioned solvent for example has: butyl acetate, methyl ethyl ketone, ethylene glycol monobutyl ether (EGMBE), propylene glycol monomethyl ether etc.

Form in the material at above-mentioned antiglare hardcoat, can add various levelling agents.As above-mentioned levelling agent, for example can enumerate fluorine system or silicone-based levelling agent, preferred silicone-based levelling agent.Above-mentioned silicone-based levelling agent for example has: reactive silicone, dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, poly-methyl alkyl siloxane etc.In these silicone-based levelling agents, preferred especially above-mentioned reactive silicone.By adding above-mentioned reactive silicone, give sliding and long term maintenance mar resistance to the surface.If use and have the material of hydroxyl as above-mentioned reactive silicone, as described later, when form the layer during as anti-reflection layer (low-index layer) contain silicone component on above-mentioned antiglare hardcoat, the adhesiveness of then above-mentioned anti-reflection layer and above-mentioned antiglare hardcoat improves.

With respect to above-mentioned resinous principle total amount 100 weight portions, the use level of above-mentioned levelling agent for example is below 5 weight portions, to be preferably the scope of 0.01～5 weight portion.

In the formation material of above-mentioned antiglare hardcoat, in the scope that does not influence performance, can add pigment, filling agent, spreading agent, plastifier, ultraviolet light absorber, surfactant, antioxidant, thixotropic agent etc. as required.Above-mentioned adjuvant can be used alone, can also be also with more than 2 kinds.

Form in the material at above-mentioned antiglare hardcoat, can use known in the past Photoepolymerizationinitiater initiater.As above-mentioned Photoepolymerizationinitiater initiater, for example can enumerate 2,2-dimethoxy-2-phenyl acetophenone, acetophenone, benzophenone, xanthone, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone, benzisoxa propyl ether, benzyl dimethyl ketal, N, N, N ', N '-tetramethyl-4,4 '-diaminobenzophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone etc. can also use thioxanthones based compound etc. in addition.

As the method for the above-mentioned antiglare hardcoat formation of coating on above-mentioned transparent plastic film base material material, for example can use: spray coating processs such as coating (fountain coating) method, punch die formula coating (diecoating) method, spin-coating method, spraying process, intaglio printing rubbing method, rolling method, excellent Tu Fa.

Apply above-mentioned antiglare hardcoat and form material, on above-mentioned transparent plastic film base material, form and film, make above-mentioned curing of coating.Before above-mentioned curing, preferably make above-mentioned dried coating film.With regard to above-mentioned drying, for example, can be air dry, also can be the air-dry of blowing, can also be heat drying, can also be the method that these drying means are combined.

The curing means of filming that above-mentioned antiglare hardcoat formed material are not particularly limited.The preferred ionizing radiation of above-mentioned curing means solidifies.In above-mentioned curing means, can use various active-energies.Above-mentioned active-energy is ultraviolet ray preferably.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 above-mentioned energy line source, as the accumulated exposure amount at ultraviolet wavelength 365nm place, preferred 50～5000mJ/cm ²As long as above-mentioned exposure is 50mJ/cm ²More than, just can make curing more abundant, it is more abundant that the hardness of the antiglare hardcoat of formation also becomes.As long as above-mentioned exposure is 5000mJ/cm ²Below, just can prevent that the antiglare hardcoat that forms is painted, can improve the transparency.

As mentioned above, form above-mentioned antiglare hardcoat, can make hard-coated antiglare film of the present invention by at least one face at above-mentioned transparent plastic film base material.Need to prove that hard-coated antiglare film of the present invention also can utilize the manufacture method beyond the said method to make.The hardness of hard-coated antiglare film of the present invention in pencil hardness, for example has the above hardness of 4H.

Fig. 1 represents the profile schema diagram of an example of hard-coated antiglare film of the present invention.As shown in Figure 1, this routine hard-coated antiglare film 4 comprises transparent plastic film base material 1, is to be formed with antiglare hardcoat 2 on the one side of above-mentioned transparent plastic film base material 1.Above-mentioned antiglare hardcoat 2 contains particulate 3, and like this, the surface of antiglare hardcoat 2 becomes concaveconvex shape.In this embodiment, be on the one side of transparent plastic film base material 1, to be formed with antiglare hardcoat 2.But the present invention is not limited thereto.Hard-coated antiglare film of the present invention also can be the hard-coated antiglare film that is formed with antiglare hardcoat 2 on the two sides of transparent plastic film base material 1.This routine antiglare hardcoat 2 is individual layers.But the present invention is not limited thereto.Above-mentioned antiglare hardcoat 2 can also be the sandwich construction that is laminated more than 2 layers.

