CN1842727A - Optical multilayer film, polarizing plate and optical product - Google Patents

Abstract

An optical multilayer film comprising a hard coat layer and a low refractive index layer of aerogel formed, in this order, directly or through a different layer on one surface of a basic material film containing transparent resin, and satisfying following expressions [1], [2] and [3], where nH is the refractive index of the hard coat layer and nL is the refractive index of the low refractive index layer. Expression [1]: nL<=1.37; Expression [2]: nH>=1.53; Expression [3]: [square root of]nH-0.2<nL<nH+0.2. The optical multilayer film is useful as the antireflection protective film of an optical member, especially as the polarizing plate protective film.

Description

Optical multilayer film, polaroid and optical goods

Technical field

The present invention relates to optical multilayer film, relate in more detail the low-index layer that can effectively the realize low light reflectivity optical multilayer film of the useful pressure such as the antireflection diaphragm as optics of lamination or polaroid protective film in addition.In addition, also relate to and adopt the polaroid with anti-reflective function of this optical multilayer film and the optical goods with this polaroid.

Background technology

Light polarizing film to liquid crystal indicator (being called LCD below) use, in order to prevent image reflection, sometimes arranges low-index layer and implements processing processing.Particularly, the light polarizing film in the LCD that locates to use in field etc., requires to give high performance anti-reflective function.Will carry out forming the low-index layer of multilayer film or monofilm here, on matrix material film surface.

As the low-index layer of multilayer film, can adopt by have the film of relative high index of refraction and the film of relative low-refraction stack gradually formation layer (for example,, referring to patent documentation 1).

About forming the method for film, can enumerate sol-gal process, vacuum vapour deposition, sputtering method, chemical gaseous phase deposition method etc., but any operation that includes high temperature or vacuum wherein, particularly when comprising the operation of matrix material under high temperature, in high-temperature process, reisn base material has the possibility that produces Deformation And Metamorphism, and the chemical characteristic of film is changed, and is difficult to form desirable antireflection film.In addition, while adopting vacuum film formation operation, in vacuum plant, owing to emitting gas from resin, therefore, the high vacuum of necessity while can not get film formation, is difficult to form the antireflection film with desired characteristic.

In addition, when forming low-index layer by 2 kinds or film of more than two kinds, because the coating operation of film must be carried out more than 2 times or 2 times, thus complex procedures, and manufacturing cost is high, and film thickness monitoring difficulty, is difficult to the problems such as light reflectivity that reach low.

Low-index layer as monofilm, at the metal oxide film that forms Multiple components with sol-gal process on glass, then pass through heat treated, make the metal oxide film phase-splitting of Multiple components, again the metal oxide film of phase-splitting is carried out to etching with hydrofluorite, utilize the etching speed official post of each phase (for example to become Porous, referring to non-patent literature 1) or at employing sol-gal process on glass, form after the composite membrane of magnesium oxide and carbon dioxide, being exposed in the fluoro-gas of high temperature further makes fluorine replace oxygen (for example,, referring to non-patent literature 2).

In addition, the low reflection resin base material of recording in patent documentation 2, it is characterized in that, at least containing a kind of above organo-silicon compound with amino organo-silicon compound, or the coating fluid that contains its hydrolysate is coated with on resin base material surface, by dry above-mentioned coating fluid, on resin base material surface, form coating film the 1st time, on the 1st coating film, forming refractive index is below 1.40 or 1.40, and surface is the silicon dioxide film of concaveconvex shape.In patent documentation 2, recorded, adopted low temperature process can form on the good whole resin base material of adaptation simultaneously.

But, the antireflection resin base material of recording in this communique, when using on liquid crystal indicator especially, sometimes, visibility (for example brightness) variation, the degradation in contrast that light and shade shows.Therefore require further to improve.

Patent documentation 1: Unexamined Patent 4-357134 communique

Patent documentation 2: JP 2002-328202 communique

Non-patent literature 1:S.P.Mukherjee etc., J.Non-Cryst.Solids, Vol.48, p177 (1982)

Non-patent literature 2:J.H.Simmons etc., J.Non-Cryst.Solids, Vol.178, p166 (1994)

Summary of the invention

The object of this invention is to provide a kind of with former optics press mold and compare, its light reflectivity is low, dazzle or reflection less, visibility is good, and while further using on liquid crystal indicator, the optical multilayer film of the excellent contrast that light and shade shows.

According to the present invention, can provide respectively:

(1) optical multilayer film, its on the face of matrix material film forming containing transparent resin, directly or by other layers, stack gradually that the low-index layer that consists of hard conating and aerogel forms, when the refractive index of hard conating is n _h, low-index layer refractive index be n _ltime, meet following formula [1], [2] and [3]:

Formula [1]: n _l≤ 1.37

Formula [2]: n _h>=1.53

Formula [3]: $\sqrt{n_H}-0.2<n_L<\sqrt{n_H}+0.2$

(2) optical multilayer film of recording in above-mentioned (1), meets the relation of following formula [4], [5] and [6]:

Wherein, the refractive index n of hard conating _hrefractive index n with low-refraction _l

Formula [4]: 1.25≤n _l≤ 1.35

Formula [5]: n _h>=1.55

Formula [6]: $\sqrt{n_H}-0.15<n_L<\sqrt{N_h}+0.15$

(3) optical multilayer film of recording in above-mentioned (1) or (2), is below 0.7% or 0.7% at the reflectivity of wavelength 550nm, at the reflectivity of wavelength 430～700nm, is below 1.5% or 1.5%;

(4) optical multilayer film that any one is recorded in above-mentioned (1)～(3), the shape of the mouth as one speaks line degree of depth of matrix material film or be highly 0.1 μ m or below 0.1 μ m;

(5) optical multilayer film that in above-mentioned (1)～(4), any one is recorded, wherein transparent resin is the resin being selected from fluoropolymer resin, celluosic resin and the vibrin with ester ring type structure.

(6) optical multilayer film that in above-mentioned (1)～(4), any one is recorded, wherein transparent resin is the fluoropolymer resin with ester ring type structure;

(7) optical multilayer film that in above-mentioned (1)～(6), any one is recorded, the antireflection diaphragm that it is optics;

(8) optical multilayer film of recording in above-mentioned (7), it is polaroid protective film;

(9) have a polaroid for anti-reflective function, it is layered polarization film on the reverse side of face of low-index layer is set on the polaroid protective film of recording in above-mentioned (8) and forms; And

(10) optical goods, wherein have the polaroid with anti-reflective function of recording in above-mentioned (9).

The effect of invention

According to the present invention, can provide that a kind of light reflectivity is low, dazzle and reflection less, visibility is good and while further using on liquid crystal indicator, the optical multilayer film that light and shade display comparison degree is good.

Accompanying drawing explanation

Fig. 1 is the layer structural section figure of optical multilayer film of the present invention.

Fig. 2 is the layer structural section figure with the polaroid of anti-reflective function of the present invention.

Fig. 3 is the layer structural section figure of the polarizing plate sticking with anti-reflective function of the present invention on liquid crystal display cells.

Fig. 4 is the layer structural section figure of the liquid crystal display cells shown in Fig. 3.

Embodiment

The transparent resin using in matrix material film as optical multilayer film of the present invention, adopts total light transmittance that 1mm is thick at more than 80% or 80% transparent resin conventionally.Kind to resin is not particularly limited; for example, can enumerate the polyolefin polymers such as fluoropolymer resin, tygon or polypropylene, polycarbonate polymer, polyester polymer, polysulfones-like polymer, polyether sulfone polymkeric substance, polystyrene base polymer, polyvinyl alcohol based polymer, acyl group modified cellulose base polymer, poly chlorine polyvinyl and the polymethacrylate polymkeric substance etc. with ester ring type structure.These polymkeric substance both can be used alone a kind, also can 2 kinds or two or more be used in combination.Wherein, the viewpoint good from the transparency, birefringence is little, the acyl group modified cellulose resins such as diacetyl cellulose, propiono cellulose, tri acetyl cellulose, bytyry cellulose; The vibrin such as polyethylene terephthalate, polybutylene terephthalate, PEN and the fluoropolymer resin with ester ring type structure are preferred; from the viewpoint of the transparency and light weight, tri acetyl cellulose, polyethylene terephthalate and the fluoropolymer resin with ester ring type structure are preferred.From the viewpoint of dimensional stability and film thickness monitoring, polyethylene terephthalate and the fluoropolymer resin with ester ring type structure are particularly preferred.

The fluoropolymer resin with ester ring type structure, its main chain and/or side chain have ester ring type structure, and wherein, from viewpoints such as physical strength and thermotolerances, it is preferred that main chain has ester ring type structure.

