CN102933993B - Optical film, anti-glare film, and polarizing plate - Google Patents

Abstract

Disclosed is an optical film which is configured from a resin lubricant composition that contains 100 parts by weight of an acrylic resin composition and 0.01-0.09 part by weight of a lubricant. The optical film is characterized in that the acrylic resin composition contains a transparent acrylic resin and rubber elastic particles having an average particle diameter of 10-300 nm, and the content of the rubber elastic particles is 25-45% by weight of the acrylic resin composition. An anti-glare film can be obtained by forming an anti-glare layer on the optical film. A polarizing plate or an anti-glare polarizing plate can be obtained by bonding the optical film or the anti-glare film to a polyvinyl alcohol-based polarizing film.

Description

Blooming, anti-glare film and polaroid

Technical field

The present invention relates to the blooming being suitable for the diaphragm being used as the polyethenol series polarizing coating forming polaroid; This blooming is formed the anti-glare film of antiglare layer; With the polaroid being pressed with this blooming or anti-glare film on polarizing coating upper strata.

Background technology

Centered by the component parts of liquid crystal indicator, polaroid is widely used.Polaroid usually to be pressed with the state circulation of diaphragm at least one surface layer of the polarizing coating comprising polyvinyl alcohol resin, and in being assembled into liquid crystal indicator etc.As the diaphragm of the polyethenol series polarizing coating of this polaroid of formation, use tri acetyl cellulose membrane traditionally always.But the humidity resistance of triacetyl cellulose is insufficient, the polaroid that tri acetyl cellulose membrane is used as diaphragm is reduced sometimes with the performance such as degree of polarization, tone under high wet heat condition under the high temperature conditions.

Therefore, the instead diaphragm of triacetyl cellulose, is discussing the acrylic resin using the transparency and humidity resistance excellence.Such as, JP2007-25008-A discloses following content: make the thickness of acrylic resin layer be less than 40 μm, and form the thermoplastic resin that can peel off on its two sides, the thermoplastic resin on two sides is peeled off before use, makes the diaphragm of polaroid.JP2007-41563-A discloses following content: fitted in this polyvinyl alcohol resin layer side and polyethenol series polarizing coating by the diaphragm be made up of the three-decker of acrylic resin film/polyethyleneimine: amine layer/polyvinyl alcohol resin layer, make polaroid.JP2007-52404-A discloses following content: set gradually bond layer/metal salt/diaphragm in a face of polyethenol series polarizing coating, make polaroid; And utilize acrylic resin to form this diaphragm.JP2009-25762-A discloses following content: relative to resinous principle 100 weight portion based on acrylic resin, and lubricant 0.1 ~ 1.5 weight portion that mixture is made up of slaine, makes the diaphragm of polaroid.In addition, JP2009-163216-A discloses following content: the anti-glare film be made up of the acrylic resin film with hard membrane layer in a surface layer pressure of polyethenol series polarizing coating, makes the polaroid of the visual confirmation side being configured at liquid crystal indicator; Also describe following content: from the resistance to impact of film and the viewpoint of masking, form the acrylic resin of this anti-glare film preferably containing acrylic rubber particle.

When acrylic resin is used as the blooming headed by the diaphragm of polyethenol series polarizing coating, in order to improve processability and throughput rate, improve film smoothness of the surface very important.Namely, be not limited to optics use, film to be generally winding to after fabrication on columned core and to carry out keeping with roll, if film smoothness of the surface is poor, then after the keeping scheduled period, such as can bind with the state be wound around, produce sometimes and observe in the most surface of roll film the phenomenon that being called as of depression etc. takes up (volume I Parties ま り).If produce such taking up, then this depression etc. can form defect, in fact cannot be applicable to blooming.

Therefore, in order to improve film smoothness of the surface, in above-mentioned JP2009-25762-A, disclose following content: by lubricant specifically for after slaine, relative to resinous principle 100 weight portion, lubricant 0.1 ~ 1.5 weight portion that mixture is made up of this slaine.In addition, JP2004-151573-A discloses following content: relative to resin 100 weight portion containing ester ring type structure taking norbornene resin as typical example, mixture is carried out with the ratio of inorganic particles to be 0.01 ~ 1.0 weight portion and lubricant be 0.01 ~ 1.0 weight portion, the ratio that is preferably respectively 0.1 ~ 0.8 weight portion, make film, improve film smoothness of the surface thus.About the formula disclosed in JP2004-151573-A, think: utilize inorganic particles while the formation of film surface is concavo-convex, utilize lubricant to improve slickness further, for acrylic resin, also the inorganic particles disclosed in the mixture document and lubricant, improve film smoothness of the surface.

But, when there is lubricant and improve film smoothness of the surface in the resin making formation film, produce following problem sometimes: the transparency of film is reduced, or lubricant oozes out from film and floats the material of white powder on surface.In addition, by making to there is inorganic particles in the resin of formation film, when film surface is formed concavo-convex, in the manufacturing process of film, inorganic particles is likely accumulated in manufacturing installation.Due to this reason, also worry to be blocked by device and operation is polluted and causes throughput rate to reduce.

An object of the present invention is to provide a kind of blooming, and it take acrylic resin as main body and mixture rubber elastomer particle wherein, thus improves resistance to impact and the masking of film, is difficult to generation simultaneously takes up when making roll.Another object of the present invention is to provide a kind of blooming, and it also gives this blooming ultraviolet absorption ability, is suitable as the diaphragm of polarizing coating.Another object of the present invention is to be provided in the anti-glare film these bloomings being formed with antiglare layer.In addition, another object of invention is to provide a kind of polaroid, and these bloomings or anti-glare film are fitted as diaphragm with polarizing coating by it, be still difficult to generation take up when making roll.

The present inventor finds: by taking acrylic resin as main body and the lubricant that in the acrylic resin composition of the rubber elastomer particle of mixture scheduled volume wherein, mixture is a small amount of, slickness when making film improves, therefore be difficult to take up, oozing out of lubricant can also be suppressed simultaneously, this completes the present invention.

Summary of the invention

That is, the present invention comprises following proposal.

[1] a kind of blooming, it is the blooming formed by the resin lubrication agent composition comprising acrylic resin composition 100 weight portion and lubricant 0.01 ~ 0.09 weight portion, wherein, this acrylic resin composition comprises the rubber elastomer particle that transparent acrylic resin and mean grain size are 10 ~ 300nm, and in acrylic resin composition, the content of this rubber elastomer particle is 25 ~ 45 % by weight.

[2] blooming as described in [1], wherein, lubricant is stearic acid based compound.

[3] blooming as described in [1] or [2], wherein, containing ultraviolet light absorber in resin lubrication agent composition, the transmitance of the wavelength 380nm of blooming is less than 25%.

[4] an anti-glare film, the surface of its blooming according to any one of [1] ~ [3] is formed with antiglare layer.

[5] the anti-glare film as described in [4], wherein, antiglare layer is formed by the composition comprising transparent resin 100 weight portion and particulate 3 ~ 30 weight portion, and mist degree is 5 ~ 50%, the mean grain size of described particulate is 0.5 ~ 5 μm and is 0.02 ~ 0.2 with the refringence of above-mentioned transparent resin.

[6] polaroid, it comprises polarizing coating and the blooming according to any one of [1] ~ [3], and described polarizing coating comprises polyvinyl alcohol resin, and described blooming and this polarizing coating are fitted.

[7] anti-dazzle polarizer, it comprises polarizing coating and [4] or the anti-glare film described in [5], and described polarizing coating comprises polyvinyl alcohol resin, described anti-glare film be fitted in this polarizing coating with antiglare layer opposite side.

Blooming of the present invention is in transparent acrylic resin the mixture rubber elastomer particle with predetermined mean particle diameter of scheduled volume, and a small amount of lubricant of mixture, film smoothness of the surface becomes good thus.Therefore, when film is made roll, be difficult to generation and take up, throughput rate is excellent.For transparent acrylic resin, if with rubber elastomer particle mixture ultraviolet light absorber and give ultraviolet absorption ability together with lubricant, then the diaphragm as polarizing coating is preferably.The anti-glare film defining antiglare layer at these bloomings or its surface is useful as the diaphragm of polyethenol series polarizing coating; the polaroid that these bloomings or anti-glare film fit on above-mentioned polarizing coating is difficult to generation similarly take up, throughput rate is excellent.

In addition, as another effect that the present invention produces, following effect can be enumerated: by adding rubber elastomer particle in acrylic resin, slightly formed concavo-convex on film surface, in order to improve film smoothness of the surface, the addition of lubricant can be reduced, oozing out of lubricant can be suppressed.

Embodiment

(blooming)

The blooming that blooming of the present invention is made up of the resin lubrication agent composition comprising acrylic resin composition 100 weight portion and lubricant 0.01 ~ 0.09 weight portion, this acrylic resin composition comprises the rubber elastomer particle that transparent acrylic resin and mean grain size are 10 ~ 300nm, and in acrylic resin composition, the content of this rubber elastomer particle is 25 ~ 45 % by weight.

(acrylic resin)

The polymkeric substance of acrylic resin normally based on alkyl methacrylate.Specifically, can be the homopolymer of alkyl methacrylate or employ the multipolymer of two or more alkyl methacrylate, also can be the multipolymer of the alkyl methacrylate of more than 50 % by weight and the monomer except alkyl methacrylate of less than 50 % by weight.As alkyl methacrylate, the carbon number usually using its alkyl is the material of 1 ~ 4, wherein preferably uses methyl methacrylate.

In addition, the monomer except alkyl methacrylate can be the monofunctional monomer in molecule with 1 polymerism carbon-to-carbon double bond, also can be the polyfunctional monomer in molecule with more than 2 polymerism carbon-to-carbon double bonds, particularly preferably use monofunctional monomer.As the example, the alkyl acrylate of methyl acrylate or ethyl acrylate and so on, the styrenic monomers of styrene or ring-alkylated styrenes and so on, the unsaturated nitrile etc. of vinyl cyanide or methacrylonitrile and so on can be enumerated.When using alkyl acrylate as copolymer composition, the usual carbon number of its alkyl is about 1 ~ 8.Monomer about acrylic resin forms, and with the amount of whole monomer for benchmark, alkyl methacrylate is preferably more than 70 % by weight, is more preferably more than 80 % by weight, more preferably more than 90 % by weight, and is preferably less than 99 % by weight.