In hard-coated antiglare film of the present invention, can on above-mentioned antiglare hardcoat, form anti-reflection layer (low-index layer).Fig. 2 represents to comprise the profile schema diagram of an example of the hard-coated film of the present invention of above-mentioned anti-reflection layer.As shown in Figure 2, this routine hard-coated antiglare film 6 has following formation, promptly forms the antiglare hardcoat 2 that contains particulate 3 on the one side of transparent plastic film base material 1, forms anti-reflection layer 5 on this antiglare hardcoat 2.When illumination is mapped to object, repeats in the reflection at its interface, in the absorption of inside, the phenomenon of scattering, and see through to the back side of object.For example, when on image display device, hard-coated antiglare film being installed,, can enumerate reflection of light in air and Antidazzle hard coating bed interface as the one of the main reasons that the identification that makes image reduces.Above-mentioned anti-reflection layer is the layer that reduces its surface reflection.In hard-coated antiglare film shown in Figure 26, above-mentioned antiglare hardcoat 2 and above-mentioned anti-reflection layer 5 are to form on the one side of above-mentioned transparent plastic film base material 1.But the present invention is not limited thereto.In hard-coated antiglare film of the present invention, also above-mentioned antiglare hardcoat 2 and above-mentioned anti-reflection layer 5 can be arranged on the two sides of above-mentioned transparent plastic film base material 1.In hard-coated antiglare film shown in Figure 2, antiglare hardcoat 2 and anti-reflection layer 5 are respectively individual layer.But the present invention is not limited thereto.Above-mentioned antiglare hardcoat 2 and above-mentioned anti-reflection layer 5 can be respectively the sandwich construction that is laminated more than 2 layers.

In the present invention, above-mentioned anti-reflection layer is the layer that the strict optical thin film of having controlled thickness and refractive index or stacked above-mentioned optical thin film more than 2 layers form.In above-mentioned anti-reflection layer, show anti-reflective function by the phase place of utilizing the interference of light effect to eliminate incident light and catoptrical reverse mutually.Demonstrate the wavelength region may of the luminous ray of above-mentioned anti-reflective function, for example be 380～780nm, particularly the wavelength region may that visibility is high is the scope of 450～650nm, the above-mentioned anti-reflection layer of decision design, and make its reflectivity become minimum as the 550nm of its centre wavelength.

In design,, for example, the method for the refringence that increases above-mentioned anti-reflection layer and above-mentioned antiglare hardcoat is arranged as the means of improving its interference effect based on the above-mentioned anti-reflection layer of interference of light effect.Usually, with regard to being laminated with 2～5 layers the multilayer anti-reflection layer of structure of optics thin layer (film of thickness and refractive index has been controlled in strictness), only the thickness with regulation forms the different composition of multilayer refractive index.Thereby degree of freedom increases aspect the optical design of above-mentioned anti-reflection layer, can further improve anti-reflection effect, and (smooth) also becomes possibility to divide reflective character to become evenly in the visible region.In above-mentioned optical thin film, the thickness and precision of requirement is very high.So, usually adopt vacuum evaporation as the dry type mode, sputter, CVD etc. to carry out the formation of each layer.

As above-mentioned multilayer anti-reflection layer, preferably in the high titanium oxide layer of refractive index (refractive index: the about 1.8) silicon oxide layer that the folded refractive index in upper strata is low (refractive index: the anti-reflection layer of 2 layers of structure that about 1.45) obtain, more preferably stacked silicon oxide layer and stacked thereon other titanium oxide layers, stacked other silicon oxide layers and the anti-reflection layer of 4 layers of structure forming thereon on titanium oxide layer.By forming these 2 layers of anti-reflection layers or 4 layers of anti-reflection layer, can reduce the reflection of the wavelength region may (for example scope of 380～780nm) of luminous ray equably.

By on above-mentioned antiglare hardcoat, forming the optical thin film (anti-reflection layer) of individual layer, can demonstrate anti-reflection effect.Usually when forming the individual layer anti-reflection layer, coating process such as for example can adopt that injection coating, the coating of punch die formula, spin coating, spraying, intaglio printing coating, roller coat, rod as the wet type mode is coated with.

As the formation material of above-mentioned individual layer anti-reflection layer, for example can enumerate resin system materials such as ultraviolet curing based acrylic resin, in resin, disperseed inorganic particles such as colloidal silica mixed stocker material, tetraethoxysilane, used the sol-gel based material of metal alkoxides such as purity titanium tetraethoxide etc.In above-mentioned formation material,, preferably contain fluorine-based material in order to give anti fouling performance to the surface.In above-mentioned formation material, from reasons such as mar resistances, the many formation materials of preferred inorganic constituents content, more preferably above-mentioned sol-gel based material.Above-mentioned sol-gel based material can use after the part condensation.

In anti-reflection layer (low-index layer), can contain inorganic sol in order to improve film strength.Above-mentioned inorganic sol is not particularly limited, for example can enumerates monox, aluminium oxide, magnesium fluoride etc.Wherein, preferred silica sol.With regard to the cooperation ratio of above-mentioned inorganic sol, for example form total solid composition 100 weight portions of material with respect to above-mentioned anti-reflection layer, be the scope of 10～80 weight portions.The particle diameter of the inorganic particles in the above-mentioned inorganic sol is 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, preferably contain hollow and spherical monox ultra micron.The ultramicronized mean grain size of above-mentioned monox is preferably about 5～300nm, more preferably the scope of 10～200nm.Above-mentioned monox ultra micron is to be formed with the hollow sphere that the cavity forms in the enclosure with pore, and solvent and at least a of gas when including the above-mentioned monox ultra micron of modulation in this cavity form.In addition, the precursor substance that is preferred for forming the ultramicronized above-mentioned cavity of above-mentioned monox remains in the above-mentioned cavity.The thickness of above-mentioned shell is preferably in the scope about 1～50nm, and in about 1/50～1/5 scope of the ultramicronized mean grain size of above-mentioned monox.Above-mentioned shell preferably is made of the overlayer of multilayer.In above-mentioned monox ultra micron, preferred above-mentioned pore is sealed, and above-mentioned cavity is by above-mentioned body seal.Its reason is, in above-mentioned anti-reflection layer, keeps ultramicronized porous matter of above-mentioned monox or cavity, can further reduce the refractive index of above-mentioned anti-reflection layer.As such hollow and the spherical ultramicronized manufacture method of monox, for example, can suitably adopt the spy to open that disclosed monox is the manufacture method of particulate in the 2000-233611 communique.