As ester ring type structure, can enumerate saturated alicyclic hydrocarbon structure (loop chain alkane), unsaturated lipid cyclic hydrocarbon structure (cycloolefin) etc., but from viewpoints such as physical strength and thermotolerances, loop chain alkane structure and cycloolefin structure are preferred.Wherein, loop chain alkane structure is most preferred.To forming the carbon number of ester ring type structure, be not particularly limited, but conventionally at 4～30, preferably 5～20, more preferably during the scope of 5～15, from physical strength, thermotolerance and film mouldability, reach height balance, be preferred.The ratio of the recurring unit forming containing the ester ring type structure in the polymkeric substance of ester ring type structure, can suitably select according to application target, but preferred 30 % by weight or more than 30 % by weight, more preferably 50 % by weight or more than 50 % by weight, 70 % by weight or more than 70 % by weight particularly preferably, most preferably 90 % by weight or more than 90 % by weight.When the ratio of the recurring unit that the ester ring type structure in containing the polymkeric substance of ester ring type structure forms is so large, the transparency and the thermotolerance of matrix material film increase.

As the fluoropolymer resin with ester ring type structure, concrete can enumerate (1) norbornene polymer; (2) the cyclic olefin base polymer of monocycle; (3) cyclic conjugated diene base polymer; (4) alicyclic vinyl ring type hydrocarbon polymer; And the hydrogenation thing of these polymkeric substance etc.Wherein, from the transparency and mouldability viewpoint, norbornene polymer is preferred.

As norbornene polymer, concrete can enumerate the ring opening copolymer compound that Norbornene derivative ring-opening polymerization polymer, Norbornene derivative and other monomers that can ring opening copolymer form; And the hydrogenation thing of these polymkeric substance is, the addition copolymerization compound that the addition polymer of Norbornene derivative, Norbornene derivative and other monomers that can ring opening copolymer form etc.Wherein, from transparent viewpoint, consider, the hydrogenation thing of Norbornene derivative open loop (being total to) polymkeric substance is particularly preferred.

The fluoropolymer resin with above-mentioned ester ring type structure, can from such as JP 2002-321302 communique etc. disclosed oneself know in polymkeric substance and select.

The glass transition temperature of the transparent resin using in matrix material film, preferably more than 80 ℃ or 80 ℃, more preferably 100～250 ℃ of scopes.The matrix material film consisting of the high transparent resin of glass transition temperature, does not deform or stress while at high temperature using, and permanance is good.

The molecular weight of the transparent resin using in matrix material film, be that employing cyclohexane give is solvent (toluene when fluoropolymer resin does not dissolve), measure and be converted into the weight-average molecular weight (Mw) of polyisoprene or polystyrene with gel permeation chromatography (being called for short GPC below), weight-average molecular weight is 10 conventionally, 000～100,000, preferably 25,000～80,000, more preferably 25,000～50,000.When weight-average molecular weight is during in this scope, physical strength and the processing and forming of film reach optimum condition, are preferred.

The molecular weight distribution of transparent resin (weight-average molecular weight (Mw)/number-average molecular weight (Mn)) is not particularly limited, but is generally 1.0～10.0, preferably 1.0～4.0, more preferably 1.2～3.5 scope.

The matrix material film using in optical multilayer film of the present invention also contains other adjuvants except transparent resin.As adjuvant, be not particularly limited, but can enumerate, for example inorganic particles; The stabilizing agents such as antioxidant, thermal stabilizer, light stabilizer, Weather-stable agent, ultraviolet light absorber, near infrared ray absorption; The resin such as lubricant, plastifier modifying agent; The colorants such as dye well pigment; Antistatic agent etc.These adjuvants, both can be used separately, also can 2 kinds or two or more be used in combination.Its addition can suitably be selected in the scope of not damaging the object of the invention, but relative transparent resin 100 weight portions are generally 0～5 weight portion, preferably 0～3 weight portion.

The thickness of matrix material film, from viewpoints such as physical strengths, preferably 30～300 μ m, more preferably 40～200 μ m.

In addition, preferred substrate material membrane is homogeneous film thickness, concrete, all the change of the thickness of matrix material film fabric widths 3% with interior be preferred.By making the thickness change of matrix material film in 3%, can make the adaptation of hard conating and the surface smoothness of upper stacked low-index layer thereof improve.

The shape of the mouth as one speaks line degree of depth of preferred substrate material membrane or be highly 0.1 μ m or below 0.1 μ m, more preferably 0.05 μ m or below 0.05 μ m.By making the shape of the mouth as one speaks line degree of depth of matrix material film or highly diminishing, when optical multilayer film of the present invention is used as polarizing plate protective film, shape of the mouth as one speaks line is not remarkable, and visibility is good.

Shape of the mouth as one speaks line can be measured with 3 contactless dimension surface configuration roughometers.The volatile component content of matrix material film is preferably 0.1 % by weight or below 0.1 % by weight, more preferably 0.05 % by weight or below 0.05 % by weight.When the volatile component content of matrix material film so lacks, the dimensional stability of matrix material film improves, and can reduce stacked irregular when stacked hard conating.In addition, on whole film, can form uniform low-index layer.Result is on whole face, to reach equably anti-reflection effect.

Volatile ingredient is molecular weight that in matrix material film, content is the very few material below 200 or 200, such as enumerating residual monomer or solvent etc.Volatile component content, is the amount of substance below 200 or 200 as the molecular weight containing in transparent resin, can be undertaken quantitatively by gc analysis matrix material film.

The saturated water absorption of matrix material film is 0.01 % by weight or below 0.01 % by weight preferably, more preferably 0.007 % by weight or below 0.007 % by weight.When saturated water absorption is greater than 0.01 % by weight, the adaptation of hard conating and matrix material film, and the reduction of the adaptation of hard conating and low-index layer, when long-time use, low-index layer easily produces and peels off.

The saturated water absorption of matrix material film is according to ASTM D530, and in 23 ℃ of dippings 1 week, the weight increasing by mensuration was obtained.

As matrix material film, also can use single or double to implement the matrix material film of surface modification treatment.By carrying out surface modification treatment, can improve the adaptation with hard conating.As surface modification treatment, can enumerate the processing of energy illuminated line or medicine processing etc.As energy illuminated line, process, can enumerate Corona discharge Treatment, Cement Composite Treated by Plasma, electron beam irradiation processing, ultraviolet treatment with irradiation etc.From considerations such as treatment effeciencies, Corona discharge Treatment, Cement Composite Treated by Plasma are preferred, and Corona discharge Treatment is particularly preferred.

As medicine, process preferred method, the method that can adopt is to flood in the aqueous oxidizing agent solutions such as potassium dichromate solution, the concentrated sulphuric acid, and then water fully washs.When vibrating under impregnation state, dipping effect is large.When long time treatment, there is surface dissolution, or the problem that declines of the transparency, according to the reactivity of medicine used, concentration etc., also capable of regulating processing time etc.

As the forming method of matrix material film, can enumerate solution rolling process or melt extrude the method for forming.Wherein, from reduce matrix material film, the content of volatile ingredient and thickness offset are considered, it is preferred melt extruding the method for forming.In addition, as melt extruding the method for forming, can enumerate and adopt the method for mould and blow molding method etc., but from production efficiency and the good consideration of thickness and precision, preferably adopt T-shaped die methods.

When adopt T-shaped mould melt extrude the method for forming time, the melt temperature of transparent resin in thering is the extruder of T-shaped mould, preferably high 80～180 ℃ than the glass transition temperature of transparent resin, more preferably high 100～150 ℃ than the glass transition temperature of transparent resin.When the melt temperature of extruder is too low, the insufficient flow of transparent resin, otherwise, when melt temperature is too high, resin possible deviation.

The shape of the mouth as one speaks line degree of depth of the matrix material film using for the present invention or highly reach 0.1 μ m or the method below 0.1 μ m, can enumerate following method: (1) adopts the mould of having implemented chromium plating, nickel, titanium etc. at the leading section of mould otch; (2) adopt the mould that passes through the tunicles such as formation TiN, TiAlN, TiC, CrN, DLC (diamond-like-carbon) such as PVD method (physical vapor deposition) at the inner face of mould otch; (3) adopt other the ceramic moulds of leading section thermojet at mould otch; (4) adopt the mould that carries out nitrided surface processing at the leading section of mould otch.

Described mould, because skin hardness is high, little with the friction of resin, thus in the matrix material film of gained, can prevent from sneaking into the rubbish etc. of calcination, meanwhile, the shape of the mouth as one speaks line degree of depth or highly can reach 0.1 μ m or below 0.1 μ m.

In addition, by adopting the good mould of surface accuracy, the unevenness of thickness can be reduced.The concavo-convex relevant surfaceness trickle with surface, available " average height Ra " represent, at the mould inner surface preferred 0.2 μ m or below 0.2 μ m of average height Ra of the leading section of mould otch particularly, more preferably 0.1 μ m or below 0.1 μ m.

So-called average height Ra, " the arithmetic mean height Ra " coming from according to JIS B 0601-2001 definition, concrete is that 0.8mm place obtains roughness curve by differing the high region of offset-type optical filter measuring curve at cut-off numerical value, from this roughness curve, in its average line direction, cut certain standard length, average line to the absolute value of the bias of roughness curve that cuts part from this is added up to, and asks its mean value.

As making in matrix material film the shape of the mouth as one speaks line degree of depth or highly reaching 0.1 μ m or other measures below 0.1 μ m, can enumerate to remove and be attached to material on mould otch (for example burnt shape thing or dust); Improve the release property of mould otch; Make comprehensive wettability of mould otch reach even; The dissolved oxygen content of resin particle and/or resin-oatmeal reach minimum; Polymer filter is set in melt extruder; Etc. method.