This acrylic resin does not preferably have glutarimide derivant, glutaric anhydride derivant, lactonic ring structure etc.The acrylic resin with the such ring texture of glutarimide derivant, glutaric anhydride derivant or lactonic ring structure has the tendency being difficult to obtain sufficient physical strength and humidity resistance as blooming.In other words, this acrylic resin is preferably the polymkeric substance that monomer is in fact only made up of alkyl methacrylate; Or alkyl methacrylate account for monomer composition such as more than 70 % by weight, be preferably more than 90 % by weight and be this alkyl methacrylate only with the multipolymer of monomer being selected from fact alkyl acrylate, styrenic monomers and unsaturated nitrile.

(rubber elastomer particle)

The rubber elastomer particle that mixture forms acrylic resin composition in acrylic resin is the particle comprising the layer showing caoutchouc elasticity.

This rubber elastomer particle can be the particle be only made up of the layer of display caoutchouc elasticity, also can be the particle with the display layer of caoutchouc elasticity and the sandwich construction of other layer.As rubber elastomer, such as, alkene hydrocarbon system elastomeric polymer, diene series elastomeric polymer, styrenic-diene system elastocopolymer, acrylic flexible polymer etc. can be enumerated.Wherein, from the viewpoint of the skin hardness of blooming, photostability and the transparency, preferably acrylic flexible polymer is used.

Acrylic flexible polymer can be made up of the polymkeric substance based on alkyl acrylate.It can be the homopolymer of alkyl acrylate, also can be the multipolymer of the alkyl acrylate of more than 50 % by weight and the monomer in addition of less than 50 % by weight.As alkyl acrylate, the carbon number usually using its alkyl is the material of 4 ~ 8.When with monomer copolymerization except alkyl acrylate, as the example, the alkyl methacrylate of methyl methacrylate or β-dimethyl-aminoethylmethacrylate and so on can be enumerated, the styrenic monomers of styrene or ring-alkylated styrenes and so on, the monofunctional monomers such as the unsaturated nitrile of vinyl cyanide or methacrylonitrile and so on, and the alkenyl ester of the unsaturated carboxylic acid of (methyl) allyl acrylate or (methyl) methallyl acrylate and so on, two alkenyl esters of the dibasic acid of diallyl maleate and so on, the polyfunctional monomers such as the unsaturated carboxylic acid diester of the glycols of aklylene glycol two (methyl) acrylate and so on.

The rubber elastomer particle comprising acrylic flexible polymer preferably has the particle of the sandwich construction of the layer of acrylic flexible polymer.Specifically, the particle of the 3-tier architecture of the particle can enumerating 2 Rotating fields in the outside of acrylic elastomer with the polymeric layer of the hard based on alkyl methacrylate and then the polymeric layer in the inner side of acrylic elastomer with the hard based on alkyl methacrylate.About be formed in the hard that the outside of acrylic elastomer or inner side are formed polymeric layer, the example of monomer composition in polymkeric substance based on alkyl methacrylate, previous crops is that the example of the monomer composition of the polymkeric substance based on alkyl methacrylate that the example of acrylic resin is enumerated is identical with it, particularly preferably uses the monomer based on methyl methacrylate to form.The acrylic rubber elastomer particles of such sandwich construction such as can according to the method manufacture recorded in JPS55-27576-B.

In the present invention, as rubber elastomer particle, the mean grain size using wherein contained rubber elastomer layer is the particle of 10 ~ 300nm.Thus, when using bonding agent and polarizing coating to fit, the diaphragm being difficult to peel off from bond layer can be obtained.The mean grain size of this rubber elastomer particle is preferably more than 50nm and is preferably below 250nm.

The mean grain size of the rubber elastomer particle containing acrylic flexible polymer measures as follows.That is, be mixed in acrylic resin by such rubber elastomer particle and form film, if dyeed in its cross section by the aqueous solution of ruthenium-oxide, then only rubber elastomer layer is painted and substantially observe circle, and the acrylic resin of mother layer is not colored.Therefore, use microtome etc. to prepare thin slice by the film cross section of so dyeing, utilize electron microscope to observe it.Further, the rubber elastomer particle that extraction 100 is dyed randomly, after calculating each particle diameter, is counted average as mean grain size.Owing to utilizing such method to measure, the mean grain size of the rubber elastomer thus specified in the present invention is number average bead diameter.

When using outermost layer be the polymkeric substance of hard based on methyl methacrylate and wherein wrap into the rubber elastomer particle of acrylic flexible polymer, if be mixed in the acrylic resin of parent, then the outermost layer of rubber elastomer particle mixes with the acrylic resin of parent.Therefore, if to be dyeed in its cross section with oxidation nail and to utilize electron microscope to observe, then this rubber elastomer particle is viewed as the particle eliminating outermost state.Specifically, internal layer is being used to be acrylic flexible polymer, when skin is the rubber elastomer particle of 2 Rotating fields of the polymkeric substance of hard based on methyl methacrylate, the acrylic flexible polymer part of internal layer is colored and is viewed as the particle of single layer structure, in addition, at the polymkeric substance that use innermost layer is the hard based on methyl methacrylate, middle layer is acrylic flexible polymer, when outermost layer is the rubber elastomer particle of the 3-tier architecture of the polymkeric substance of hard based on methyl methacrylate, the particulate central portion of innermost layer is not colored, the particle of 2 Rotating fields that the acrylic flexible polymer part being viewed as only middle layer is colored.

With above-mentioned acrylic resin composition (total amount of transparent acrylic resin and rubber elastomer particle) for benchmark, this rubber elastomer particle with 25 ~ 45 % by weight ratio mixture.By with this ratio mixture rubber elastomer particle, the masking to film can be improved, improve the resistance to impact of blooming obtained, and then it is concavo-convex to be formed on film surface slightly, therefore shows the effect improving slickness.

(lubricant)

In the present invention, in the acrylic resin in above-mentioned explanation the rubber elastomer particle of mixture scheduled volume acrylic resin composition in a small amount of lubricant of mixture, manufacture resin lubrication agent composition, masking becomes blooming thus.As long as this lubricant used has the function improving acrylic resin film smoothness of the surface.There is if enumerate the example of the compound of such function, have stearic acid based compound, acrylic compounds, ester based compound etc.Wherein, in the present invention, stearic acid based compound is preferably used as lubricant.

Become the example of the stearic acid based compound of lubricant if enumerate, except stearic acid self, the stearate of methyl stearate or ethyl stearte, glyceryl monostearate and so on can be enumerated; Stearic amide; The Metallic stearates of odium stearate or calcium stearate, zinc stearate, lithium stearate, dolomol and so on; The 12-hydroxy stearic acid of 12-hydroxy stearic acid, 12-hydroxyl sodium stearate, 12-hydroxy stearic acid zinc, 12-hydroxy stearic acid calcium, 12-hydroxy lithium stearate, 12-hydroxy stearic acid magnesium and so on and its slaine etc.Wherein, in the present invention, preferably use stearic acid.

Relative to aforesaid propylene acid based resin composition (total of acrylic resin and rubber elastomer particle) 100 weight portions, the blend amount of lubricant is the scope of 0.01 ~ 0.09 weight portion.The preferred blend amount of lubricant is more than 0.03 weight portion relative to acrylic resin composition 100 weight portion and is below 0.07 weight portion.If be less than 0.01 weight portion relative to the blend amount of the lubricant of acrylic resin composition 100 weight portion, then cannot obtain sufficient film smoothness of the surface, easily produce and take up.On the other hand, if its blend amount is more than 0.09 weight portion, then lubricant likely can ooze out from film, or the transparency of film reduces.

As long as mixture finally forms described so far forming by the resin lubrication agent composition of rubber elastomer particle and lubricant in acrylic resin, its manufacture method is arbitrary.Such as, following method can be enumerated: first manufacture rubber elastomer particle, in the presence using the monomer polymerization of the raw material as acrylic resin, generate the acrylic resin of parent, make the acrylic resin composition containing rubber elastomer particle, and the lubricant of scheduled volume is added into wherein; By rubber elastomer particle and acrylic resin mixing, make the acrylic resin composition of predetermined composition, add the lubricant of scheduled volume wherein, and mixed by melting mixing etc.; Etc..

(ultraviolet light absorber)

The resin lubrication agent composition that the mixture in acrylic resin composition used in the present invention has a lubricant also containing ultraviolet light absorber, has ultraviolet absorption ability when making film, this film is applicable to polaroid in be preferred.That is, the two sides at liquid crystal cells is fitted with the liquid crystal panel of polaroid as main composition key element by the liquid crystal indicator being used as the main application of polaroid of the present invention, and result is enclosed in the many deteriorations because of ultraviolet of liquid crystal material in liquid crystal cells.And, the exterior light headed by sunshine is irradiated in the visual confirmation side of liquid crystal panel, side is irradiated to the light from backlight overleaf in addition, and it all comprises ultraviolet, thus gives polaroid ultraviolet absorption ability effective for the deterioration of the liquid crystal material prevented in liquid crystal cells.