The drying when forming above-mentioned anti-reflection layer (low-index layer) and the temperature of curing are not particularly limited, and for example are 60 ℃～150 ℃ scope, preferred 70 ℃～130 ℃ scope.The time of above-mentioned drying and curing for example is 1～30 minute scope, under the situation of considering throughput rate, is preferably 1～10 minute scope.In addition,, further carry out heat treated, obtain having the hard-coated antiglare film of the high rigidity of anti-reflection layer thus in above-mentioned drying with after solidifying.Temperature to above-mentioned heat treated is not particularly limited, and the temperature of above-mentioned heat treated for example is 40～130 ℃ a scope, preferred 50 ℃～100 ℃ scope.The above-mentioned heat treated time is not particularly limited.The above-mentioned heat treated time for example is 1 minute～100 hours, considers from improving the mar resistance aspect, more preferably carries out more than 10 hours.Above-mentioned heat treated can adopt by the method for heating plate, baker, band oven etc. and implement.

When the above-mentioned hard-coated antiglare film that will comprise above-mentioned anti-reflection layer was installed on the image display device, it is higher that above-mentioned anti-reflection layer becomes the most surperficial frequency.Therefore, above-mentioned anti-reflection layer is subjected to the pollution from external environment condition easily.Above-mentioned anti-reflection layer is compared with simple transparent panel etc., pollutes more obvious.For example, above-mentioned anti-reflection layer is easily because of adhering to pollutants such as fingerprint, hand dirt, sweat or the material of getting a haircut, and surface reflectivity changed or attachment turns white and floats, and seems that displaying contents can be unclear.In order to prevent easily the removing property of adhering to and improve the above-mentioned pollutant that has adhered to of above-mentioned pollutant, the preferred stacked anti-contamination layer that forms by fluorine-containing silane based compound or fluorine-containing organic compound etc. on above-mentioned anti-reflection layer.

In hard-coated antiglare film of the present invention, preferably at least one of above-mentioned transparent plastic film base material and above-mentioned antiglare hardcoat carried out surface treatment.As long as above-mentioned transparent plastic film substrate surface is carried out surface treatment, just can further improve adhesiveness with above-mentioned antiglare hardcoat or polariscope or polaroid.As long as above-mentioned Antidazzle hard coating laminar surface is carried out surface treatment, just can further improve adhesiveness with above-mentioned anti-reflection layer or polariscope or polaroid.As above-mentioned surface treatment, for example can use low pressure plasma processing, ultraviolet treatment with irradiation, corona treatment, flame treatment, acid or alkali treatment.As the surface treatment during as above-mentioned transparent plastic film base material with triacetylcellulose film, preferred bases is handled.For example, after making triacetylcellulose film surface contact aqueous slkali, wash and drying, can carry out this alkali treatment thus.As above-mentioned aqueous slkali, for example can use potassium hydroxide solution, sodium hydroxide solution.The normal concentration of the hydroxide ion of above-mentioned aqueous slkali (volumetric molar concentration) is preferably the scope of 0.1N～3.0N (mol/L), more preferably the scope of 0.5N～2.0N (mol/L).

Comprising the transparent plastic film base material and on the one side of above-mentioned transparent plastic film base material, be formed with in the hard-coated antiglare film of above-mentioned antiglare hardcoat,, can carry out solvent processing its another side in order to prevent crimping.Above-mentioned solvent processing can make the solvent of its dissolving that the solvent of its swelling is carried out by making above-mentioned transparent plastic film base material contact.By above-mentioned solvent processing, give the power of above-mentioned transparent plastic film base material to above-mentioned its another side side crimping, thus, offset the power of the generation crimping that above-mentioned transparent plastic film base material causes because of the formation of above-mentioned antiglare hardcoat, can prevent the generation of crimping.Equally, comprising above-mentioned transparent plastic film base material and on the one side of above-mentioned transparent plastic film base material, being formed with in the hard-coated antiglare film of above-mentioned antiglare hardcoat,, also can form transparent resin layer at its another side in order to prevent the generation of crimping.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.

Hard-coated antiglare film of the present invention can be fitted in the optical component that is used for LCD or ELD with above-mentioned transparent plastic film base material side by bonding agent or tackifier usually.When fitting, can implement and above-mentioned same various surface treatments above-mentioned transparent plastic film substrate surface.

As above-mentioned optical component, for example can enumerate polariscope or polaroid.Polaroid uses the polaroid that comprises polariscope and formed transparent protective film in above-mentioned polariscopic one or both sides usually.When on above-mentioned 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.Above-mentioned polaroid is so that the roughly mutually orthogonal mode of the absorption axes of two polaroids disposes.

Then, in being laminated with the optical component of hard-coated antiglare film of the present invention, be that example describes with the polaroid.By using tackifier or bonding agent etc. that hard-coated antiglare film of the present invention and polariscope or polaroid is stacked, the polaroid that can obtain having function of the present invention.

Above-mentioned polariscope is not particularly limited.As above-mentioned 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, by the polariscope that dichroic substance such as polyvinyl alcohol film and iodine are formed, its polarization dichroic ratio height, preferred.Above-mentioned polariscopic thickness is not particularly limited, and above-mentioned polariscopic thickness for example is about 5～80 μ m.