In addition, as for reducing the measure of the volatile component content of matrix material film, can enumerate (1) as transparent resin self, adopt volatile ingredient few; (2) adopt and melt extrude method of forming moulding matrix material film; (3), before shaping membrane, transparent resin used is dried in advance etc.Dry in advance, such as forms such as raw material granulations, with air drier etc., carry out.Baking temperature is preferably more than 100 ℃ or 100 ℃, and drying time is preferably more than 2 hours or 2 hours.By being dried in advance, can significantly reduce the volatile component content in film, thereby can prevent that bubble from appearring in the transparent resin of extruding.

Form the hard conating of optical multilayer film of the present invention, adopt and take the pencil hardness test shown in JIS K5600-5-4 (breadboard is glass plate), by the material of " 2H " or " 2H " above hardness, formed.As long as adopt the material with this hardness to get final product and be not particularly limited.As object lesson, can enumerate the organics such as organosilicon ketone, melamine class, epoxies, acrylic compounds, urethane acrylate class and firmly be coated with material; And the mineral-type such as silicon dioxide are coated with material firmly; Deng.Wherein, viewpoint good from bonding force, highly productive is considered, preferably uses urethane acrylate class and polyfunctional acrylic ester class to be firmly coated with material.

In the present invention, in order to obtain the optical multilayer film that light reflectivity is low and mar resistance is good, the refractive index n of hard conating _hrefractive index n with the low-index layer of lamination on it _lbetween must meet following relationship [2] and [3], and preferably meet following relationship [5] and [6].Refractive index n when hard conating _hduring less than foot formula [2], on it, the design of the low-index layer of lamination becomes difficult, and low-index layer becomes fragile.

Formula [2]: n _h>=1.53

Formula [3]: $\sqrt{n_H}-0.2<n_L<\sqrt{n_H}+0.2$

Formula [5]: n _h>=1.55

Formula [6]: $\sqrt{n_H}-0.15<n_L<\sqrt{n_H}+0.15$

In hard conating, according to hope, in order to seek refractive index adjustment, the raising of elasticity of flexure modulus, the stability of volumetric shrinkage, thermotolerance, static electricity resistance, anti-glare of hard conating etc., such as also containing the various fillers such as silicon dioxide, aluminium oxide, hydrated alumina.In addition, can also coordinate the various adjuvants such as antioxidant, ultraviolet light absorber, light stabilizer, antistatic agent, levelling agent, defoamer.

In hard conating, contain Packed occasion, when adjusting refractive index and static electricity resistance, in various fillers, from easy adjustment hard conating low-refraction and this point of static electricity resistance, consider, the tin oxide (FTO) of the tin oxide (IZO) of the indium oxide of titanium dioxide, zirconia, zinc paste, tin oxide, cerium oxide, antimony pentaoxide, doped tin (ITO), antimony dopant, adulterate plumbous zinc paste (AZO), doped with fluorine is preferred, from keeping transparent viewpoint to consider, antimony pentaoxide, ITO, IZO, ATO, FTO are preferred.The size of these filler particles, primary particle size is 1nm～100nm, preferably 30nm or below 30nm.

In hard conating, contain Packed occasion, in order to give anti-glare, preferred mean grain size 0.5～10 μ m, more preferably 1～7 μ m.As the filler object lesson of giving anti-glare, can enumerate the organic resin fillers such as plexiglass, polyvinylidene fluoride resin and other fluororesin, silicone resin, epoxy resin, nylon resin, polystyrene resin, phenolics, urethane resin, crosslinked acrylic resin, cross-linked polystyrene resin, melamine resin, benzoguanamine resin; Or the inorganic fillers such as titanium dioxide, aluminium oxide, indium oxide, zinc paste, antimony oxide, tin oxide, zirconia, ITO, magnesium fluoride, monox.

Formation method to hard conating is not particularly limited, and for example, can enumerate hard conating is formed with covering with paint, lacquer, colour wash, etc. liquid and covered with paint, lacquer, colour wash, etc. on matrix material film with known coating method, by heating or irradiation ultraviolet radiation, makes the method being solidified to form.

The thickness of hard conating is 0.5～30 μ m preferably, more preferably 3～15 μ m.When the thickness of hard conating, cross when thin, each layer of hardness forming on it can not keep, otherwise when hard conating is blocked up, the whole flexibility of optical multilayer film reduces, and solidifies and needs the time, has the danger that causes that production efficiency declines.

The low-index layer of optical multilayer film of the present invention consists of aerogel.As aerogel, the refractive index n of low-index layer _las long as meeting following relationship [1] and [3] gets final product and is not particularly limited.

Formula [1]: n _l≤ 1.37

Formula [3]: $\sqrt{n_H}-0.2<n_L<\sqrt{n_H}+0.2$

Wherein, n _hrefractive index for hard conating.

Particularly meet following relationship [4] and [6] person is preferred.

Formula [4]: 1.25≤n _l≤ 1.35

Formula [6]: $\sqrt{n_H}-0.15<n_L<\sqrt{n_H}+0.5$

The formation of low-index layer both can form by least 1 layer, can be also multilayer.When low-index layer consists of multilayer, can at least approach the hard conating refractive index n of that layer recently _lmeet above-mentioned various.

Aerogel is that tiny bubble is dispersed in matrix and the transparent porous body that forms.The size of bubble, most of at 200nm or below 200nm, the content of bubble is generally 10～60 volume %, preferably 20～40 volume %.

The aerogel object lesson disperseing as tiny bubble, can enumerate that aerosil and hollow-particle are dispersed in matrix and the porous body forming.

Aerosil, as United States Patent (USP) the 4th, 402, No. 927 communiques, United States Patent (USP) the 4th, 432, No. 956 communiques and United States Patent (USP) the 4th, 610, No. 863 communiques etc. are disclosed, the gel compound of the moisture state that the silicon dioxide skeleton that the hydrolytic-polymeric reaction by alkoxy silane obtains forms, under alcohol or carbon dioxide equal solvent (dispersion medium) exist, dry and manufacture under the supercriticality more than the critical point of this solvent.Supercritical drying, for example gel compound is immersed in liquefied carbon dioxide, the solvent containing gel compound, all or part of uses the liquefied carbon dioxide displacement lower than the critical point of this solvent, then, in the independent system of carbon dioxide or under the super critical condition of the mixed system of carbon dioxide and solvent, be dried and the supercritical drying that carries out.In addition, aerosil, as United States Patent (USP) the 5th, 137, No. 279 communiques, United States Patent (USP) the 5th, 124, No. 364 communiques etc. are disclosed, with sodium silicate, make raw material, manufacture equally with above-mentioned.

Here, as Unexamined Patent 5-279011 communique and Unexamined Patent 7-138375 communique disclosed, the gel compound that the hydrolysis of above-mentioned alkoxy silane, polyreaction are obtained, processes by hydrophobization, and giving aerosil is preferred with hydrophobicity.Therefore, the aerosil of hydrophobic property, is difficult to immerse moisture and water etc., can prevent the deteriorated of the performances such as the refractive index of aerosil or photopermeability.

This hydrophobization treatment process can be carried out before supercritical drying gel compound or in supercritical drying process.It is that the hydroxyl of the silanol group that exists on gel compound surface reacts with the functional group of hydrophobization treating agent that hydrophobization is processed, and the hydrophobic group replacement by hydrophobic treating agent reaches hydrophobization.As the method for carrying out hydrophobization processing, can enumerate and gel is immersed in to hydrophobization treating agent is dissolved in the hydrophobization treating fluid in colloidal sol, mix etc., after hydrophobization treating agent infiltrates in gel, heat as required, implement the method for hydrophobization reaction.

The solvent using in processing as hydrophobization, for example, can enumerate methyl alcohol, ethanol, isopropyl alcohol, dimethylbenzene, toluene, benzene, N, dinethylformamide, HMDO etc., but as long as hydrophobization treating agent easily dissolves, and the gel before hydrophobization is processed can with contained solvent exchange, but be not limited to these.

While carrying out supercritical drying in operation thereafter, overcritical easily dry solvent can preferably be used such as similar with methyl alcohol, ethanol, isopropyl alcohol, liquid CO 2 etc. or can be with its displacement.In addition, as hydrophobization treating agent, for example, can enumerate hexamethyldisilazane, HMDO, trimethyl methoxy silane, dimethyldimethoxysil,ne, methyltrimethoxy silane, ethyl trimethoxy silane, trimethylethoxysilane, dimethyldiethoxysilane, methyl triethoxysilane etc.The refractive index of aerosil, freely changes according to the raw material proportioning of aerosil.

Formation method when low-index layer is aerosil is not particularly limited, and for example, can enumerate, and adopts known coating method to cover with paint, lacquer, colour wash, etc. above-mentioned gel compound on hard conating, carries out above-mentioned supercritical drying and the method that forms.In addition, before supercritical drying or in supercritical drying process, carrying out hydrophobization processing also can.Supercritical drying, for example above-mentioned gel compound is immersed in liquefied carbon dioxide, the solvent containing gel compound, all or part of uses the liquefied carbon dioxide displacement lower than the critical point of this solvent, then, in the independent system of carbon dioxide or under the super critical condition of the mixed system of carbon dioxide and solvent, be dried and the supercritical drying that carries out.