The ultraviolet compound of ultraviolet light absorber to be absorbing wavelength be below 400nm.When blooming of the present invention is used as the diaphragm of polyethenol series polarizing coating; by mixture ultraviolet light absorber; can be improved the effect of permanance of the polaroid being fitted with this diaphragm on polarizing coating; and; as mentioned above, the effect that relaying configuration has the liquid crystal material in the liquid crystal cells of this polaroid can also be obtained.As ultraviolet light absorber, the known ultraviolet light absorbers such as benzophenone series ultraviolet light absorber, benzotriazole system ultraviolet light absorber, acrylic ultraviolet light absorber can be used.If enumerate concrete example, have 2,2 '-di-2-ethylhexylphosphine oxide (4-(1,1,3,3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol), 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2,4-di-t-butyl-6-(5-chlorobenzotriazole-2-base) phenol, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone etc.Among these, preferred benzotriazole system ultraviolet light absorber, such as, and 2,2 '-di-2-ethylhexylphosphine oxide (4-(1,1,3,3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol) is one of preferred ultraviolet light absorber.

About the blend amount of ultraviolet light absorber, less than 10% can be preferably in the transmitance of below the wavelength 370nm of blooming, be more preferably in the scope of less than 5%, more preferably less than 2% and select.In addition, also the transmitance of the wavelength 380nm of preferred blooming be less than 25% so that be less than 15%, be especially the mode mixture ultraviolet light absorber of less than 7%.As long as the mode meeting condition shown here with the transmitance of blooming decides the blend amount of ultraviolet light absorber, specifically, such as, relative to aforesaid propylene acid based resin composition (total of acrylic resin and rubber elastomer particle) 100 weight portions, preferably decide the blend amount of ultraviolet light absorber in the mode meeting above-mentioned transmitance from the scope about 0.1 ~ 2.5 weight portion, especially about 0.5 ~ 2 weight portion.As the method containing ultraviolet light absorber, following method can be enumerated: be compounded in acrylic resin by ultraviolet light absorber in advance and make particle in advance, utilize and to melt extrude its film forming etc.; Directly ultraviolet light absorber is added when melt extruding shaping; Etc., arbitrary method can be used.

(optional member of resin combination)

For mixture in acrylic resin have the resin lubrication agent composition of rubber elastomer particle and lubricant or further mixture have for the composition of ultraviolet light absorber, as required, the various adjuvants such as fluorescer, spreading agent, thermal stabilizer, light stabilizer, infrared absorbent, antistatic agent, antioxidant can also be contained.

The ultrared compound of infrared absorbent to be absorbing wavelength be more than 800nm.Such as, nitroso compound, its metallic complex salt, flower cyanines based compound, the sour based compound in side, mercaptan nickel complex salt based compound, phthalocyanine based compound, naphthalene phthalocyanine based compound, triarylmethane based compound, imonium based compound, diimmonium based compound, naphthoquinones based compound, anthraquinone based compound, amino-compound, ammonium salt based compound, carbon black, tin indium oxide, antimony tin, the 4A race belonging to the periodic table of elements, the oxide of metal of 5A race or 6A race, carbonide or boride etc. can be enumerated.These infrared absorbents preferably can absorb the way selection of whole infrared ray (light of the scope of wavelength about 800 ~ 1100nm), also can share two or more.About the blend amount of infrared absorbent, such as, the mode that can be less than 10% with the light penetration of more than the wavelength 800nm of blooming is suitable for adjustment.

(other explanation about blooming)

Form acrylic resin composition its glass transition temperature Tg preferred of blooming of the present invention in the scope of 80 ~ 120 DEG C.In addition, the hardness on surface when said composition is preferably moulded as film is high, specifically, the pencil hardness measured with load 500g according to JIS K 5600-5-4:1999 " coating ordinary test method-5: engineering properties-Section 4 of film: scratch hardness (pencil method) " is preferably H or harder than H.

In addition, from the viewpoint of the flexibility of blooming, the modulus of elasticity in static bending that said composition preferably measures according to JIS K 7171:2008 " the asking method of plastics-flexural property " is below 1500MPa.This modulus of elasticity in static bending is more preferably below 1300MPa, more preferably below 1200MPa.This modulus of elasticity in static bending because of the acrylic resin in acrylic resin composition and rubber elastomer particle kind and amount etc. and change, such as, the content of rubber elastomer particle is more, then general bending elastic modulus is less.In addition, as acrylic resin, compared with using the homopolymer of alkyl methacrylate, when using the multipolymer of alkyl methacrylate and alkyl acrylate etc., general bending elastic modulus diminishes.On the other hand, as rubber elastomer particle, with the acrylic flexible polymer Particle Phase ratio using above-mentioned 3-tier architecture, when using the acrylic flexible polymer particle of above-mentioned 2 Rotating fields, general bending elastic modulus diminishes, and when using the acrylic flexible polymer particle of single layer structure, the modulus of elasticity in static bending diminishes further.In addition, the mean grain size of rubber elastomer particle elastomer is less or elastomeric amount is more, and general bending elastic modulus is less.Therefore, as long as adjust kind and the amount of acrylic resin and rubber elastomer particle in described predetermined scope, the modulus of elasticity in static bending is made to be below 1500MPa.

As mentioned above, blooming of the present invention is by the resin lubrication agent composition of the rubber elastomer particle of mixture scheduled volume in acrylic resin and then a small amount of lubricant of mixture, preferred further mixture ultraviolet light absorber and being formed in addition, can also be formed the layer that formed by this resin lubrication agent composition sandwich construction as a layer.When blooming is made sandwich construction, about the layer that can exist beyond the layer formed by above-mentioned resin lubrication agent composition, its composition is not particularly limited, such as, can be not containing the acrylic resin of rubber elastomer particle or the layer of its composition, also can be the layer that the composition of extraneous rubber elastomer particle and the acrylic resin specified in the present invention by content or mean grain size is formed.Typically be 2 layers or 3-tier architecture, such as, the 3-tier architecture etc. that the layer can enumerating the resin lubrication agent composition that the layer of 2 Rotating fields that the layer of the resin lubrication agent composition specified by the present invention/ forms containing the acrylic resin of rubber elastomer particle or the layer of its composition or the resin lubrication agent composition specified by the present invention/ specifies containing the acrylic resin of rubber elastomer particle or layer/the present invention of its composition is formed.When the blooming of sandwich construction being fitted to polarizing coating and makes polaroid, as long as the layer formed by the resin lubrication agent composition specified by the present invention is as the binding face with polarizing coating.

In addition, when blooming is made sandwich construction, the content in each layer of rubber elastomer particle and described adjuvant can be made mutually different.Such as, following structure can also be adopted: the layer not containing ultraviolet light absorber and infrared absorbent holds layer containing ultraviolet light absorber and/or infrared absorbent and lamination.In addition, the content of the ultraviolet light absorber in the layer that the resin lubrication agent composition specified by the present invention can be made to form is higher than the content of the ultraviolet light absorber in the layer be made up of the acrylic resin not containing rubber elastomer particle or its composition, thus, the tone of polaroid can not be made to worsen, effectively can block ultraviolet, the reduction of degree of polarization when can prevent Long-Time Service.

Blooming of the present invention can be manufactured by following manner: by the resin lubrication agent composition masking of the resin lubrication agent composition of the rubber elastomer particle of mixture scheduled volume in acrylic resin described above and then a small amount of lubricant of mixture or mixture ultraviolet light absorber further, manufacture blooming of the present invention thus.When this blooming is used as the diaphragm of polyethenol series polarizing coating, its thickness at random can be selected the scope of about 5 ~ 200 μm usually.Its thickness be preferably more than 10 μm and be preferably less than 150 μm, be more preferably less than 100 μm.

Masking preferably adopts following method: melt extruded by resin lubrication agent composition illustrated up to now, be filmed with the state sandwiched with two metal rollers.In this situation, metal roller is preferably mirror roller, thereby, it is possible to obtain the blooming of surface smoothness excellence.When manufacturing blooming with sandwich construction, as long as resin lubrication agent composition the present invention specified carries out multi-layer co-extruded and masking together with other acrylic resin or its composition.

(function to blooming can add arbitrarily)

The viewpoint of the galled spots from the assembling procedure preventing Liquid crystal module, can implement dura mater process to blooming.In addition, the surface treatments such as electrostatic prevention process can also be implemented.Wherein, when forming polaroid when blooming of the present invention is used as the diaphragm of polarizing coating; electrostatic-proof function, except can giving by implementing surface treatment to above-mentioned blooming, can also assemble the other parts imparting of the polaroid of this blooming to adhesive phase etc.As the surface treatment to blooming, in addition, antireflection process and antifouling process etc. can also be enumerated.In addition, from improve visual confirmatory, prevent exterior light the interference of mirroring, reducing prismatic lens and colored filter caused by the viewpoint such as interference line, can also non-glare treated be implemented.Make the form of anti-glare film about implementing non-glare treated, change project is described, and herein for other functional layer, is described successively.

(hard membrane layer)

Hard membrane layer has the function of skin hardness improving blooming, and it is arranged to prevent the scratch on surface etc.Hard membrane layer preferably demonstrates the value of 2H or harder in the pencil hardness test (be positioned on glass plate by the blooming being formed with hard membrane layer and measure) of JIS K 5600-5-4:1999 " coating ordinary test method-5: engineering properties-Section 4 of film: scratch hardness (pencil method) " defined.The material forming this hard membrane layer generally solidifies because of heat or light.Such as, the inorganic dura mater materials such as organic dura mater material such as organic silicone system, melamine series, epoxy, acrylic acid series, urethane acrylate system and silicon dioxide can be used.Among these, the bonding force due to the acrylic resin film for base material is good and throughput rate is excellent, thus optimization polyurethane acrylic ester and polyfunctional acrylic ester system dura mater material.

According to expectation, in order to realize the raising of the adjustment of refractive index, the raising of the modulus of elasticity in static bending, the stabilization of volumetric shrinkage and thermotolerance, static electricity resistance, anti-glare etc., hard membrane layer can contain various filler.In addition, hard membrane layer can also contain the adjuvants such as antioxidant, ultraviolet light absorber, light stabilizer, antistatic agent, levelling agent, defoamer.

(antistatic backing)

Impact that antistatic backing is surface conductivity in order to give film, suppress electrostatic to produce etc. and arranging.The formation of antistatic backing such as can adopt the method for the resin combination of coating containing conductive material (antistatic agent).Such as, by making antistatic agent coexist with the dura mater material for the formation of above-mentioned hard membrane layer, the hard membrane layer of static electricity resistance can be formed.