With polyvinyl alcohol film with iodine staining after the polariscope that unilateral stretching forms for example, can make for 3～7 times that be stretched to raw footage by after dyeing in the aqueous solution that polyvinyl alcohol film be impregnated in iodine.As required, the aqueous solution of above-mentioned iodine also can contain boric acid or zinc sulfate, zinc chloride etc.In addition, also polyvinyl alcohol film can be impregnated in the aqueous solution that comprises boric acid or zinc sulfate, zinc chloride etc.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 or 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, preferably stability of its transparency, physical strength, thermal stability, moisture shielding, phase difference value etc. is good.As the material that forms above-mentioned transparent protective film, for example can enumerate and the same material of above-mentioned transparent plastic film base material.

As above-mentioned transparent protective film, can enumerate the macromolecule membrane of opening record in the 2001-343529 communique (WO01/37007) the spy.The macromolecule membrane of putting down in writing in the above-mentioned communique for example can be enumerated by containing (A) and has substituted imido and the thermoplastic resin of at least a imino group and (B) have the macromolecule membrane that the resin combination of the thermoplastic resin of at least a phenyl and itrile group in substituted-phenyl and the unsubstituted phenyl forms at side chain in the substituted imido not at side chain.As the macromolecule membrane that forms by above-mentioned resin combination, can be exemplified as the macromolecule membrane that forms by the resin combination that contains the alternating copolymer formed by isobutylene and N-methyl maleimide and acrylonitritrile-styrene resin.Above-mentioned macromolecule membrane can be by being that film like is made with above-mentioned resin combination extrusion molding.Because the phase differential of above-mentioned macromolecule membrane is little, 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 deformation.Because the moisture permeability of above-mentioned macromolecule membrane is less, so the humidification permanance is outstanding.

As described transparent protective film, from viewpoints such as polarization characteristic or permanance, the film of cellulose-based resinous film such as preferred triacetyl cellulose and norbornene resin system.As the commercially available product of above-mentioned transparent protective film, for example can enumerate trade name " FUJITAC " (Fuji Photo Film Co., Ltd.'s system), trade name " ZEONOA " (Japanese Zeon corporate system), trade name " ARTON " (JSR corporate system) etc.

Thickness to described transparent protective film is not particularly limited.From viewpoints such as operability, thin layer such as intensity, the property handled, the thickness of described transparent protective film for example is the scope of 1～500 μ m.If in above-mentioned scope, just can mechanically protect polariscope, also do not shrink even be exposed to hot and humid polariscope down, guarantee stable optical characteristics.The thickness of described transparent protective film is preferably the scope of 5～200 μ m, more preferably the scope of 10～150 μ m.

Formation to the polaroid that is laminated with hard-coated antiglare film is not particularly limited.Described polaroid for example can be the formation that stacked above one another has transparent protective film, polariscope and transparent protective film on hard-coated antiglare film.Described polaroid for example can also be the formation that stacked above one another has polariscope, transparent protective film on hard-coated antiglare film.

Hard-coated antiglare film of the present invention and the various optical components such as polaroid that used this hard-coated antiglare film can be preferred for various image display devices such as liquid crystal indicator.Liquid crystal indicator of the present invention except using hard-coated antiglare film of the present invention and liquid crystal indicator in the past be same formation.Liquid crystal indicator of the present invention for example can wait by optical components such as appropriate combination liquid crystal cells, polaroid and the illuminator various component parts such as (backlights etc.) that add as required and the driving circuit of packing into and make.Above-mentioned liquid crystal cells is not particularly limited, can uses for example various types of liquid crystal cells such as TN type, STN type, π type.

In the present invention, the formation to liquid crystal indicator is not particularly limited.The one or both sides that liquid crystal indicator of the present invention for example is included in liquid crystal cells have disposed the liquid crystal indicator of above-mentioned optical element, used the liquid crystal indicator of backlight or reflecting plate etc. in illuminators.In these liquid crystal indicators, optical element of the present invention can be arranged on the one or both sides of liquid crystal cells.When above-mentioned optical element was arranged on the both sides of above-mentioned liquid crystal cells, they both can be identical, also can be different.On above-mentioned liquid crystal indicator, can dispose for example various optical components and opticses such as diffuser plate, antiglare layer, anti-reflection layer, fender, prism array, lens arra thin slice, light diffusing sheet, backlight.

Embodiment

Below, embodiments of the invention and comparative example are described.But the present invention is not limited to the following examples and comparative example.

(embodiment 1)

Be ready to resin raw material (solid component concentration 66 weight %, big Japanese ink corporate system, trade name: GRANDIC PC1097), that this resin raw material contains is as follows, (A) composition, (B) composition, (C) composition, Photoepolymerizationinitiater initiater and mixed solvent.In solid constituent 100 weight portions of this resin raw material, (ponding changes into corporate system to the PMMA particle of cooperation weight average particle diameter 8 μ m, trade name: MBX-8SSTN) 70 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PC-F479) 0.1 weight portion and mixing.Use solvent (ethyl acetate) to dilute this potpourri,, modulate antiglare hardcoat thus and form material so that solid component concentration is 55 weight %.(triacetylcellulose film of thick 80 μ m, refractive index: 1.48), use the #24 rod to be coated with machine and apply above-mentioned antiglare hardcoat formation material, formation is filmed at the transparent plastic film base material.After above-mentioned coating, heat above-mentioned filming 1 minute down at 100 ℃, make above-mentioned dried coating film.Then, with high-pressure mercury light irradiation accumulative total light quantity 300mJ/cm ²Ultraviolet ray, above-mentioned filming implement to solidify handled, form the antiglare hardcoat of thick 25 μ m.Obtain the target hard-coated antiglare film thus.Above-mentioned PMMA particulate almost is asperratio less than 1.05.