As hollow-particle, be dispersed in the porous body in matrix, can enumerate JP 2001-233611 communique and JP 2003-149642 communique disclosed inner at particulate, the hollow-particle with space is dispersed in to the porous body in adhesive resin.

As adhesive resin, can be from being appropriate to hollow-particle dispersiveness, the porous body transparency, choice for use in the conditions such as resin of the conditions such as porous body intensity, for example, the vibrin that early oneself adopts, acryl resin, urethane resin, vestolit, epoxy resin, melamine resin, fluororesin, silicones, butyral resin, phenolics, vinyl acetate resin, ultraviolet curable resin, electron beam curing resin, latex resin, water soluble resin, hydrophilic resin, the potpourri of these resins, also have the coating resins such as the multipolymer of these resins and modification body, or the hydrolyzable organo-silicon compound such as alkoxy silane and hydrolysate thereof etc.

Wherein, from dispersiveness, the porous body intensity of particulate, consider, the hydrolyzable organo-silicon compound such as acryl resin, epoxy resin, urethane resin, silicones, alkoxy silane and hydrolysate thereof are preferred.

In the present invention, as low-index layer, adopt hollow-particle to be dispersed in matrix and during the porous body forming, from improving reflection characteristic and the soil resistance of low-index layer, consider, also fluororesin can be blended in above-mentioned resin.

As long as fluororesin, be non-crystallizable in fact generation light scattering amorphism fluoropolymer can and do not do any special restriction, wherein, the amorphism fluoroolefins polymkeric substance such as terpolymer of % by weight/26～44, % by weight/15～35, tetrafluoroethene/vinylidene/hexafluoropropylene=37～48 % by weight, and the polymkeric substance with fluorine-containing aliphatics ring structure, because mechanical property is good, be preferred.

The hydrolyzable organo-silicon compound such as above-mentioned alkoxy silane and hydrolysate thereof are selected more than a kind or a kind compound formation from following (a)～(c), in molecule, have-(O-Si) _m-O-(in formula, m represents natural number) chemical bond.

(a) formula (ii): use SiX ₄the compound (being called compound (ii) below) representing.

(b) at least a kind of partial hydrolysate (being called compound (ii ii) below) in above-claimed cpd (ii).

(c) at least a kind of complete hydrolyzable product (being called compound (iii) below) in above-claimed cpd (i).

In above-mentioned (a) compound (i), X represents the halogen atoms such as chlorine atom, bromine atoms; There is substituent monovalence alkyl; Oxygen atom; The organic acid such as acetate, nitrate radical; The beta-diketon acidic groups such as acetyl group acetic acid esters; The inorganic acid radical such as nitrate radical, sulfate radical; The alkoxys such as methoxyl, ethoxy, positive propoxy, n-butoxy; Or hydroxyl.

Wherein, as compound (i), with formula (i)-1:R _asiY _4-a[in formula, R indicates substituent monovalence alkyl; A represents 0～2 integer, and a is 2 o'clock, R both can be identical also can be different.Y represents hydrolyzable group, Y both can be identical also can be different] silicon compound (being called compound (i)-1 below) that represents is preferred.

As there being substituent monovalence alkyl, can enumerate the alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group; The naphthenic base such as cyclopentyl, cyclohexyl; Phenyl, 4-aminomethyl phenyl, 1-naphthyl, 2-naphthyl etc. can have substituent aryl; The alkenyl such as vinyl, allyl; The aralkyl such as benzyl, ethoxyphenyl, 3-phenylpropyl; The haloalkyl such as chloromethyl, γ-chloropropyl, 3,3,3-trifluoro propyl, methyl-3, the perfluoroalkyls such as 3,3-trifluoro propyl, 17 fluorine decyls, trifluoro propyl, ten trifluoro octyl groups; The alkenyl carbonyl oxygen base alkyl such as γ-metacryloxy propyl group; γ-glycidoxypropyl, 3,4-epoxycyclohexyl ethyl etc. has the alkyl of epoxy radicals; γ-sulfydryl propyl group etc. has the alkyl of sulfydryl; 3-aminopropyl etc. has amino alkyl; Deng.Wherein, from synthetic easiness, easily acquired, low reflection characteristic consideration, alkyl, perfluoroalkyl, the phenyl of preferred carbon number 1～4.

In above formula (i)-1, Y represents hydrolyzable group.Wherein, this hydrolyzable group means according to hope, or is hydrolyzed under acid or base catalyst existence, generate-(O-Si) _mthe group of-O-key.

As the object lesson of hydrolyzable group, can enumerate the alkoxys such as methoxyl, ethoxy, propoxyl group; The acyloxy such as acetoxyl group, propionyloxy; Oximido (O-N=C-R ' (R ")), enol oxygen base (O-C (R ')=C (R ") R ), amino, amino oxygen base (O-N (R ') R "), amide group (N (R ')-C (=O)-R ") etc.In these groups, R ', R ", R  represents respectively hydrogen atom or 1 valency alkyl independently.Wherein, as Y, from easy acquisition, considering, is preferred alkoxy.

As compound (i)-1, in formula (i)-1, the silicon compound of the integer that a is 0～2 is preferred.As its object lesson, can enumerate alkoxyl silicone alkanes, acetoxylsilane class, oximino silane class, Ethoxysilane class, amino silane class, aminooxy group silanes, amide group silanes etc.Wherein, from easy acquired consideration, alkoxyl silicone alkanes is preferred.

In formula (i)-1, the tetraalkoxysilane that is 0 as a, can enumerate tetramethoxy-silicane, tetraethoxysilane etc., the organotrialkoxysilane that is 1 as a, can enumerate methyltrimethoxy silane, methyl triethoxysilane, methyl three isopropoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane etc.In addition, organic dialkoxy silicane that a is 2, can enumerate dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxy silane etc.

Molecular weight to compound (i)-1 is not particularly limited, but preferably 40～300, and more preferably 100～200.

In compound (i), the product of at least a kind of partial hydrolysis is compound (ii), and in compound (i) at least 1 to finish fully hydrolyzed product be compound (iii), can pass through the more than a kind or a kind of compound (i), by being all or part ofly hydrolyzed, condensation obtains.

Compound (ii) and compound (iii), for example, using Si (Or) ₄the metal tetrol salt that (r represents 1 valency alkyl) represents, at mol ratio [H ₂o]/[Or] be more than 1.0 or 1.0 for example 1.0～5.0, preferably 1.0～3.0 the water yield under existing, be hydrolyzed and obtain.Hydrolysis, at the temperature of 5～100 ℃, makes all to dissolve by stirring 2～100 hours.

When compound (i) is hydrolyzed, can use as required catalyzer.Catalyzer as using, is not particularly limited, but from resulting partial hydrolystate and/or hydrolysate easily become 2 yuan of cross-linked structures, its condensation compound easily becomes porous and shortens required hydrolysis time and consider, acid catalyst is preferred.

Acid catalyst as used, is not particularly limited, and can enumerate the organic acids such as acetic acid, chloracetic acid, citric acid, benzoic acid, dimethyl malonic acid, formic acid, propionic acid, glutaric acid, glycollic acid, maleic acid, malonic acid, toluenesulfonic acid, oxalic acid; The mineral acids such as hydrochloric acid, nitric acid, halogenated silanes; The acidic sol shape fillers such as acidoid silicon dioxide, ferric oxide/titanium dioxide colloidal sol; Deng.These acid catalysts, both can be used separately, can 2 kinds or two or more be used in combination.

In addition, also can adopt the aqueous solution of the alkaline metal such as NaOH, calcium hydroxide or alkaline earth metal hydroxide, ammoniacal liquor, the base catalysts such as amine aqueous solution replace above-mentioned acid catalyst.

Molecular weight to compound (ii) and compound (iii) is not particularly limited, but conventionally its weight-average molecular weight in 200～5000 scope.

As long as hollow minute particle is mineral compound particulate, gets final product and be not particularly limited, is preferred but enclosure forms empty inorganic hollow particulate, and it is particularly preferred using silicon dioxide hollow minute particle.

As mineral compound, be generally inorganic oxide.As inorganic oxide, can enumerate SiO ₂, Al ₂o ₃, B ₂o ₃, TiO ₂, ZrO ₂, SnO ₂, Ce ₂o ₃, P ₂o ₅, Sb ₂o ₃, MoO ₃, ZnO ₂, WO ₃deng a kind or 2 kinds or two or more.As inorganic oxide of more than two kinds, can enumerate TiO ₂-Al ₂o ₃, TiO ₂-ZrO ₂, In ₂o ₃-SnO ₂, Sb ₂o ₃-SnO ₂.These can use separately a kind or use 2 kinds or combination of more than two kinds.

As inorganic hollow particulate, can use (A) inorganic oxide individual layer; (B) the composite oxides individual layer being formed by inorganic oxide not of the same race; And (C) comprise above-mentioned (A) and bilayer (B).