(anti-reflection layer)

Anti-reflection layer is the layer of the reflection for preventing exterior light, and it directly or be arranged at the surface (being exposed to outside face) of blooming across other layers such as hard membrane layers.The blooming being provided with anti-reflection layer preferably for the light of wavelength 430 ~ 700nm with the reflectivity of incident angle 5 ° for less than 2%, the especially preferred light for wavelength 550nm with the reflectivity of identical incident angle for less than 1%.

The thickness of anti-reflection layer can be about 0.01 ~ 1 μm, is more preferably the scope of 0.02 ~ 0.5 μm.Anti-reflection layer can be provided with by refractive index ratio the layer that the refractive index of its layer (blooming or the hard membrane layer etc.) low-index layer of refractive index that is little, that specifically have 1.30 ~ 1.45 forms; The high refractive index layer of the low-index layer comprising the film of mineral compound and the film comprising mineral compound alternately laminated multilayer and the layer that obtains; Etc..

As long as the material refractive index forming above-mentioned low-index layer is little, be not particularly limited.

Such as, the resin material of ultra-violet solidified acrylic resin and so on can be enumerated, in resin the inorganic particles of dispersoid silicon dioxide and so on hybrid material, comprise the sol-gel material etc. of alkoxy silane.Such low-index layer can be formed by being coated with the polymkeric substance that be polymerized, and also by using as the monomer of precursor or the state coating of oligomer, can make its polymerizing curable afterwards and formed.In addition, in order to give soil resistance, each material preferably comprises in molecule the compound with fluorine atom.

As the sol-gel material for the formation of low-index layer, be suitable for using in molecule the material with fluorine atom.If enumerate in molecule the representative instance of the sol-gel material with fluorine atom, there is poly-alkoxysilane.Poly-alkoxysilane can be such as the compound that formula represents:

CF ₃(CF ₂) _nCH ₂CH ₂Si(OR) ₃

Herein, R represents that carbon number is the alkyl of 1 ~ 5, and n represents the integer of 0 ~ 12.Wherein, the n in preferred above-mentioned formula is the compound of 2 ~ 6.

As poly-alkoxysilane, specifically, following compound can be enumerated.

3,3,3-trifluoro propyl trimethoxy silane,

3,3,3-trifluoro propyl triethoxysilane,

3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl group trimethoxy silane,

3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyltri-ethoxysilane,

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine decyl trimethoxy silane,

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine decyl triethoxysilane etc.

Low-index layer can also be made up of the solidfied material of Thermocurable fluorochemicals or ionizing radiation curable fluorochemicals.This solidfied material preferably its kinetic friction coefficient is the scope of 0.03 ~ 0.15, is preferably the scope of 90 ~ 120 ° for the contact angle of water.As curable fluorine-containing compound, except the silane compound (such as, above-mentioned 3,3,4,4,5 containing poly-fluoroalkyl, 5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine decyl triethoxysilane etc.) beyond, the fluoropolymer with cross-linking functional group can also be enumerated.

The fluoropolymer with cross-linking functional group can be manufactured by following method: make fluorochemical monomer and the method for monomer copolymerization with cross-linking functional group; Or, make fluorochemical monomer and the monomer copolymerization with functional group, then the functional group in polymkeric substance added to the method for the compound with cross-linking functional group.

As fluorochemical monomer used herein, such as, fluorothene, vinylidene fluoride, tetrafluoroethene, hexafluoropropylene, perfluor-2 can be enumerated, the fluoroolefins hydro carbons of 2-dimethyl-1,3-bis-oxazole and so on and (methyl) acrylic acid partially or completely fluorinated alkyl ester derivant class, wholly or in part fluorinated vinyl ethers etc.

As there is the monomer of cross-linking functional group or there is the compound of cross-linking functional group, the monomer with glycidyl of glycidyl acrylate or glycidyl methacrylate and so on can be enumerated; The monomer with carboxyl of acrylic or methacrylic acid and so on; The monomer with hydroxyl of hydroxyalkyl acrylates or haloalkylacrylates and so on; The monomer with alkenyl of allyl acrylate or allyl methacrylate and so on; There is amino monomer; There is sulfonic monomer; Etc..

From the aspect that can improve scratch resistance, the material for the formation of low-index layer can be comprise the material that the mineral compound microparticulate such as silicon dioxide, aluminium oxide, titania, zirconia, magnesium fluoride form colloidal sol in alcoholic solvent.From the viewpoint of antireflection, the refractive index for this mineral compound particulate used is more little more preferred.This mineral compound particulate can be the particulate with space, particularly preferably the hollow minute particle of silicon dioxide.The mean grain size of hollow minute particle is preferably the scope of 5 ~ 2000nm, is especially more preferably the scope of 20 ~ 100nm.Said mean grain size utilizes the number average bead diameter calculated by transmission electron microscope observation herein.

(stain-proofing layer)

Stain-proofing layer is arranged to give water proofing property, grease proofness, absorption of perspiration, soil resistance etc.Preferred material for the formation of stain-proofing layer is fluorinated organic compound.As fluorinated organic compound, fluorocarbon, perfluor silane, their macromolecular compound etc. can be enumerated.According to formed material, the formation method of stain-proofing layer can use with evaporation or the physical vaporous deposition, chemical vapour deposition technique, wet coating method etc. that are sputtered to typical example.The average thickness of stain-proofing layer is generally about 1 ~ 50nm, is preferably 3 ~ 35nm.

(anti-glare film)

Antiglare layer can be formed on its surface by the resin lubrication agent composition of the rubber elastomer particle of mixture scheduled volume in acrylic resin and then a small amount of lubricant of mixture or the blooming of the present invention that formed by the resin lubrication agent composition of further mixture ultraviolet light absorber, thus make anti-glare film.That is, anti-glare film is made up of blooming and the antiglare layer with the fine surface unevenness profile being formed at its surface.Antiglare layer is the layer that surface has fine concaveconvex shape, is preferably formed by above-mentioned dura mater material.

The antiglare layer that surface has fine concaveconvex shape can be formed by following method: form the film containing organic fine particles or inorganic particles on the surface of blooming, and what arrange based on this particulate is concavo-convex; Formed containing or not containing the film of organic fine particles or inorganic particles after, pressing surface imparts the roller of concaveconvex shape and transfer printing concaveconvex shape (also referred to as embossing method); Etc..As the method forming above-mentioned film, such as, the method for the coating fluid that the composition that can be illustrated in the surperficial particulate being coated with by mixture in the transparent resin of curability organic or inorganic of blooming is formed.

(particulate)

In order to form antiglare layer and mixture particulate when, this particulate preferably uses mean grain size to be 0.5 ~ 5 μm and is the particulate of 0.02 ~ 0.2 with the refringence of transparent resin.By use mean grain size and with the refringence of transparent resin at the particulate of this scope, effectively can show mist degree.The mean grain size of this particulate can be obtained by dynamic light scattering method etc.In this instructions, the mean grain size of particulate directly uses the value obtained from manufacturer.This mean grain size is weight average particle diameter.

As the inorganic particles for the formation of antiglare layer, silicon dioxide, cataloid, aluminium oxide, alumina sol, alumina silicate, alumina silica composite oxides, porcelain earth, talcum, mica, calcium carbonate, calcium phosphate etc. can be used.In addition, as organic fine particles, general use resin particle, such as, can enumerate crosslinked polypropylene granulates, methyl methacrylate/styrene copolymer resin particle, crosslinked polystyrene particle, crosslinked polymethylmethacrylaparticles particle, silicone resin particle, polyimide particles etc.

(transparent resin for the formation of antiglare layer)

Preferably select from the material forming high rigidity (dura mater) for making the transparent resin of inorganic particles or organic fine particles dispersion.As this transparent resin, light-cured resin, heat-curing resin, electron ray curing resin etc. can be used, from the viewpoint such as throughput rate and the hardness of tunicle that obtains, preferably use light-cured resin.As light-cured resin, generally use polyfunctional acrylic ester.If enumerate the example, have two of trimethylolpropane or triacrylate, three or tetraacrylate of pentaerythrite, the multifunctional urethane acrylate etc. as the reaction product of the acrylate and diisocyanate in molecule with at least 1 hydroxyl.These polyfunctional acrylic esters can individually use or two or more be combinationally used as required.

In addition, multifunctional urethane acrylate, polyvalent alcohol (methyl) acrylate and the potpourri with (methyl) acrylate copolymer of alkyl comprising more than 2 hydroxyls can also be made light-cured resin.The multifunctional urethane acrylate forming this light-cured resin such as uses (methyl) acrylic acid and/or (methyl) acrylate, polyvalent alcohol and diisocyanate to manufacture.Specifically, hydroxyl (methyl) acrylate with at least 1 hydroxyl is prepared in molecule by (methyl) acrylic acid and/or (methyl) acrylate and polyvalent alcohol, and make itself and di-isocyanate reaction, thus multifunctional urethane acrylate can be manufactured.The light-cured resin self enumerated before the multifunctional urethane acrylate of manufacture like this also becomes.When it manufactures, (methyl) acrylic acid and/or (methyl) acrylate can use a kind respectively, also two or more can be combinationally used, polyvalent alcohol and diisocyanate can use a kind similarly respectively, also two or more can be combinationally used.

(methyl) acrylate as one of the raw material of multifunctional urethane acrylate can be (methyl) acrylic acid chain or cyclic alkyl ester.As its concrete example, (methyl) acrylate base ester of (methyl) alkyl acrylate and (methyl) cyclohexyl acrylate and so on of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate and so on can be enumerated.