(A) composition: isophorone diisocyanate urethane acrylate (100 weight portion)

(B) composition: six acrylic acid dipentaerythritol ester (38 weight portion), pentaerythritol tetracrylate (40 weight portion) and pentaerythritol triacrylate (15.5 weight portion)

(C) composition: potpourri (30 weight portion) with polymkeric substance, multipolymer or above-mentioned polymkeric substance and multipolymer of the repetitive of representing with above-mentioned general formula (1)

Photoepolymerizationinitiater initiater: trade name Irgacure 184 (Ciba Specialty Chemicals corporate system) 1.8 weight portions and Lucirin type Photoepolymerizationinitiater initiater 5.6 weight portions

Mixed solvent: butyl acetate: ethyl acetate (weight ratio)=3: 4

(embodiment 2)

Be ready to resin raw material (solid component concentration 66 weight %, big Japanese ink corporate system, trade name: GRANDIC PC1071), that this resin raw material contains is as follows, (A) composition, (B) composition, (C) composition, Photoepolymerizationinitiater initiater and mixed solvent.In solid constituent 100 weight portions of this resin raw material, cooperate the PMMA particle of weight average particle diameter 10 μ m (to combine the chemical company's system of grinding, trade name: MX1000) 50 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PC4-4133) 0.5 weight portion and mixing.Dilute this potpourri with solvent (normal butyl alcohol),, modulate antiglare hardcoat thus and form material so that solid component concentration is 35 weight %.Use above-mentioned antiglare hardcoat to form material, use the #40 rod to be coated with machine, in addition, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of present embodiment is 24 μ m.Above-mentioned PMMA particulate almost is asperratio less than 1.05.

(A) composition: by pentaerythrite is the urethane acrylate (100 weight portion) that acrylate and hydrogenated xylene diisocyanate constitute

(B) composition: six acrylic acid dipentaerythritol ester (49 weight portion), pentaerythritol tetracrylate (41 weight portion) and pentaerythritol triacrylate (24 weight portion)

(C) composition: potpourri (59 weight portion) with polymkeric substance, multipolymer or above-mentioned polymkeric substance and multipolymer of the repetitive of representing with above-mentioned general formula (1)

Photoepolymerizationinitiater initiater: trade name Irgacure 184 (Ciba Specialty Chemicals corporate system) 3 weight portions

Mixed solvent: butyl acetate: ethyl acetate (weight ratio)=89: 11

(embodiment 3)

Use the resin raw material identical with embodiment 2.In solid constituent 100 weight portions of this resin raw material, cooperate the PMMA particle of weight average particle diameter 10 μ m (to combine the chemical company's system of grinding, trade name: MX1000) 30 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDICPC4-4133) 0.5 weight portion and mixing.Dilute this potpourri with solvent (cellosolve acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 35 weight %.Use above-mentioned antiglare hardcoat to form material, use the #40 rod to be coated with machine, in addition, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of present embodiment is 25 μ m.Above-mentioned PMMA particulate almost is asperratio less than 1.05.

(embodiment 4)

Use the resin raw material identical with embodiment 1.In solid constituent 100 weight portions of this resin raw material, (ponding changes into corporate system to the PMMA particle of cooperation weight average particle diameter 7.2 μ m, trade name: XX40AA) 20 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDICPC4-4133) 0.5 weight portion and mixing.Dilute this potpourri with solvent (ethyl acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 55 weight %.Use above-mentioned antiglare hardcoat to form material, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of present embodiment is 22 μ m.Above-mentioned PMMA particulate almost is asperratio less than 1.05.

(embodiment 5)

Use the resin raw material identical with embodiment 1.In solid constituent 100 weight portions of this resin raw material, (ponding changes into corporate system to the PMMA particle of cooperation weight average particle diameter 8 μ m, trade name: the MBX-8SSTN) silicon oxide particle (SILYSIA of the Fuji corporate system of 20 weight portions, weight average particle diameter 2.5 μ m, trade name: SYLOPHOBIC 702) 25 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PCF479) 0.1 weight portion and mixing.Dilute this potpourri with solvent (ethyl acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 55 weight %.Use above-mentioned antiglare hardcoat to form material, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of present embodiment is 25 μ m.Above-mentioned PMMA particulate almost is asperratio less than 1.05.Above-mentioned silicon oxide particle almost is asperratio more than 1.6.

(embodiment 6)

Use the resin raw material identical with embodiment 2.In solid constituent 100 weight of this resin raw material, cooperate the PMMA particle of weight average particle diameter 10 μ m (to combine the chemical company's system of grinding, trade name: MX1000) 30 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PC4-4133) 0.5 weight portion and mixing.Dilute this potpourri with solvent (cellosolve acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 35 weight %.Use above-mentioned antiglare hardcoat to form material, use the #40 rod to be coated with machine, in addition, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of present embodiment is 23 μ m.Above-mentioned PMMA particulate almost is asperratio less than 1.05.