The shell of hollow minute particle can be the foraminate porous body of tool, can be also aperture by blocking cavity, with respect to the outside of shell, is sealed.The multilayer inorganic oxide clad that shell preferably consists of the 1st inorganic oxide clad of inner side and the 2nd inorganic oxide clad in outside.In outside, by the 2nd inorganic oxide clad is set, the aperture of shell is closed, and it is fine and close that shell becomes, and can also obtain the sealed inorganic hollow particulate of interior void.While particularly using fluorine-containing organic silicon compound in order to form the 2nd inorganic oxide clad, in order to form the clad of contain fluorine atoms, it is lower that gained particle becomes refractive index, simultaneously, dispersiveness in organic solvent, low-refraction also has the effect of the soil resistance of giving, and is preferred.Object lesson as this fluorine-containing organic silicon compound, can enumerate 3,3,3-trifluoro propyl trimethoxy silane, methyl-3,3,3-trifluoro propyl dimethoxy silane, 17 fluorine decyl methyl dimethoxysilanes, 17 fluorine decyltrichlorosilanes, 17 fluorine decyl trimethoxy silanes, trifluoro propyl trimethoxy silane, ten trifluoro octyl group trimethoxy silanes etc.

The thickness of shell is preferably 1～50nm, particularly preferred 5～20nm.When the thickness of shell is during lower than 1nm, inorganic hollow particulate can not keep the particle shape of regulation sometimes.Otherwise when the thickness of shell surpasses 50nm, the cavity in inorganic hollow particulate is little, result is that empty ratio reduces, and cannot reach low-refraction.In addition, preferred 1/50～1/5 scope of the mean grain size in inorganic hollow particulate of the thickness of shell.

As mentioned above, when the 1st inorganic oxide clad and the 2nd inorganic oxide clad being set being shell, the gross thickness of these layers reaches the scope of above-mentioned 1～50nm, the shell to densification particularly, and the scope that the thickness of the 2nd inorganic oxide clad reaches 20～40nm is preferred.

In addition, the solvent that can use when preparation inorganic hollow particulate and/or the gas immersing when dry are present in cavity, and the parent material that also can be used to form following cavity residues in cavity.

Parent material is that core grain from being surrounded by shell is except residual porous mass a coring grain constituent part.In core grain, adopt the porous composite oxide particle being formed by diverse inorganic oxide.Parent material is a small amount of residual being attached on shell sometimes, sometimes accounts for most of cavity.

Also have, in the aperture of this porous mass, also can have above-mentioned solvent or gas.Now when the removal amount of core grain constituent increases, the volume in cavity increases, and obtains the inorganic hollow particulate that refractive index is low, is combined with the resulting transparent epithelium of this inorganic hollow particulate, because of antiradar reflectivity antireflection property good.

Particle diameter to inorganic hollow particulate is not particularly limited, but the scope of 5～2,000nm is preferred, and 20～100nm is preferred.When being less than 5nm, the effect that reaches low-refraction due to hollow is little, otherwise, when being greater than 2,000nm, transparent extreme difference, the impact of scattered reflection strengthens.Here, mean grain size is the number average bead diameter with infiltration type electron microscope observation.

The manufacture method of above-mentioned inorganic hollow particulate, for example JP 2001-233611 communique oneself be documented, the method that the inorganic hollow particulate using in the present invention is recorded according to there is manufactured, but the inorganic hollow particulate that sell open market also can be used.

The use level of inorganic particles, is not particularly limited, but is preferably 10～30 % by weight with respect to whole low-index layer.When the use level of inorganic particles is during in this scope, can obtain having the optical multilayer film that low-refraction and mar resistance have both.

Above-mentioned inorganic particles also can be used with the form of dispersion liquid.The kind of the organic solvent using in dispersion liquid, is not particularly limited, and for example, can enumerate the lower aliphatic alcohols such as methyl alcohol, ethanol, isopropyl alcohol (IPA), normal butyl alcohol, isobutyl alcohol; The ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, acetic acid ethylene glycol monoethyl ether; The diglycol derivative such as diglycol, diethylene glycol monobutyl ether; Two acetone ethanol; The aromatic hydrocarbon such as toluene, dimethylbenzene; The aliphatic hydrocarbon such as normal hexane, normal heptane; The ester such as ethyl acetate, butyl acetate class; The ketones such as acetone, MEK, methylisobutylketone; Deng.These organic solvents both can be used alone, also can 2 kinds or two or more be used in combination.

When low-index layer is that hollow-particle is while being dispersed in the porous body in matrix, its formation method is not particularly limited, for example, the method is on hard conating, at least in the inner hollow minute particle thering is space of particulate, coating fluid with forming containing adhesive resin, is coated with by known coating method, implements as required dry heat and processes.The temperature heating is as required generally 50～200 ℃, preferably 80～150 ℃.

In the present invention, the thickness of low-index layer is 10～1000nm, preferably 30～500nm.As mentioned above, low-index layer at least forms by 1 layer, also can consist of multilayer.

Optical multilayer film of the present invention, as mentioned above, the refractive index n of hard conating _hrefractive index n with low-index layer _l, must meet formula [1]: n _l≤ 1.37, formula [2]: n _h>=1.53, formula [3]: $\sqrt{n_H}-0.2<n_L<\sqrt{n_H}+0.2,$ But also preferably meet formula [4]: 1.25≤n _l≤ 1.35, formula [5]: n _h>=1.55, formula [6]: $\sqrt{n_H}-0.15<n_L<\sqrt{n_H}+0.5.$ By meeting these formula, can make the optical index of optical multilayer film reduce, obtain the optical goods of visibility, mar resistance and good strength.

Optical multilayer film of the present invention, the reflectivity of optimal wavelength when 550nm is below 0.7% or 0.7%, and reflectivity when wavelength is 430～700nm is below 1.5% or 1.5%, reflectivity when more preferably wavelength is 550nm is below 0.6% or 0.6%, and the reflectivity of wavelength while being 430～700nm is below 1.4% or 1.4%.

One of layer formation of optical multilayer film of the present invention is illustrated in Fig. 1.Optical multilayer film 50 shown in Fig. 1, downside from figure, consists of matrix material rete 11, hard conating 21, low-index layer 31 and stain-proofing layer 41.

In optical multilayer film of the present invention, other layers can be set between matrix material rete 11 and hard conating 21.As other layers, can enumerate prime coat (not shown).

Prime coat forms for the cohesive of giving and improve between matrix material film and hard conating.As the material that forms prime coat, can enumerate resin, polyamide, acrylic resin, polyester resin, vinyl chloride-vinyl acetate copolymer, chlorinated rubber, the thermoprene on Amino-Polyester ethyl formate resinoid, polyether urethane resinoid, polyisocyanate esters resin, polyolefin resin, main chain with hydrocarbon skeleton and/or polybutadiene skeleton or the modifier that imports polar group in these polymkeric substance.

Wherein, the modifier of resin and the modifier of thermoprene that on main chain, have hydrocarbon skeleton and/or a polybutadiene skeleton are preferred.

As the resin on main chain with hydrocarbon skeleton and/or polybutadiene skeleton, can enumerate the resin that polybutadiene skeleton or its at least a portion have hydrogenation skeleton, polybutadiene that concrete is, hydrogenation polybutadiene, styrene butadiene styrene segmented copolymer (SBS multipolymer) with and hydrogenation thing (SEBS multipolymer) etc.Wherein, the modifier of the hydrogenation thing of styrene butadiene styrene segmented copolymer is preferred.

As the polar group importing, carboxylic acid or derivatives thereof is preferred, and concrete can enumerate the unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid; The modifier that the derivants such as the halogenide of the unsaturated carboxylic acids such as chloromaleic acid, maleimide, maleic anhydride, citraconic anhydride, acid amides, the sub-glue of acyl, acid anhydrides, ester etc. form, from the good consideration of adaptation, the modifier of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides is preferred, acrylic acid, methacrylic acid, maleic acid, maleic anhydride are preferred, and maleic acid, maleic anhydride are particularly preferred.These unsaturated carboxylic acids etc. can 2 kinds or two or more mixing use, also correctability.

Formation method to prime coat is not particularly limited, and for example, can enumerate the formation coating fluid prime coat, adopts known coating method on matrix material film, to be coated with, to form.

The thickness of prime coat is not particularly limited, and is generally 0.3～5 μ m, preferably 0.5～2 μ m.

In optical multilayer film of the present invention, in order to protect low-index layer, and improve antifouling property, on low-index layer, also can be provided with again stain-proofing layer (reference number 41 in Fig. 1).

As the material that forms stain-proofing layer, only otherwise hinder the function of low-index layer, meet as the desired performance of stain-proofing layer and can and not be particularly limited.Conventionally, the compound that has a hydrophobic group is preferred.As concrete example, can use perfluoroalkyl silane compound, Perfluoropolyether silanes compound, fluorine silicon ketonic compound.As the formation method of stain-proofing layer, according to the material forming, such as adopting the chemical vapor deposition methods such as physical vapor flop-in method, the CVD such as evaporation, sputter, wet type rubbing method etc.Thickness to stain-proofing layer is not particularly limited, but conventionally preferably 20nm or below 20nm, more preferably 1～10nm.