Polyvalent alcohol as the another kind of raw material of multifunctional urethane acrylate is the compound in molecule with at least 2 hydroxyls.Such as, ethylene glycol can be enumerated, propylene glycol, 1, ammediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 1, 6-hexanediol, 1, 9-nonanediol, 1, 10-decanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, the DOPCP of 3-hydroxypivalic acid, hydroxymethyl-cyclohexane, 1, 4-cyclohexanediol, spiral shell glycol, dihydroxymethyl tristane, hydrogenated bisphenol A, ethyleneoxide addition bisphenol-A, epoxypropane addition bisphenol-A, trimethylolethane, trimethylolpropane, glycerine, 3-methylpentane-1, 3, 5-triol, pentaerythrite, dipentaerythritol, tripentaerythritol, glucose etc.

Diisocyanate as the another kind of raw material of multifunctional urethane acrylate is the compound in molecule with 2 isocyanato-bases (-NCO), can use the various diisocyanate of aromatic series, aliphatics or ester ring type.As concrete example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2 can be enumerated, 4-toluene diisocyanate, 4,4 '-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3 '-dimethyl-4,4 '-diphenyl diisocyanate, Xylene Diisocyanate, trimethyl hexamethylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate and there is among these core hydride etc. of diisocyanate of aromatic rings.

Together with multifunctional urethane acrylate, polyvalent alcohol (methyl) acrylate forming above-mentioned light-cured resin is (methyl) acrylate of the compound (that is, polyvalent alcohol) in molecule with at least 2 hydroxyls.As its concrete example, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate etc. can be enumerated.These polyvalent alcohols (methyl) acrylate can individually use, and also can combinationally use.Polyvalent alcohol (methyl) acrylate preferably comprises pentaerythritol triacrylate and/or tetramethylol methane tetraacrylate.

In addition, with these multifunctional urethane acrylates together with polyvalent alcohol (methyl) acrylate, (methyl) acrylate copolymer with the alkyl comprising more than 2 hydroxyls forming light-cured resin has the alkyl comprising more than 2 hydroxyls in a Component units.Such as, can enumerate and comprise (methyl) acrylic acid 2,3-dihydroxy propyl ester is as the polymkeric substance of Component units and comprise the polymkeric substance etc. of (methyl) acrylic acid 2-hydroxy methacrylate as Component units together with (methyl) acrylic acid 2,3-dihydroxy propyl ester.

Above, by using the light-cured resin of illustrated acrylic acid series, can obtain a kind of anti-glare film, the adaptation of itself and blooming improves, and physical strength improves simultaneously, effectively can prevent the damage on surface.

(Photoepolymerizationinitiater initiater)

Such light-cured resin and Photoepolymerizationinitiater initiater combine, and are made into Photocurable resin composition.Photoepolymerizationinitiater initiater comprises the various Photoepolymerizationinitiater initiaters such as acetophenone system, benzophenone series, benzoin ether system, amine system, phosphine oxide system.The example of the compound of acetophenone system Photoepolymerizationinitiater initiater is categorized into if enumerate, have 2,2-dimethoxy-2-phenyl acetophenone (another name benzil dimethyl ketal), 2,2-diethoxy acetophenones, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino-1-(4-methylphenyl-sulfanyl) propane-1-ketone etc.Be categorized into the example of the compound of benzophenone series Photoepolymerizationinitiater initiater if enumerate, have benzophenone, 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone etc.Be categorized into the example of the compound of benzoin ether system Photoepolymerizationinitiater initiater if enumerate, have benzoin methylether, benzoin propyl ether etc.Be categorized into the example of the compound of amine system Photoepolymerizationinitiater initiater if enumerate, have N, N, N ', N '-tetramethyl-4,4 '-diaminobenzophenone (another name Michler's keton) etc.If enumerate the example of phosphine oxide system Photoepolymerizationinitiater initiater, there is TMDPO etc.In addition, as Photoepolymerizationinitiater initiater also known xanthone based compound or thioxanthones based compound etc.

These Photoepolymerizationinitiater initiaters are commercially available.If enumerate the example of representational commercially available product with trade name, there are " IRGACURE 907 " and " IRGACURE 184 " of vapour bar Company of Switzerland, " the Lucirin TPO " of BASF AG's sale of Germany etc.

(mixture is to other composition in Photocurable resin composition)

Solvent is added as required in Photocurable resin composition.In this situation, such as, ethyl acetate, butyl acetate etc. can be used can to dissolve the arbitrary organic solvent of each composition forming composition.Certainly, can also by used in combination for organic solvent of more than two kinds.

In addition, Photocurable resin composition also containing levelling agent, such as, can enumerate the levelling agent of fluorine system or silicone-based.The levelling agent of silicone-based comprises reactive silicone, dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, poly-methyl alkyl siloxane etc.In silicone-based levelling agent, preferred reactive silicone and siloxane-based levelling agent.If use the levelling agent be made up of reactive silicone, then can give hard membrane layer surface smoothness, excellent mar resistance can be made to continue for a long time.In addition, if use siloxane-based levelling agent, then film mouldability can be improved.

(formation of antiglare layer)

When using above-mentioned light-cured resin in the formation of antiglare layer, dispersed inorganic or organically after particulate in each composition of Photocurable resin composition forming above-mentioned explanation, this resin combination is coated on blooming, and irradiate light, can be formed in thus in transparent resin and disperse fine-grained hard membrane layer (antiglare layer).

On the other hand, when utilizing the formation of embossing method to have the antiglare layer of fine surface unevenness profile, as long as use the metal die being formed with micro concavo-convex shape, by the shape transfer of metal die to the resin bed be formed on blooming.When utilizing embossing method to form fine surface unevenness profile, the resin bed transferred with concaveconvex shape can contain inorganic or organic particulate, also can not contain inorganic or organic particulate.The transfer printing of the concaveconvex shape of embossing method is utilized preferably to adopt the UV embossing method using uv curing resin.

In UV embossing method, form uv curing resin layer on the surface of blooming, this uv curing resin layer is pressed into the male and fomale(M&F) of metal die while make it solidify, thus the male and fomale(M&F) of metal die is transferred to uv curing resin layer.Specifically, coated UV line curable resin on blooming, make be coated with uv curing resin with the state closely sealed with the male and fomale(M&F) of metal die, from blooming side irradiation ultraviolet radiation, uv curing resin is solidified, then, peel off the blooming being formed with the uv curing resin layer after solidification from metal die, thus by the shape transfer of metal die to uv curing resin.The kind of uv curing resin is not particularly limited, above-mentioned various uv curing resin can be used.In addition, also can be suitable for selective light polymerization initiator to replace uv curing resin, thus can use and can utilize the visible ray longer than ultraviolet wavelength and the visible-light curing resin solidified.

The thickness of antiglare layer is not particularly limited, is generally more than 2 μm and less than 30 μm, preferably more than 3 μm, and is preferably less than 20 μm.If the thickness of antiglare layer is less than 2 μm, then cannot obtain sufficient hardness, surface has the vulnerable tendency of appearance, in addition, if thicker than 30 μm, then there is following tendency: easily break, or anti-glare film is curling because of the cure shrinkage of antiglare layer, thus throughput rate reduces.

As mentioned above, anti-glare film has been endowed mist degree by antiglare layer.The haze value of anti-glare film is preferably the scope of 5 ~ 50%.If haze value is less than 5%, then cannot obtain sufficient anti-dazzle performance, exterior light easily produces at picture and mirrors.On the other hand, in the region of its haze value more than 50%, although mirroring of exterior light can reduce, the resolution (ま り) of the picture of black display reduces.Haze value is the ratio of diffuse transmission relative to total light penetration, and it measures according to the JIS K 7136:2000 mist degree of the plastics-transparent material " ask method ".

(polaroid and anti-dazzle polarizer)

The blooming formed by resin lubrication agent composition for the above-described or be provided with the anti-glare film of antiglare layer on its surface, fits on polarizing coating as diaphragm, can make polaroid.When anti-glare film is fitted on polarizing coating, fit with polarizing coating in the one side with this antiglare layer opposition side.Can also to fit in of a polarizing coating face blooming of the present invention or anti-glare film, to comprise the diaphragm of other resin in another face of polarizing coating laminating.Below, when referred to as " blooming ", anti-glare film is also comprised.

(polarizing coating)

Polarizing coating makes polyvinyl alcohol resin film gas absorption quantity dichroic dye, thus can obtain predetermined polarization characteristic.As dichroic dye, use iodine or dichroic organic dye.Such polarizing coating comprises the dyestuff system polarizing coating making the iodine system polarizing coating of polyvinyl alcohol resin film gas absorption quantity iodine and make polyvinyl alcohol resin film gas absorption quantity dichroic organic dye.

Form the polyvinyl alcohol resin of polarizing coating by the resin saponification of polyvinyl acetate system being obtained.As polyvinyl acetate system resin, can enumerate as the polyvinyl acetate of the homopolymer of vinyl acetate and vinyl acetate and can with the multipolymer etc. of other monomer of its copolymerization.As can with other monomer of vinyl acetate copolymerization, such as, unsaturated carboxylic acid class, unsaturated sulfonic acid class, alkenes, vinyl ethers etc. can be enumerated.In addition, polyvinyl alcohol resin can be modified, and such as, can also use by the polyvinyl formal of aldehydes modification, polyvinyl acetal, polyvinyl butyral etc.

Polaroid manufactures through following operation usually: the damping operation of the moisture of adjustment polyvinyl alcohol resin film; Polyvinyl alcohol resin film is carried out to the operation of uniaxial tension; It is made to adsorb the operation of this dichroic dye the dyeing of polyvinyl alcohol resin film dichroic dye; The operation that the polyvinyl alcohol resin film of the dichroic dye that utilized boric acid aqueous solution to gas absorption quantity processes; The matting of the free boric acid of surface attachment etc. is washed off after boric acid process; With implementing these operations and the operation of diaphragm that the gas absorption quantity uniaxial tension polyvinyl alcohol resin film of dichroic dye is fitted.