(embodiment 7)

The operating weight mean grain size is that the PMMA particle of 10 μ m (is combined the chemical company's system of grinding, trade name: MX1000) 45 weight portions, solvent is altered to ethyl acetate, being diluted to solid component concentration is 55 weight %, use the #22 rod to be coated with machine, in addition, adopt and embodiment 3 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of present embodiment is 18 μ m.Above-mentioned PMMA particulate almost is asperratio less than 1.05.

(comparative example 1)

Use the resin raw material identical with embodiment 1.In solid constituent 100 weight portions of this resin raw material, (ponding changes into corporate system to the PMMA particle of cooperation weight average particle diameter 8 μ m, trade name: MBX8SSTN) 80 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PC-F479) 0.1 weight portion and mixing.Dilute this potpourri with solvent (ethyl acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 55 weight %.Use above-mentioned antiglare hardcoat to form material, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of this comparative example is 25 μ m.

(comparative example 2)

Use the resin raw material identical with embodiment 1.In solid constituent 100 weight portions of this resin raw material, (ponding changes into corporate system to the PMMA particle of cooperation weight average particle diameter 8 μ m, trade name: the MBX8SSTN) silicon oxide particle (SILYSIA of the Fuji corporate system of 30 weight portions, weight average particle diameter 1.4 μ m, trade name: SYLOPHOBIC 100) 10 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PC-F479) 0.1 weight portion and mixing.Dilute this potpourri with solvent (ethyl acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 55 weight %.Use above-mentioned antiglare hardcoat to form material, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of this comparative example is 25 μ m.Above-mentioned PMMA particulate almost is asperratio less than 1.05.Above-mentioned silicon oxide particle almost is asperratio more than 1.6.

(comparative example 3)

Use the resin raw material identical with embodiment 1.Solid constituent 100 weight portions at this resin raw material, (ponding changes into corporate system to the PMMA particle of cooperation weight average particle diameter 8 μ m, trade name: the MBX8SSTN) silicon oxide particle (SILYSIA of the Fuji corporate system of 30 weight portions, weight average particle diameter 2.5 μ m, trade name: SYLOPHOBIC 702) silicon oxide particle (SILICONES of the Toshiba corporate system of 15 weight portions, weight average particle diameter 4.5 μ m, trade name: TOSPEAR) 6 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PC-F479) 0.1 weight portion and mixing.Dilute this potpourri with solvent (ethyl acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 55 weight %.Use above-mentioned antiglare hardcoat to form material, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of this comparative example is 25 μ m.The silicon oxide particle of above-mentioned PMMA particulate and above-mentioned weight average particle diameter 4.5 μ m almost is asperratio less than 1.05.The silicon oxide particle of above-mentioned weight average particle diameter 1.4 μ m almost is asperratio more than 1.6.

(comparative example 4)

Use the resin raw material identical with embodiment 1.In solid constituent 100 weight portions of this resin raw material, (ponding changes into corporate system to the PMMA particle of cooperation weight average particle diameter 7.2 μ m, trade name: XX40AA) 30 weight portions and levelling agent (big Japanese ink corporate system, trade name GRANDIC PC4-4133) 0.5 weight portion and mixing.Dilute this potpourri with solvent (ethyl acetate),, modulate antiglare hardcoat thus and form material so that solid component concentration is 55 weight %.Use above-mentioned antiglare hardcoat to form material, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of this comparative example is 22 μ m.

(comparative example 5)

As resinizing firmly, use the ultraviolet curing resin of match ratio with urethane acrylate 40 weight %, polyester acrylate 40 weight %, butyl acetate 20 weight %.In this resinizes 100 weight portions firmly, silicon oxide particle (the SILYSIA of the Fuji corporate system that cooperates weight average particle diameter 1.3 μ m, trade name: SYLOPHOBIC 100) silicon oxide particle (SILYSIA of the Fuji corporate system of 6.5 weight portions, weight average particle diameter 2.5 μ m, trade name: SYLOPHOBIC 702) 7.5 weight portions, levelling agent (big Japanese ink corporate system, trade name DEFENSAMCF323) 0.5 part and Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals corporate system, trade name: Irgacure184) 5 weight portions and mixing.Dilute this potpourri with solvent (toluene),, modulate antiglare hardcoat thus and form material so that solid component concentration is 45 weight %.Use above-mentioned antiglare hardcoat to form material, utilize and the foregoing description 1 identical operations and condition, make hard-coated antiglare film.The thickness of the antiglare hardcoat of the hard-coated antiglare film of this comparative example is 3 μ m.Above-mentioned each particulate almost is asperratio more than 1.6.

(comparative example 6)

As above-mentioned particulate, the silicon oxide particle of the operating weight mean grain size 1.8 μ m (SILYSIA of Fuji corporate system, trade name: SYLOPHOBIC 200) silicon oxide particle (SILYSIA of the Fuji corporate system of 6.5 weight portions and weight average particle diameter 2.5 μ m, trade name: SYLOPHOBIC 702) 6.5 weight portions, the thickness that makes antiglare hardcoat is 8 μ m, in addition, utilize and above-mentioned comparative example 5 identical operations and condition, make hard-coated antiglare film.Above-mentioned each particulate almost is asperratio more than 1.6.

(comparative example 7)

As above-mentioned particulate, the granules of polystyrene of operating weight mean grain size 3.5 μ m (is combined the chemical company's system of grinding, trade name: SX350H) 14 weight portions, the thickness that makes antiglare hardcoat is 5 μ m, in addition, utilize and above-mentioned comparative example 5 identical operations and condition, make hard-coated antiglare film.