Optical multilayer film of the present invention, because excellent optical characteristics, light reflectivity is low, is suitable for doing the antireflection diaphragm of optics.

Antireflection diaphragm; generally in the optical devices such as the image display devices such as liquid crystal indicator, plasm display panel, EL element, cathode tube display device and touch panel, for the contrast that prevents from causing because of external light reflection, decline and the reflection of image.These antireflection diaphragms, in each optical devices, most the superiors in visual side arrange as the antireflection diaphragm of the optics forming conventionally.

Optical multilayer film of the present invention, as above-mentioned optics, is particularly preferred as polaroid protective film in liquid crystal indicator.

Polaroid with anti-reflective function of the present invention, is characterized in that, on that face that anti-reflection layer is not set of the matrix material film of optical multilayer film of the present invention, and lamination polaroid and forming.

The light polarizing film that the present invention uses, gets final product and is not particularly limited as long as have the function of polariscope.For example, can enumerate polyvinyl alcohol (PVA) (PVA) class or polyalkenes light polarizing film.

In the present invention, as the light polarizing film of using, more than degree of polarization 99.9% or 99.9% be preferred, more than 99.95% or 99.95% be preferred.Degree of polarization is to make polarizing axis carry out abreast transmitance (H when overlapping 2 light polarizing film ₀), and transmitance (H during polarizing axis vertically superposed ₉₀) respectively according to the 2 degree visual fields (illuminant-C) of JIS Z8701, with spectrophotometer, measure, according to following formula, obtain degree of polarization.Also has H ₀and H ₉₀y value for visual degree correction.

Degree of polarization (%)=[(H ₀-H ₉₀)/(H ₀+ H ₉₀)] ^1/2* 100

The manufacture method of light polarizing film, is not particularly limited.As the manufacture method of PVA class light polarizing film, can enumerate following several method: make PVA class film adsorb the method for carrying out an axle stretching after iodide ion; The method of absorption iodide ion after PVA class film one axle is stretched; The method that PVA class film absorption iodide ion and an axle stretch and carry out simultaneously; The method of carrying out an axle stretching after dichromatic dye dyeing for PVA class film; PVA class film carries out the method for adsorbing with dichromatic dye after an axle stretching; The method that PVA class film stretches and carries out simultaneously with dichromatic dye dyeing and an axle.In addition, as the manufacture method of polyalkenes light polarizing film, can enumerate with inferior known method and make in the presence of dehydration catalyst, to carry out thermal dehydration after the one axle stretching of PVA class film; After stretching, polyvinyl chloride film one axle carries out thermal dehydration under desalination acid catalyst exists.

Polaroid with anti-reflective function of the present invention, can be on that face that anti-reflection layer is not set of the matrix material film of optical multilayer film of the present invention, lamination polaroid and manufacturing.

The lamination of matrix material film and light polarizing film, can adopt the suitable bonding measures such as bonding agent or bonding agent to paste.As bonding agent or bonding agent, for example, can enumerate acrylic compounds, silicone, polyesters, polyurethanes, polyethers, rubber-like etc.Wherein, from viewpoints such as thermotolerance or the transparencys, consider, acrylic compounds is preferred.

The layer structural profile of the polaroid with anti-reflective function of the present invention is illustrated in Fig. 2.The polaroid 81 with anti-reflective function shown in Fig. 2 has following structure, on that side that low-index layer 31 is not set of the matrix material film 11 of optical multilayer film 50 of the present invention, by the layer 61 consisting of bonding agent or bonding agent, lamination light polarizing film 71.

In the polaroid with anti-reflective function of the present invention, on that face of lamination light polarizing film matrix material film not, by the layer 61 being formed by bonding agent or bonding agent, also can lamination other diaphragm (diagram is omitted).As diaphragm, by the low material constitutor of optical anisotropy, be preferred.As the low material of optical anisotropy; be not particularly limited; for example; can enumerate the fluoropolymer resin of cellulose esters such as thering is tri acetyl cellulose or ester ring type structure etc.; but from good viewpoints such as the transparency, forthright, the dimensional stabilitys of low-birefringence, the fluoropolymer resin with ester ring type structure is preferred.As the fluoropolymer resin with ester ring type structure, can enumerate with matrix material membrane portions of the present invention in the same resin recorded.As bonding agent and bonding agent, the same bonding agent or the bonding agent that in the time of can enumerating polaroid protective film and light polarizing film lamination, use.The thickness of the polaroid with anti-reflective function of the present invention, is not particularly limited, but conventionally in the scope of 60 μ m～2mm.

Optical goods of the present invention, is characterized in that, have the polaroid with anti-reflective function of the present invention.As the optical goods object lesson of the preferred polaroid with anti-reflective function of the present invention, can enumerate liquid crystal indicator, touch panel etc.

As one of the optical goods example with the polaroid with anti-reflective function of the present invention, the layer structure example with the liquid crystal display cells of the polaroid with anti-reflective function of the present invention is shown in Fig. 3.Be shown in the liquid crystal display cells 98 of Fig. 3, from down, start as order, by polaroid 91, phase difference plate 92, liquid crystal cell 93 and polaroid 81 with anti-reflective function of the present invention, formed.With the polaroid 81 of anti-reflective function, on liquid crystal cell 93, by bonding agent or bonding agent (not shown), form with the unilateral stickup of polarization.Liquid crystal cell 93, for example, as shown in Figure 4, has 2 cube electrode substrates 95 of transparency electrode 94, and respectively with facing to the state of transparency electrode 94, configuration at certain intervals, meanwhile, encloses liquid crystal 96 betwixt and make in gap.The edges at two ends of liquid crystal 96 inclosure portions seals with seal 97.

When liquid crystal display cells forms, for example, at suitable position, brightness is improved to the suitable parts that film, prism array sheet, lens array sheet, light guide plate, light diffusing sheet, back light lamp etc. configure more than 1 layer or 2 layers or 2 layers these on suitable position.

The liquid crystal form of liquid crystal 96 is not particularly limited.As liquid crystal form, for example, can enumerate TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, HAN (HybridAlignment Nematic) type, MVA (Multiple Vertical Alignment) type, IPS (In PlaneSwitching) type and OCB (Optical Compensated Bend) type etc.

In addition, the liquid crystal display cells 98 shown in Fig. 3, both can adopt apply voltage when low for obviously showing, Gao Shiwei shows slinkingly the positive normally white showing, can adopt again apply voltage when low be show slinkingly show, positive common-black type that Gao Shiwei obviously shows.

Optical goods of the present invention have the polaroid that the band reflection that reaches low light reflectivity in broad region prevents function.Therefore, while particularly using in liquid crystal indicator, visibility good (free from glare or reflected light), and the excellent contrast of light and shade demonstration.

Embodiment

Limit of the present invention illustrates embodiment limit and at length describes, but the present invention is not limited by the following example.Also have, " part " is the outer weight that all represents except as otherwise noted.

The evaluation of physical property of the present embodiment carries out by the following method.

(1) thickness of matrix material film (standard film thickness, thickness change value)

Film is respectively cut out to 100mm at length direction, the film that this is cut out, and employing contact wafer thickness meter (Ming Chan society system, RC-101), Width at film is measured every 0.48mm, usings the arithmetic mean of this measured value as standard film thickness T (μ m).Thickness change, using the thickness maximal value of said determination as T _mAX(μ m), minimum value are as T _mIN(μ m), calculates according to following formula.

Thickness change (%)=(T _mAX-T _mIN)/T * 100

(2) the volatile ingredient content (% by weight) of matrix material film

Matrix material film 200g, put into and remove the moisture of adsorption or the glass pipe type test sample that organic internal diameter is 4mm completely.Then, this container in 100 ℃ of heating 60 minutes, the gas that continuously trapping discharges from container.Then, the gas of trapping being analyzed with thermal desorption gas chromatography mass analyser (TDS-GC-MS), is that the total amount of 200 or 200 following compositions is as residual volatile ingredient using molecular weight wherein.

(3) saturated water absorption of matrix material film (% by weight)

According to ASTM D530, in 23 ℃ of dippings 1 week, by measuring weight increase, obtain.

(4) shape of the mouth as one speaks line degree of depth of matrix material film or height (μ m)

Adopt noncontact 3 dimension surface configuration roughness measuring machines (manufactures of ザイ go society), in the visual field of horizontal 5.6mm * longitudinal 4.4mm, be longitudinally divided into 480, be horizontally divided into the component of 640 * 480 liters of bucket amounts of 640 use, carry out visual inspection.

(5) refractive index of hard conating and low-index layer

(J.A.Woollam society manufactures, and M-2000U), with 55 °, 60 ° and 65 ° of mensuration wavelength 245～1000nm, incident angle, measures, and the calculated value using this measured value as initial value is as refractive index to adopt high speed light splitting ellipsometer.