Uniaxial tension can carry out before dyeing, also can carry out in dyeing, can also carry out in boric acid process after dyeing.Also uniaxial tension can be carried out in these multiple stages.Uniaxial tension can carry out between the roller that peripheral speed is different, and hot-rolling also can be used to carry out.In addition, can be the dry type stretching carrying out in an atmosphere stretching, also can be that the wet type of carrying out stretching with the state making it swelling with solvent stretches.Stretching ratio is generally about 4 ~ 8 times.The thickness implementing the polyethenol series polarizing coating stretched and dye such as can be about about 1 ~ 50 μm, is preferably about 10 ~ 35 μm.

(laminating of polarizing coating and blooming)

Then, the applying method of polarizing coating and blooming is described.Generally bonding agent is used in the laminating of polarizing coating and blooming.As bonding agent, can use the material as bonding agent composition such as epoxy system resin, polyurethane series resin, cyanoacrylate system resin, acrylamide resin.One of bonding agent of preferred use is the bonding agent of no-solvent type.The bonding agent of no-solvent type does not comprise the solvent of significant quantity, comprise by heating or active energy beam (such as, ultraviolet, visible ray, electron ray, X ray etc.) irradiation and react the curability compound (monomer or oligomer) of solidification, it is solidified to form bond layer by this curability compound, typically, comprise and utilize the irradiation of heating or active energy beam and react the curability compound of solidification and polymerization initiator and form.In no-solvent type bonding agent, from reactive viewpoint, preferably utilize cationic polymerization and the material solidified, especially, for using epoxy compound for the epoxy bonding agent of the no-solvent type of curability compound, polarizing coating and blooming excellent in adhesion comprising acrylic resin or other resin molding, therefore preferably use.

As no-solvent type epoxy bonding agent contained by the material that solidifies preferably by cationic polymerization of the epoxy compound of curability compound, particularly, from the viewpoint such as weatherability and refractive index, more preferably use the epoxy compound not comprising aromatic rings in molecule.As the epoxy compound not comprising aromatic rings in such molecule, the hydride of aromatic epoxy compound, cycloaliphatic epoxy, aliphatic epoxy compound etc. can be illustrated.It should be noted that, the epoxy compound as curability compound has the epoxy radicals of more than 2 usually in molecule.

First, the hydride of aromatic epoxy compound is described.The hydride of aromatic epoxy compound can be obtained by following method: making the aromatic series poly hydroxyl compound as the raw material of aromatic epoxy compound optionally carry out hydrogenation with adding to depress to aromatic rings in the presence of a catalyst, making obtained core hydrogenation poly hydroxyl compound carry out glycidyl etherified.As aromatic epoxy compound, such as, the biphenol type epoxy compound of the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F, the diglycidyl ether of bisphenol S and so on can be enumerated; The epoxy resin of the phenolic varnish type of phenol novolac epoxy resins, cresol novolac epoxy, hydroxy benzaldehyde phenol novolac epoxy resins and so on; The epoxy resin etc. of the multifunctional type of the glycidyl ether of tetrahydroxy benzene methylmethane, the glycidyl ether of tetrahydroxybenzophenone, epoxidation polyvinylphenol and so on.For taking bisphenols as the aromatic series poly hydroxyl compound of typical example as these raw materials, carrying out core hydrogenation as mentioned above, making chloropropylene oxide and this hydroxyl reaction, then obtain the hydride of aromatic epoxy compound.Wherein, as the hydride of aromatic epoxy compound, the glycidyl ether of the bisphenol-A of preferred hydrogenation.

Then, cycloaliphatic epoxy is described.Cycloaliphatic epoxy refers in molecule the epoxy compound with the epoxy radicals that at least 1 is closed with ester ring type ring key, and " having at least 1 epoxy radicals of closing with ester ring type ring key in molecule " refers to the structure had shown in following formula.In formula, m is the integer of 2 ~ 5.

Therefore, cycloaliphatic epoxy refers in molecule have the structure shown at least 1 above formula and comprise the compound that it has the epoxy radicals of total more than 2 in interior molecule.More specifically, (the CH in above-mentioned formula is eliminated ₂) _min the group of form of the hydrogen atom of more than 1 or 2 and the compound of other chemical constitution bonding can form cycloaliphatic epoxy.(CH ₂) _min the hydrogen atom of more than 1 or 2 can be replaced by the straight-chain such as methyl or ethyl alkyl is suitable.In such cycloaliphatic epoxy, the epoxy compound with cyclopentane epoxide ring (in above-mentioned formula m=3) or 7-oxa-bicyclo[4.1.0 ring (in above-mentioned formula m=4) can obtain the bonding agent of bonding strength excellence, thus more preferably uses.Below, the structure of suitable cycloaliphatic epoxy is exemplified particularly.

3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexane carboxylate,

3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylic acid ester,

Ethylenebis (3,4-epoxycyclohexane carboxylate),

Two (3,4-epoxycyclohexyl-methyl) adipate,

Two (3,4-epoxy-6-methylcyclohexylmethyl) adipate,

Diethylene glycol bis-(3,4-epoxycyclohexyl methyl ether),

Ethylene glycol bis (3,4-epoxycyclohexyl methyl ether),

2,3,14,15-diepoxy-7,11,18,21-tetra-oxa-three spiral shell-[5.2.2.5.2.2] 21 alkane (all right called after 3, the 4-7-oxa-bicyclo[4.1.0 spiral shell-2 of this compound ', 6 '-dioxane spiral shell-3 ", 5 "-dioxane spiral shell-3 " ', 4 " '-7-oxa-bicyclo[4.1.0),

3-(3,4-epoxycyclohexyl)-8,9-epoxy-1,5-dioxo spiro [5.5] undecane,

4 vinyl cyclohexene dioxide,

Two-2,3-epoxycyclopentyl ethers,

Dicyclopentadiene etc.

In addition, aliphatic epoxy compound can be the poly epihydric alcohol base ether of aliphatic polyol or its alkylene oxide addition product.More specifically, can 1 be enumerated, the diglycidyl ether of the triglycidyl group ether of the diglycidyl ether of 4-butylene glycol, the diglycidyl ether of 1,6-hexanediol, glycerine, the triglycidyl group ether of trimethylolpropane, polyglycol, the diglycidyl ether of propylene glycol, to the one kind or two or more alkylene oxide (oxirane or epoxypropane) of the aliphatic polyol addition of ethylene glycol or propylene glycol, glycerine and so on and the poly epihydric alcohol base ether etc. of the polyether glycol obtained.

Epoxy compound described above can only be used alone a kind, also two or more can be combinationally used.

The epoxide equivalent of the epoxy compound that the epoxy bonding agent of no-solvent type comprises is generally 30 ~ 3000g/ equivalent, is preferably the scope of 50 ~ 1500g/ equivalent.If epoxide equivalent is less than 30g/ equivalent, then there is following possibility: the flexibility of the blooming after being solidified by this bond layer reduces, or bonding strength reduces.On the other hand, if epoxide equivalent is more than 3000g/ equivalent, then may reduce with the compatibility of other composition contained by epoxy bonding agent.

In order to make above-mentioned epoxy compound carry out cationic polymerization, the epoxy bonding agent of no-solvent type comprises cationic polymerization initiators usually.Cationic polymerization initiators produces kation kind or lewis acid by the irradiation of luminous ray, ultraviolet, X ray, electron ray isoreactivity energy-ray or heating, thus cause the material of the polyreaction of epoxy radicals.The cationic polymerization initiators of these any types can be used, from the viewpoint of operability, preferably impart potentiality.It should be noted that, below, irradiation by luminous ray, ultraviolet, X ray, electron ray isoreactivity energy-ray is produced kation kind or lewis acid, thus the cationic polymerization initiators of the polyreaction of initiation epoxy radicals is also referred to as light cationic polymerization initiators.

Use light cationic polymerization initiators if make, then bonding agent composition can be made at normal temperatures to solidify, therefore consider that the necessity of the thermotolerance of polarizing coating or the distortion caused by expansion reduces, blooming can be formed with good adaptation on polarizing coating.In addition, use light cationic polymerization initiators if make, then light plays the effect of catalyzer, even if be therefore mixed in epoxy bonding agent, storage stability and operability are also excellent.

As light cationic polymerization initiators, such as, aromatic diazonium salt can be used; The salt of aromatic iodonium salts or aromatic series sulfonium salt and so on; Iron-allene complex thing etc.These light cationic polymerization initiators can individually use, also can be used in combination by two or more.Among these, particularly aromatic series sulfonium salt also has Ultraviolet Light at the wave band of more than 300nm, curability thus can be provided excellent and have good physical strength and the solidfied material of bonding strength, therefore preferably using.

These light cationic polymerization initiators can easily obtain as commercially available product, such as, all represent with trade name, can enumerate " KAYARAD PCI-220 " that Nippon Kayaku K. K sells, " KAYARAD PCI-620 ", " UVI-6990 " of Union Carbide Company, " ADEKA OPTOMER SP-150 " and " ADEKA OPTOMERSP-170 " that Asahi Denka Co., Ltd. sells, " CI-5102 " that Tso Tat Co., Ltd., Japan sells, " CIT-1370 ", " CIT-1682 ", " CIP-1866S " ', " CIP-2048S " ' and " CIP-2064S ", " DPI-101 " that green KCC sells, " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", " BBI-102 ", " BBI-103 ", " BBI-105 ", " TPS-101 ", " TPS-102 ", " TPS-103 ", " TPS-105 ", " MDS-103 ", " MDS-105 ", " DTS-102 " and " DTS-103 ", " PI-2074 " of Rhodia Company etc.

Relative to epoxy compound 100 weight portion, the blend amount of light cationic polymerization initiators is generally 0.5 ~ 20 weight portion, is preferably more than 1 weight portion, is preferably below 15 weight portions in addition.

Except light cationic polymerization initiators, the epoxy bonding agent of no-solvent type can contain photosensitizer as required.By using photosensitizer, reactive raising, can improve physical strength and the bonding strength of solidfied material.As photosensitizer, such as, carbonyls, organosulfur compound, persulfide, redox based compound, azo and two azo-compounds, halogen compounds, photo-reduction pigment etc. can be enumerated.When mixture photosensitizer, relative to epoxy compound 100 weight portion, its amount is about 0.1 ~ 20 weight portion.