Estimate

Utilize following method evaluation or measure each embodiment and each comparative example in various characteristics.

(thickness of antiglare hardcoat)

Use the micrometer formula thickness meter of (strain) Mitutoyo corporate system, measure the gross thickness of hard-coated antiglare film.Deduct the thickness of transparent plastic film base material from above-mentioned gross thickness, calculate the thickness of antiglare hardcoat thus.It the results are shown in following table 1.

(turbidity)

Turbidity (mist degree) with JIS K7136 (version in 1981) is a benchmark, uses nephelometer HR300 (trade name, color technical institute system in the village) to measure turbidity.It the results are shown in following table 1.

(glossiness)

About glossiness, will take measurement of an angle is made as 60 °, is benchmark with JIS K7105 (version in 1981), and commodity in use name numeral varied-angle glossmeter UGV-5DP (Suga testing machine corporate system) measures.It the results are shown in following table 1.

(pencil hardness)

Make not form facing down of antiglare hardcoat mounting hard-coated antiglare film on glass plate.Then, to above-mentioned Antidazzle hard coating laminar surface,, measure pencil hardness according to the described pencil hardness test of JIS K-5400 (wherein, load 500g).It the results are shown in following table 1.

(arithmetic mean surface roughness Ra and average tiltangle are a)

Use bonding agent, on the face that does not form antiglare hardcoat of hard-coated antiglare film, the glass plate of applying MATSUNAMI corporate system (thick 1.3mm), use high precision fine shape measuring appliance (trade name: Surfcorder ET4000, little slope research institute corporate system), measure the surface configuration of above-mentioned antiglare hardcoat, obtain the arithmetic mean surface roughness Ra value and the average tiltangle a value of JIS B 0601 (version in 1994) record.It the results are shown in following table 1.Described high precision fine shape measuring appliance is calculated described arithmetic mean surface roughness Ra and described average slope angle θ a automatically.

(reflectivity)

By the adhesive phase that on the face that does not form antiglare hardcoat of hard-coated antiglare film, forms the about 20 μ m of the thickness black acrylic panel (thick 2.0mm, the Rayon of Mitsubishi corporate system) of fitting, make the areflexia at the described hard-coated antiglare film back side thus.For this hard-coated antiglare film, obtain the reflectivity of Antidazzle hard coating laminar surface.Described reflectivity uses trade name UV2400PC (the having 8 ° of inclination integrating spheres) spectrophotometer of Shimadzu Seisakusho Ltd.'s system, measures spectral reflectance (specular reflectance+diffuse reflectance), obtains the total reflectivity (Y value) in ° visual field, illuminant-C/2 by calculating.It the results are shown in following table 1.

(refractive index of antiglare hardcoat)

Use multi-wavelength Abbe refractometer (Atago of Co., Ltd. corporate system, trade name: the DR-M2/1550) refractive index of mensuration antiglare hardcoat.It the results are shown in following table 1.

(refractive index of particulate)

Mounting particulate on microslide drops in the refractive index titer on the particulate, and covered makes sample.With this sample of microscopic examination, the refractive index of the refractive index titer that the profile of particulate is difficult to see at the interface of itself and refractive index titer most is set at the refractive index of particulate.It the results are shown in following table 1.

(the white stain when 60 ° of vergence directions are observed)

On the face that does not form antiglare hardcoat of each hard-coated antiglare film, utilize the fit black acrylic panel (thick 1.0mm) of day eastern resin industrial group system of bonding agent, make the test film of no backside reflection thus.As shown in Figure 4, in the environment of the office that uses display usually, becoming vertical direction with the plane with respect to test film is benchmark (0 °), observes from 60 ° directions, with the white stain phenomenon of visualization, estimates this test film with following criterion.It the results are shown in following table 1.In Fig. 4,7 expression hard-coated antiglare films, 8 expression black acrylic panels.

Criterion

A: almost do not have white stain

B: white stain is arranged, but little to the influence of identification

C: white stain is arranged, but can identify the reduction of identification.

D: white stain is strong, and identification is significantly reduced

(mirroring when 60 ° are observed)

(1) on the face that does not form antiglare hardcoat of hard-coated antiglare film,, makes the test film of no backside reflection thus with bonding agent applying black acrylic panel (thick 1.0mm, day eastern resin industrial group system).

(2) be 0 ° to become vertical direction with the face of this test film,, estimate with following criterion from the reflection image that-60 ° of direction Visual Confirmations are mirrored at the object surfaces processing layer (antiglare hardcoat) that is positioned at 60 ° of directions.It the results are shown in following table 1.

A: can not recognition object.

B: contour of object is fuzzy, as seen.

C: some is fuzzy for object, as seen.

D: object is high-visible.

(weight average particle diameter of particulate)

As mentioned above, utilize the Ku Erte counting method, use has utilized the particle size distribution device (trade name: Coulter multisizer of pore electric-resistivity method, the BechmanCoulter corporate system), the resistance of electrolytic solution that is equivalent to the volume of above-mentioned particulate when measuring above-mentioned particulate by above-mentioned pore, measure the quantity and the volume of above-mentioned particulate thus, calculate the weight average particle diameter of above-mentioned particulate.It the results are shown in following table 1.