(6) degree of polarization of light polarizing film

Make polarizing axis carry out abreast transmitance (H when overlapping 2 light polarizing film ₀), and the transmitance (H of polarizing axis when vertically superposed ₉₀) respectively according to the 2 degree visual fields (illuminant-C) of JIS Z8701, with spectrophotometer, measure, according to following formula, obtain degree of polarization.Also has H ₀and H ₉₀y value for visual degree correction.

Degree of polarization (%)=[(H ₀-H ₉₀)/(H ₀+ H ₉₀)] ^1/2* 100

(7) light reflectivity (%)

Any 3 places to optical multilayer film, with spectrophotometer, (Japanese light splitting society manufactures, UV, visible light near infrared spectrometer V-570), in 5 ° of incident angles, measure reflectance spectrum, obtain the light reflectivity that wavelength is 430～700nm, the light reflectivity that is 550nm wavelength, and the maximal value of the wavelength light reflectivity that is 430～700nm the light reflectivity that is 430～700nm as wavelength.

(8) visibility

The polaroid obtaining is cut into suitable size (10 inches of squares), using that face that forms low-index layer as above, polaroid (polaroid 21 of Fig. 3 upside) is installed in the liquid crystal display cells shown in Fig. 3, make liquid crystal display cells.Then, on the ラ イ ト ボ Star Network ス buying in market (trade name: ラ イ ト PVC ユ ア-7000PRO, Ha Network バ description industry society manufactures), liquid crystal display cells is installed, make simple liquid crystal panel, being shown as of liquid crystal display cells is black, from positive visual inspection panel, by following 3 grades, evaluate.

Zero: do not have completely dazzle (mean by watch sticky feeling that point excessively bright in the visual field or face produce or unconcerned stick with paste unclear, from light source, directly or indirectly irradiate glitter dazzling etc.) or reflection

△: see a small amount of dazzle or reflection

*: on whole picture, see dazzle or reflection

Also have, the liquid crystal display cells 98 shown in Fig. 3, in liquid crystal cell 93 one sides by the polaroid 81 with anti-reflective function, form by phase difference plate 92 lamination downside polaroids 91 on another side.Liquid crystal cell 93 as shown in Figure 4, on the face of transparency electrode 94 of electrode base board 95 with transparency electrode 94, form after oriented film, the electrode base board 95 with this transparency electrode 94, wherein, the relative state of 2 transparency electrodes 94 is configured at certain intervals, meanwhile, gap is enclosed liquid crystal 96 and is made betwixt.97 is seal.This liquid crystal display cells 98, by being fixed in plastic frame and fixed.

With the polaroid 81 of anti-reflective function, as shown in Figure 2, the layer 61 consisting of bonding agent or bonding agent in light polarizing film 71, at the upside laminated optical laminated film 50 of light polarizing film.

(9) contrast

The display panels of making in above-mentioned (8) is arranged in darkroom, leaves the brightness of the position in 5 °, the front that shows slinkingly while showing when obviously showing, with chroma-luminance meter (トプコン society manufactures, chroma-luminance meter BM-7), measure.Then, calculate brightness while obviously showing and the ratio (=brightness while obviously showing/show slinkingly the brightness while showing) that shows slinkingly the brightness while showing, it is spent as a comparison.Contrast is larger, and visibility is better.

The manufacture of Production Example 1 matrix material film A

The particle of norbornene polymer (trade name: ZEONOR 1420R, Japanese ゼオ Application society manufactures, 136 ℃ of glass transition temperatures, saturated water absorption is lower than 0.01 % by weight), with the air drier of circulation of air in 110 ℃ dry 4 hours.Then, this particle at the mould openings inner face that is provided with spiral-shaped polymer filter (filtering accuracy 30 μ m), with the enforcement of surface roughness Ra=0.05 μ m chromium plating, the minor axis extruder of the T-shaped mould with clothes hanger type of the wide 650mm of the edge of a knife, melt extrude in 260 ℃, obtain the matrix material film 1A of wide 600mm.The volatile ingredient content of resulting matrix material film 1A is 0.01 % by weight or below 0.01 % by weight, saturated water absorption is in 0.01 % by weight or below 0.01 % by weight.In addition, the standard thickness of this matrix material film 1A is 40 μ m, thickness change 2.3%, and the shape of the mouth as one speaks line degree of depth is 0.01 μ m.

Production Example 2 hard conatings form the manufacture with composition 1

Alcosol (solid component concentration 30% in antimony pentaoxide modification, catalyst changes into society and manufactures) in 100 weight portions UVA+UVB curable polyurethane acrylate (Cheng synthetic chemistry society manufactures, trade name: purple light UV7000B) (チ バ ガ イ キYi society manufactures for 10 weight portions, Photoepolymerizationinitiater initiater, trade name: イ Le ガ キ ユ ア 1) 0.4 weight portion, obtains ultraviolet hardening hard conating and form with composition 1.

The manufacture of Production Example 3 alkoxyl silicone solution 1

The oligomer of tetramethoxy-silicane, (コ Le コYi ト society manufactures, メ チ Le シ リ ケ mono-ト 51) mix at 47: 75 with mass ratio with methyl alcohol, preparation A liquid, in addition, water, ammoniacal liquor (ammonia 28 % by weight), methyl alcohol are mixed at 60: 1.2: 97.2 to preparation B liquid with weight ratio.

Then, A liquid is mixed with the weight ratio of 16: 17 with B liquid, obtain alkoxyl silicone solution 1.

The manufacture of Production Example 4 alkoxyl silicone solution 2

When preparation A liquid, except the oligomer of tetramethoxy-silicane is mixed with mass ratio with methyl alcohol at 47: 78, obtain alkoxyl silicone solution 2 with the same operation of Production Example 3.

The manufacture of Production Example 5 alkoxyl silicone solution 3

When preparation A liquid, outside the oligomer of tetramethoxy-silicane (コ Le コYi ト society manufactures, メ チ Le シ リ ケ mono-ト 51) is mixed with mass ratio with methyl alcohol at 47: 79, obtain alkoxyl silicone solution 3 with the same operation of Production Example 3.

Production Example 6 low-index layers form the manufacture with composition

Tetraethoxysilane 300g is mixed with ethanol 455g, toward wherein adding after 1.0 quality % aqueous citric acid solution 295g, in stirring at room 1 hour, make tetraethoxysilane hydrolysate A.

Then, 1020 parts of tetraethoxysilane hydrolysate A, (Japanese ユ ニ カYi society manufactures to have terminal-reactive dimethyl silicone oil, L-9000) 6300 parts of 0.42 part, 2700 parts of propylene glycol monomethyl ethers and isopropyl alcohols are mixed, and obtain low-index layer formation composition.

The manufacture of Production Example 7 light polarizing film

The PVA film of thickness 45 μ m (degree of polymerization 2400, saponification degree 99.9%) is carried out after pure swelling, be immersed in the mixed aqueous solution of iodine 1 % by weight and potassium iodide 3 % by weight, make above-mentioned PVA film dyeing.Then, this film immersion, in the boric acid aqueous solution of 4.5 % by weight, is stretched 5.3 times at length direction, be then immersed in the borax solution of 5 % by weight, make to stretch and reach 5.5 times of total stretching ratios at length direction.After stretching, remove the moisture on film surface, be dried in 50 ℃, make light polarizing film.The thickness of this light polarizing film is 18 μ m, and degree of polarization is 99.95%.

Embodiment 1

The two sides of the matrix material film 1A obtaining in Production Example 1, adopt high frequency vibrating motivation (コ ロ Na ジ エ ネ レ mono- mono-HV05-2, Tamtec society manufactures), output voltage is 100%, output power is 250W, diameter is the line electrode of 1.2mm, carries out 3 seconds of Corona discharge Treatment under the condition of 1.5mm between the long 240mm of electrode, working electrode, carries out surface modification, make surface tension reach 0.072N/m, obtain matrix material film 1B.

On 1 face of matrix material film 1B, the hard conating that is coated with continuously preparation in Production Example 2 with die coating machine forms with composition 1, makes the hard conating thickness after solidifying reach 5 μ m.Then, in 80 ℃, after dry 5 minutes, carry out ultraviolet ray irradiation (accumulated light 300mJ/cm ²), hard conating is formed with composition and solidify, obtain hard conating laminated film 1C.Hard conating thickness after solidifying is that 5 μ m, surfaceness are that 0.2 μ m, refractive index are 1.62.

The alkoxyl silicone solution 1 obtaining in Production Example 3, after mixing starts during through 1 minute, drop to above-mentioned high index of refraction laminated film 1C upper (longitudinally 15cm * horizontal 15cm), this laminated film 1C is put into the rotating room of rotary coating, make laminated film 1C rotation, rotary coating alkoxyl silicone solution on laminated film 1C surface.Here, in the rotating room of rotary coating, put in advance methyl alcohol and make to become methyl alcohol atmosphere, and the rotation of glass plate carried out for 10 seconds with the revolution of 700rpm.So, after rotary coating alkoxyl silicone solution, place 1 minute and 15 seconds, obtain alkoxyl silicone by the film of gelation.

Then, this gelatinous film, being flooded 5 minutes in the mass ratio curing fluid capable that mixes to form of 162: 4: 640 by water, 28% ammoniacal liquor and methyl alcohol, in room temperature maintenance liquid in 1 daytime.Gelatinous thin film dipped in 10% aqueous isopropanol of hexamethyldisilazane this maintenance, carries out hydrophobization processing again.