In addition, as producing kation kind or lewis acid by heating, thus cause the hot cationic polymerization initiators of the polyreaction of epoxy radicals, such as, benzylsulfonium, thiophene salt, thiophane salt (thiolanium), benzyl ammonium salt, pyridiniujm, hydrazonium salt, carboxylate, sulphonic acid ester, amine acid imide etc. can be enumerated.These hot cationic polymerization initiators also easily can obtain as commercially available product, such as, all represent with trade name, " ADEKAOPTON CP77 " and " ADEKA OPTON CP66 ", " CI-2639 " and " CI-2624 " of Tso Tat Co., Ltd., Japan's sale, " the San-Aid SI-60L ", " San-Aid SI-80L " and " San-Aid SI-100L " of three new chemical industry Co., Ltd. sale etc. that Asahi Denka Co., Ltd. sells can be enumerated.These hot cationic polymerization initiators can individually use, also can be used in combination by two or more.In addition, light cationic polymerization initiators and hot cationic polymerization initiators can also be share.

The epoxy bonding agent of no-solvent type can also promote the compound of cationic polymerization containing oxetanes class or polyalcohols etc.

When using the epoxy bonding agent of no-solvent type, polarizing coating can make both fit to carry out with the bonding of blooming by being coated with this bonding agent at the bonding plane of blooming and/or polarizing coating.The method of the epoxy bonding agent that polarizing coating and/or blooming are coated with no-solvent type is not particularly limited, such as, the various coating methods such as scraping blade, line rod, die coater, comma coating machine, gravure coater can be utilized.In addition, because each coating method has best range of viscosities respectively, a small amount of solvent therefore can be used to carry out viscosity adjustment.For this solvent used only otherwise reduce the optical property of polarizing coating and epoxy bonding agent is dissolved well, such as, can use with toluene be representative hydro carbons, take ethyl acetate as the organic solvent such as ester class of representative.

After blooming of fitting on polarizing coating, irradiate active energy beam or heating across the bond layer comprising uncured epoxy bonding agent, thus this bond layer is solidified, blooming is bonded on polarizing coating.When solidifying in the irradiation by active energy beam, preferably use ultraviolet.As concrete ultraviolet light source, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, black lamp, metal halide lamp etc. can be enumerated.About active energy beam, such as ultraviolet irradiation intensity and exposure, fully activate to make cationic polymerization initiators and the bond layer after solidification and polarizing coating, blooming do not caused to dysgenic mode is suitable to be selected.In addition, when solidifying when utilizing heating, can utilize the heating of generally known method, temperature and time is now also to make cationic polymerization initiators fully activate and the bond layer after solidification and polarizing coating, blooming not caused to dysgenic mode is suitable to be selected.

As above obtain comprise solidification after the thickness of bond layer of epoxy bonding agent can be the scope of about 0.1 ~ 50 μm usually, be preferably more than 1 μm.In addition, 1 ~ 20 μm, the more preferably scope of 2 ~ 10 μm is more preferably.

The epoxy bonding agent of no-solvent type described above can be preferred for comprising the blooming of acrylic resin and the laminating of polarizing coating or the blooming be made up of the resin molding except acrylic resin and the laminating of polarizing coating or the laminating both them.

In addition, as other the preferred bonding agent of laminating that can be used in blooming and polarizing coating, the bonding agent of water system can be enumerated, by the material of bonding agent component dissolves in water or make it be scattered in material in water.If use the bonding agent of water system, then can reduce the thickness of bond layer further.If enumerate the example of water system bonding agent, there is the material containing water-soluble cross-linked property epoxy resin or hydrophilic polyurethane series resin as bonding agent composition.

As water-soluble cross-linked property epoxy resin, such as, can enumerate following Polyamide Epoxy, it is reacted by the polyamide polyamine that makes to utilize the reaction of the dicarboxylic acid of the polyalkylene polyamine and hexane diacid and so on of diethylene triamine or trien and so on to obtain and chloropropylene oxide and is obtained.As the commercially available product of such Polyamide Epoxy, all represent with trade name, " the Sumirez Resin 650 " and " Sumirez Resin 675 " that have Sumika Chemtex Co., Ltd. to sell etc.

When using water-soluble cross-linked property epoxy resin as bonding agent composition, in order to improve coating and cementability further, other water soluble resins such as preferred mixing pva system resin.About polyvinyl alcohol resin; except partly-hydrolysed polyvinyl alcohol (PVA) and fully saponified polyvinyl alcohol (PVA), it can also be the polyvinyl alcohol resin through modification of carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinyl alcohol (PVA), methylol-modified polyvinyl alcohol (PVA), amino modified polyvinyl alcohol (PVA) and so on.Wherein, saponified, the i.e. carboxy-modified polyvinyl alcohol (PVA) of the multipolymer of vinyl acetate and unsaturated carboxylic acid or its salt is preferably used.It should be noted that, said " carboxyl " refers to the concept comprising-COOH and salt thereof herein.

If enumerate the example of commercially available preferred carboxy-modified polyvinyl alcohol (PVA), all represent with trade name, " DR-0415 " of " GohsenolT-330 " and " Gohsenol T-350 " that " the kuraray poval KL-506 ", " kuraray poval KL-318 " and " kuraray poval KL-118 " that have Co., Ltd. kuraray to sell, the Nippon Synthetic Chemical Industry Co., Ltd sell, Deuki Kagaku Kogyo Co., Ltd's sale, " AF-17 ", " AT-17 " and " AP-17 " of JAPAN VAM & POVAL CO., LTD. sale etc.

About the bonding agent comprising water-soluble cross-linked property epoxy resin, other water soluble resins such as above-mentioned epoxy resin and the polyvinyl alcohol resin added as required can be dissolved in the water, prepare with the form of bonding agent aqueous solution.In this situation, water-soluble cross-linked property epoxy resin is preferably the concentration of the scope about 0.2 ~ 2 weight portion relative to water 100 weight portion.In addition, when mixture polyvinyl alcohol resin, about its amount is preferably 1 ~ 10 weight portion relative to water 100 weight portion, more preferably about 1 ~ 5 weight portion.

On the other hand, when use comprises the bonding agent of the water system of polyurethane series resin, as the example of suitable urethane resin, the urethane resin of ionomer type, particularly Polyester ionomer type polyurethane resin can be enumerated.Herein, ionomer type refers to the type importing a small amount of ionic composition (i.e. hydrophilic component) in the urethane resin forming skeleton.In addition, Polyester ionomer type polyurethane resin refers to the urethane resin with polyester backbone, and has wherein imported a small amount of ionic composition (hydrophilic component).This ionomer type polyurethane resin does not use emulsifying agent and directly emulsification and form emulsion, the therefore suitable bonding agent as water system in water.As the commercially available product of Polyester ionomer type polyurethane resin, such as, all represent with trade name, " HYDRANAP-20 " that have Dainippon Ink Chemicals to sell and " HYDRAN APX-101H " etc., all can obtain in the form of an emulsion.

Using the urethane resin of ionomer type as bonding agent composition time, the preferably further crosslinking chemical of mixture isocyanate-based etc.Isocyanate-based crosslinking chemical is the compound in molecule with at least 2 isocyanato-bases (-NCO), as the example, except 2, 4-toluene diisocyanate, phenylene diisocyanate, 4, 4 '-methyl diphenylene diisocyanate, 1, 6-hexamethylene diisocyanate, beyond the polyisocyanate monomer of isophorone diisocyanate and so on, their multiple molecules are had to be added to the adduction object of the polyvalent alcohol of trimethylolpropane and so on, diisocyanate 3 molecule defines the isocyanuric acid ester body of 3 officials' energy of isocyanurate ring in the part that each single terminal isocyanate acid group closes base, diisocyanate 3 molecule closes the partially hydrated and decarbonate of base and the ester modified body of polyisocyanate etc. of biuret body of being formed and so at each single terminal isocyanate acid group.As the commercially available isocyanate-based crosslinking chemical that can be suitable for using, such as, the material etc. that Dainippon Ink Chemicals sells with the trade name of " Ha イ De ラ Application ア シ ス タ mono-C-1 " is had.

When use comprises the water system bonding agent of the urethane resin of ionomer type, from the viewpoint of viscosity and cementability, preferably with the concentration of this urethane resin be 10 ~ 70 about % by weight so that be more than 20 % by weight and be less than 50 % by weight mode be dissolved or dispersed in water.When mixture isocyanate-based crosslinking chemical, to be that mode about 5 ~ 100 weight portions is suitable with isocyanate-based crosslinking chemical relative to polyurethane series resin 100 weight portion select its blend amount.

When using the bonding agent of such water system, polarizing coating can make both fit to carry out with the bonding of blooming by being coated with this bonding agent at the bonding plane of blooming and/or polarizing coating.More specifically, following method can be enumerated: such as, the coating methods such as scraping blade, line rod, die coater, comma coating machine, gravure coater are utilized to be applied to equably after on polarizing coating and/or blooming by the bonding agent of water system, at coated face another film stacked, fit with roller etc. and carry out drying; Etc..Drying such as can be carried out with the temperature of about 60 ~ 100 DEG C.In order to improve cementability further, preferably cultivate about 1 ~ 10 day with the temperature about the temperature slightly higher than room temperature, such as 30 ~ 50 DEG C after the drying.

In the same manner as the epoxy bonding agent of no-solvent type described before, the bonding agent of these water systems also can be preferred for comprising the blooming of acrylic resin and the laminating of polarizing coating or the blooming be made up of the resin molding except acrylic resin and the laminating of polarizing coating or the laminating both them.The two sides lamination of polarizing coating comprise the blooming of acrylic resin situation and a surface layer pressure of polarizing coating comprise acrylic resin blooming and another surface layer pressure comprise the resin except acrylic resin blooming (comprise for wavelength plate and field angle compensate film equiphase difference film situation, identical below.) situation any one situation under, all can use the bonding identical bonding agent with the film on the two sides being laminated to polarizing coating, also can use different bonding agents, in order to the reduction of the simplification of manufacturing process and the component parts of polaroid, preferably use identical bonding agent.