Shown in above-mentioned table 1, the hard-coated antiglare film of all embodiment all has sufficient hardness, also can effectively prevent oblique white stain, and anti-dizzy property (mirroring when 60 ° are observed) is also good.With respect to this, in the hard-coated antiglare film of all comparative examples, part or all of each condition of the thickness of antiglare hardcoat, mean grain size, arithmetic mean surface roughness Ra and average slope angle θ a departs from outside the scope of the present invention, so aspect hardness, oblique white stain and anti-dizzy property, all there is undesirable feature, can not satisfies complete characteristic.

Only otherwise depart from spirit of the present invention or principal character, the present invention can be other forms.The embodiment of Jie Shiing is illustrative to the present invention in this manual, does not have any limited significance.

Claims (15)

1. hard-coated antiglare film, wherein,

It comprises the transparent plastic film base material,

On at least one face of described transparent plastic film base material by particulate with resinize firmly and form antiglare hardcoat,

Described antiglare hardcoat has the thickness of 15～30 mu m ranges,

The weight average particle diameter of described particulate is 30～75% a scope of the thickness of described antiglare hardcoat,

In the concaveconvex shape of the described Antidazzle hard coating laminar surface that is formed by described particulate, average slope angle θ a is the scope of 1.0～2.0 degree, and the arithmetic mean surface roughness Ra of regulation is the scope of 0.12～0.30 μ m among the JIS B 0601 of version in 1994.

2. hard-coated antiglare film according to claim 1, wherein,

Described particulate is the different multiple particulate more than 2 kinds of weight average particle diameter,

At least a particulate in the described multiple particulate has the weight average particle diameter of 30～75% scope of the thickness of described antiglare hardcoat.

3. hard-coated antiglare film according to claim 1, wherein,

Described particulate be shaped as sphere.

4. hard-coated antiglare film according to claim 1, wherein,

Glossiness according to the JIS K 7105 of version in 1981 is below 60.

5. hard-coated antiglare film according to claim 1, wherein,

Described resinizing firmly comprises following (A) composition, (B) composition and (C) composition,

(A) composition: urethane acrylate and carbamate methacrylate at least a;

(B) composition: polyalcohol acrylate and polyvalent alcohol methacrylate at least a;

(C) composition: by the homopolymer that following (C1) or following (C2) form, the multipolymer that monomer forms more than 2 kinds of at least a monomer in perhaps following (C1) and following (C2), the blended polymer of perhaps described homopolymer and multipolymer by containing;

(C1): alkyl acrylate with alkyl of at least a group in hydroxyl and the acryloyl group

(C2): alkyl methacrylate with alkyl of at least a group in hydroxyl and the acryloyl group.

6. hard-coated antiglare film according to claim 1, wherein,

On described antiglare hardcoat, be formed with anti-reflection layer.

7. hard-coated antiglare film according to claim 6, wherein,

Contain hollow and spherical monox ultra micron in the described anti-reflection layer.

8. polaroid, wherein,

It possesses polariscope and the described hard-coated antiglare film of claim 1.

9. image display device, wherein,

It possesses the described hard-coated antiglare film of claim 1.

10. image display device, wherein,

It possesses the described polaroid of claim 8.

11. the manufacture method of a hard-coated antiglare film is the manufacture method that is formed with the hard-coated antiglare film of antiglare hardcoat at least one face of transparent plastic film base material, it comprises:

Preparation comprises particulate, resinize firmly and the antiglare hardcoat of solvent forms the operation of material;

At least one face at described transparent plastic film base material applies described antiglare hardcoat formation material, forms the operation of filming; With

Make described curing of coating and form the operation of antiglare hardcoat;

Described antiglare hardcoat has the thickness of 15～30 mu m ranges,

The weight average particle diameter of described particulate is 30～75% a scope of the thickness of described antiglare hardcoat,

Described solvent comprises ethyl acetate with the ratio that accounts for more than the whole 50 weight %,

In the concaveconvex shape on the surface that is formed by described particulate, average slope angle θ a is the scope of 1.0～2.0 degree, and the arithmetic mean surface roughness Ra of the JIS B 0601 of version in 1994 is the scope of 0.12～0.30 μ m.

12. the manufacture method of hard-coated antiglare film according to claim 11, wherein,

Described particulate is the different multiple particulate more than 2 kinds of weight average particle diameter,

At least a particulate of described multiple particulate has the weight average particle diameter of 30～75% scope of the thickness of described antiglare hardcoat.

13. the manufacture method of hard-coated antiglare film according to claim 11, wherein,

Described particulate be shaped as sphere.

14. the manufacture method of hard-coated antiglare film according to claim 11, wherein,

According to the glossiness according to the JIS K 7105 of version in 1981 that makes the hard-coated antiglare film that obtains is that mode below 60 forms antiglare hardcoat.

15. the manufacture method of hard-coated antiglare film according to claim 11, wherein,

Described resinizing firmly comprises following (A) composition, (B) composition and (C) composition,

(A) composition: urethane acrylate and carbamate methacrylate at least a;

(B) composition: polyalcohol acrylate and polyvalent alcohol methacrylate at least a;

(C) composition: by the homopolymer that following (C1) or following (C2) form, the multipolymer that monomer forms more than 2 kinds of at least a monomer in perhaps following (C1) and following (C2), the blended polymer of perhaps described homopolymer and multipolymer by containing;

(C1): alkyl acrylate with alkyl of at least a group in hydroxyl and the acryloyl group;

(C2): alkyl methacrylate with alkyl of at least a group in hydroxyl and the acryloyl group.

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