Then, this gel compound that carried out the film of hydrophobization processing, in isopropyl alcohol, flood, after washing, put into high pressure vessel, in high pressure vessel, be full of liquefied carbon dioxide gas, in 80 ℃, 16MPa, within 2 hours, carry out supercritical drying under condition, whereby, obtain forming on laminated film 1C surface the laminated film 1D of the silica aerogel (below be called low-index layer) of thickness 100nm.The result of refractive index of measuring the low-index layer of this laminated film is 1.33.

Then, on that face forming, use dip coated method at the low-index layer of this laminated film 1D, fluorine class surface soiling smears (manufacture of ダ イ キ Application industry society, オ プ Star one Le DSX), the solution that is diluted to 0.1 % by weight with perflexane is coated with.After coating, in 60 ℃, heat drying 1 minute, form the stain-proofing layer of thick 5nm, obtain optical multilayer film 1E (polaroid protective film).

On inchoate of low-index layer of resulting optical multilayer film 1E etc., by acrylic-based adhesives, (Sumitomo ス リYiエム society manufactures, DP-8005 Network リ ア), the light polarizing film laminating with obtaining in embodiment 7, obtains the polaroid 1F that band reflection prevents function.Adopt this polaroid to carry out optical property evaluation.Evaluation result is shown in table 1.

Embodiment 2

Except tri acetyl cellulose (TAC) film with thickness 40 μ m, (コニ カ society manufactures; trade name: KC4UX2M; Tg=120 ℃, saturated water absorption=4.5 % by weight, volatile ingredient content=6.0 % by weight; be called matrix material film 2A below) replace beyond matrix material film 1A; operate similarly to Example 1, obtain the polaroid 2F that optical multilayer film 2E (polaroid protective film) and band reflection prevent function.Hard conating refractive index is now 1.62, and the refractive index of low-index layer is 1.33.Adopt this polaroid to carry out optical property evaluation.Evaluation result is shown in table 1.

Embodiment 3

Except the polyethylene terephthalate film with thickness 50 μ m, (Japan spins society and manufactures, trade name: コ ス モ シ ヤ イ Application A4300, be called matrix material film 3A below) as beyond matrix material film, operate similarly to Example 1, obtain the polaroid 3F that optical multilayer film 3E and band reflection prevent function.Hard conating refractive index is now 1.62, and the refractive index of low-index layer is 1.33.Adopt this polaroid to carry out optical property evaluation.Evaluation result is shown in table 1.

Embodiment 4

Except the polaroid with tri acetyl cellulose film, (ポラテク ノ society manufactures; trade name: ス mono-バ mono-Ha イ コ Application ト ラ ス ト polaroid; SKN-18243T; degree of polarization 99.993%) replace beyond matrix material film 1A; operate similarly to Example 1; form hard conating and low-index layer, obtain optical multilayer film 4E.This optical multilayer film 4E lamination light polarizing film, this film is directly prevented to the polaroid of function is used, and carries out optical property evaluation as band reflection.Evaluation result is shown in table 1.

Introduce comparative example below, illustrate and difference of the present invention.

Comparative example 1

When forming low-index layer, the alkoxyl silicone solution 2 obtaining in using Production Example 4 replaces, alkoxyl silicone solution 1, operating similarly to Example 1, obtains the polaroid 5F that polaroid protective film 5E and band reflection prevent function.Hard conating refractive index is now 1.62, and the refractive index of low-index layer is 1.39.Adopt this polaroid to carry out optical property evaluation.Evaluation result is shown in table 1.

Comparative example 2

When forming low-index layer; the alkoxyl silicone solution 3 obtaining in using Production Example 5 replaces alkoxyl silicone solution 1; operate similarly to Example 1, obtain the polaroid 6F that optical laminating cuticula 6E (polaroid protective film) and band reflection prevent function.Hard conating refractive index is now 1.62, and the refractive index of low-index layer is 1.40.Adopt this polaroid to carry out optical property evaluation.Evaluation result is shown in table 1.

Comparative example 3

Except using hard conating to form with composition 2 (ultraviolet hardening high index of refraction agent; Large Japanese イン キ society manufactures, ダ イ キ ユ ア Network リ ア SD-715) as hard conating formation composition, the low-refraction that further adopts Production Example 6 to obtain forms with composition as beyond low-index layer, operate similarly to Example 1, obtain the polaroid 7F that optical multilayer film 7E and band reflection prevent function.Hard conating refractive index is now 1.52, and the refractive index of low-index layer is 1.45.Adopt this polaroid to carry out optical property evaluation.Evaluation result is shown in table 1.

Table 1

		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Comparative example 1	Comparative example 2	Comparative example 3
									Matrix material film		1A	2A	3A	4A	1A	1A	1A
The degree of depth of shape of the mouth as one speaks line or height		0.01	Below 0.01	Below 0.01	Below 0.01	0.01	0.01	0.01
									Optical multilayer film		1E	2E	3E	4E	5E	6E	7E
Hard conating formation constituent		1	1	1	1	1	1	2
									Hard conating refractive index [-]		1.62	1.62	1.62	1.62	1.62	1.62	1.52
The refractive index [-] of low-index layer		1.33	1.33	1.33	1.33	1.39	1.40	1.45
									Reflectivity [%]	Wavelength 550nm	0.54	0.55	0.56	0.55	1.35	1.52	2.6
Wavelength 430nm～700 nm	1.1	1.4	1.3	1.4	2.0	2.2	3.2
								Visibility		○	○	○	○	×	×	×
Contrast		300	280	280	300	150	100										70

As can be known from the results of Table 1, according to the present invention, containing hard conating and at least 1 layer of film formed low-index layer successively lamination being formed to optical multilayer film on the matrix material film of transparent resin, when the refractive index of this hard conating is n _h, low-index layer refractive index be n _ltime, meet the optical multilayer film (embodiment 1～3) of following formula [1], [2] and [3]:

Formula [1]: n _l≤ 1.37

Formula [2]: n _h>=1.53

Formula [3]: $\sqrt{n_H}-0.2<n_L<\sqrt{n_H}+0.2$

The light reflectivity when light reflectivity when wavelength is 550nm and wavelength are 430～700nm is little, and visibility and light and shade display comparison degree are good.

On the other hand, do not meet the optical multilayer film (comparative example 1～3) of formula [1], [2] and [3], the light reflectivity when light reflectivity when wavelength is 550nm and wavelength are 430～700nm is large, and not only visibility is poor, and light and shade display comparison degree is also poor.

产业上利用的可能性

本发明的光层压，光特性优良，光反射率低，适于用作光部 件的具有反射防止性的保。

具有该光层压的带反射防止功能的偏振片，其在一个宽区域可 达到低光反射率，用于液晶显示装置、触摸面板、电致发光显示装置等光 制品中。这些光制品的光反射率低，眩光或反射小，目视性优良。特 别是液晶显示装置，用于明暗显示的对比度更加优良。

Claims (10)

1. an optical multilayer film, it is on a face of the matrix material film that contains transparent resin, directly or the laminated film that forms of the low-index layer being formed by hard conating and aerogel by other layers successively lamination, when the refractive index of this hard conating is n _h, low-index layer refractive index be n _ltime, meet following formula [1], [2] and [3]:

Formula [1]: n _l≤ 1.37

Formula [2]: n _h>=1.53

Formula [3]: $\sqrt{n_H}-0.2<n_L<\sqrt{n_H}+0.2$

2. according to the optical multilayer film of recording in claim 1, the wherein refractive index n of hard conating _hrefractive index n with low-index layer _lmeet the relation of following formula [4], [5] and [6]:

Formula [4]: 1.25≤n _l≤ 1.35

Formula [5]: n _h>=1.55

Formula [6]: $\sqrt{n_H}-0.15<n_L<\sqrt{n_H}+0.15$

3. according to the optical multilayer film of recording in claim 1 or 2, wherein, the reflectivity of 550nm wavelength is below 0.7% or 0.7%, and the reflectivity of 430～700nm wavelength is below 1.5% or 1.5%.

4. according to the optical multilayer film of any one record in claim 1～3, wherein, the shape of the mouth as one speaks line degree of depth of matrix material film or be highly 0.1 μ m or below 0.1 μ m.

5. the optical multilayer film of recording according to any one in claim 1～4, wherein transparent resin is the resin being selected from fluoropolymer resin, celluosic resin and the vibrin with ester ring type structure.

6. the optical multilayer film of recording according to any one in claim 1～4, wherein transparent resin is the fluoropolymer resin with ester ring type structure.

7. the optical multilayer film of recording according to any one in claim 1～6, the antireflection diaphragm that it is optics.

8. according to the optical multilayer film of recording in claim 7, it is polaroid protective film.

9. a polaroid with anti-reflective function, on the reverse side of the face of the low-index layer of the polaroid protective film that it records in claim 8 is set, lamination light polarizing film forms.

10. optical goods, wherein, have the polaroid of the anti-reflective function of recording in claim 9.

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