When the manufacture of polaroid, preferably to comprising the blooming of acrylic resin and comprising the fit surface of side of in the blooming of the resin except acrylic resin and polarizing coating and implement Corona discharge Treatment in advance.By implementing Corona discharge Treatment, the bonding force of these films and polarizing coating can be improved.Corona discharge Treatment refers to and between electrode, applies high voltage and discharge, thus will be configured at the process of interelectrode resin molding activation.The effect of Corona discharge Treatment is different from the kind of electrode, electrode gap, voltage, humidity, kind of resin molding of using etc., such as, preferably electrode gap is set as 1 ~ 5mm, translational speed is set as about 3 ~ 20m/ minute.After Corona discharge Treatment, at this treated side across above-mentioned bonding agent laminating polarizing coating.

Embodiment

Below, illustrate that embodiment and comparative example are to further illustrate the present invention, but the present invention not limit by these examples.In example, as long as no special declaration, then represent that the % of content or consumption and part are weight basis.

Embodiment 1

(acrylic resin and acrylic flexible polymer particle)

Be that the multipolymer of 96/4 is as acrylic resin using the weight ratio of methyl methacrylate/acrylic acid methyl esters.In addition, be that the particle of 240nm is as acrylic flexible polymer particle using the elastomer particles of following 3-tier architecture and to the mean grain size as the elastic body in middle layer, in above-mentioned 3-tier architecture, innermost layer is the polymkeric substance of the hard using a small amount of allyl methacrylate and methyl methacrylate polymerization, middle layer is using butyl acrylate as principal ingredient and uses the soft elastic body that styrene and a small amount of allyl methacrylate are polymerized further, outermost layer is the polymkeric substance of the hard using a small amount of ethyl acrylate and methyl methacrylate polymerization.

(making of acrylic acid series blooming)

The weight ratio mixture of person/the latter=70/30 before to be resin and aforesaid propylene acid by aforesaid propylene acid be flexible polymer composition granule, the particle double screw extrusion machine melting mixing that mixture is obtained, simultaneously, relative to its 100 parts, add the stearic acid 0.05 part as lubricant and mix, making the particle of resin lubrication agent composition.This particle is dropped into the single screw extrusion machine of 65mm φ, the T-shaped mould being 275 DEG C via design temperature is extruded, the two sides temperature of extruded membranaceous molten resin is set as 2 polishing rolls with minute surface of 45 DEG C sandwich and cool, makes acrylic resin film.The film obtained is wound up on the core that diameter is 6 inches (15.2mm).

Taken care of 3 months with the state be wound up into like this on core by film, result is not observed after 3 months in keeping yet and is taken up, and does not observe oozing out of lubricant.

Embodiment 2

Stearic addition is changed to 0.03 part by 0.05 part, makes acrylic resin film similarly to Example 1 in addition, and to be wound up into diameter be on the core of 6 inches.Taken care of 3 months with the state be wound up into like this on core by film, result is not observed after 3 months in keeping yet and is taken up, and does not observe oozing out of lubricant.

Embodiment 3

Stearic addition is changed to 0.07 part by 0.05 part, makes acrylic resin film similarly to Example 1 in addition, and to be wound up into diameter be on the core of 6 inches.Taken care of 3 months with the state be wound up into like this on core by film, result is not observed after 3 months in keeping yet and is taken up, and does not observe oozing out of lubricant.

Embodiment 4

In embodiment 1, together with the stearic acid as lubricant, relative to total 100 weight portion of acrylic resin and acrylic flexible polymer particle, add 2 as benzotriazole system ultraviolet light absorber, 2 '-di-2-ethylhexylphosphine oxide (4-(1, 1, 3, 3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol) 0.5 part, make the particle of resin lubrication agent composition in addition similarly to Example 1, and then utilize the extrusion by melting identical with embodiment 1 to make acrylic resin film by this particle, and to be wound up into diameter be on the core of 6 inches.This film demonstrates the transmitance of 23% under wavelength 380nm.Taken care of 3 months with the state be wound up into like this on core by film, result is not observed after 3 months in keeping yet and is taken up, and does not observe oozing out of lubricant.

Embodiment 5

In embodiment 4, relative to total 100 weight portion of acrylic resin and acrylic flexible polymer particle, the blend amount of benzotriazole system ultraviolet light absorber is made to change to 1.9 parts, make acrylic resin film similarly to Example 4 in addition, and to be wound up into diameter be on the core of 6 inches.

This film demonstrates the transmitance of 0.9% under wavelength 380nm.Taken care of 3 months with the state be wound up into like this on core by film, result is not observed after 3 months in keeping yet and is taken up, and does not observe oozing out of lubricant.

Comparative example 1

Except not adding except stearic acid, make acrylic resin film similarly to Example 1, and to be wound up into diameter be on the core of 6 inches.Taken care of 3 months with the state be wound up into like this on core by film, result is observed after 3 months in keeping and is taken up.Herein, take up the state referring to be wound in roll and bind, produce the phenomenon of depression etc. in the most surface of roll film.

Comparative example 2

Stearic addition is changed to 0.10 part by 0.05 part, makes acrylic resin film similarly to Example 1 in addition, and to be wound up into diameter be on the core of 6 inches.If film is taken care of 3 months with the state be wound up into like this on core, take up although then do not produce, produce stearic oozing out.

Embodiment 6

(preparation of antiglare layer formation coating fluid)

Prepare Photocurable resin composition, it contains pentaerythritol triacrylate and polyfunctional carbamate acrylate (reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate), the former/weight ratio of the latter is 60/40, and being dissolved in ethyl acetate in the mode that both total concentration is 60%, in described Photocurable resin composition, also mixture has levelling agent.The above-mentioned pentaerythritol triacrylate and polyfunctional carbamate acrylate that form this Photocurable resin composition are called " curability acrylate " in the lump.Relative to the curability acrylate 100 parts of this Photocurable resin composition, add mean grain size be the methyl methacrylate/styrene copolymer resin particle 5 parts of 2.7 μm and make it disperse, and then dilute in the mode that the total concentration of curability acrylate and resin particle is 30% with ethyl acetate.Afterwards, relative to the curability acrylate in this liquid 100 parts, add " IRGACURE 184 " (manufacture of vapour Bagong department) 1 part as Photoepolymerizationinitiater initiater, preparation antiglare layer formation coating fluid.

Above-mentioned Photoepolymerizationinitiater initiater is added and masking in the Photocurable resin composition used herein, and carry out Ultraviolet radiation and make it solidify, the refractive index of the resin obtained is 1.53, and on the other hand, the refractive index of above-mentioned methyl methacrylate/styrene copolymer resin particle is 1.49.Therefore, both refringences are 0.04.

(making of anti-glare film)

The surface of each acrylic resin film made in embodiment 1,4 and 5 is coated with the antiglare layer formation coating fluid of above-mentioned preparation, makes dried coating thickness be 3.4 μm, being set as keeping 3 minutes in the dryer of 60 DEG C, makes this dried coating film.After drying, from the film side of film with h ray conversion light quantity for 200mJ/cm ²mode exposure intensity be 20mW/cm ²the light from high-pressure sodium lamp, the film layer of Photocurable resin composition is solidified, makes the anti-glare film defining the irregular antiglare layer of surperficial tool in acrylic resin film.It is on the core of 6 inches that the anti-glare film obtained is wound up into diameter.Use haze meter to determine the haze value of each anti-glare film, result haze value when using arbitrary acrylic resin film is 11.5%.

By anti-glare film to be wound up into state keeping on core like this 3 months, result, after keeping 3 months, no matter when using arbitrary acrylic resin film, all not being observed and being taken up, and not observing stearic oozing out.

Embodiment 7

(making of polaroid)

If make the thickness of polyvinyl alcohol (PVA) gas absorption quantity iodine be the polarizing coating of about 30 μm a face via bonding agent laminating embodiment 6 in make each anti-glare film, in this acrylic resin film side, to fit tri acetyl cellulose membrane, norbornene resin film or polypropylene-based resin film (phase differential can be imparted respectively) via bonding agent in another face of polarizing coating, then obtain the anti-dazzle polarizer being suitable for liquid crystal indicator.

Claims (6)

1. a blooming, it is the blooming formed by the resin lubrication agent composition comprising acrylic resin composition 100 weight portion and lubricant 0.01 ~ 0.09 weight portion, wherein,

This acrylic resin composition comprises the rubber elastomer particle that transparent acrylic resin and mean grain size are 10 ~ 300nm, and in acrylic resin composition, the content of this rubber elastomer particle is 25 ~ 45 % by weight, and lubricant is stearic acid.

2. blooming as claimed in claim 1, wherein,

Containing ultraviolet light absorber in resin lubrication agent composition, the transmitance of wavelength 380nm is less than 25%.

3. an anti-glare film, the surface of its blooming described in claim 1 or 2 is formed with antiglare layer.

4. anti-glare film as claimed in claim 3, wherein,

Antiglare layer is formed by the composition comprising transparent resin 100 weight portion and particulate 3 ~ 30 weight portion, and mist degree is 5 ~ 50%, and the mean grain size of described particulate is 0.5 ~ 5 μm and is 0.02 ~ 0.2 with the refringence of described transparent resin.

5. a polaroid, it comprises the blooming described in polarizing coating and claim 1 or 2, and described polarizing coating comprises polyvinyl alcohol resin, and described blooming and this polarizing coating are fitted.

6. an anti-dazzle polarizer, it comprises the anti-glare film described in polarizing coating and claim 3 or 4, and described polarizing coating comprises polyvinyl alcohol resin, described anti-glare film be fitted in this polarizing coating with antiglare layer opposite side.