CN108349228A

CN108349228A - Laminated polyester film

Info

Publication number: CN108349228A
Application number: CN201680064365.8A
Authority: CN
Inventors: 田川理惠; 山口洋平
Original assignee: Toyobo Co Ltd
Current assignee: Toyobo Co Ltd
Priority date: 2015-11-13
Filing date: 2016-11-02
Publication date: 2018-07-31
Anticipated expiration: 2036-11-02
Also published as: JP6737364B2; WO2017082130A1; JP2017095734A; KR20180042439A; JP6521264B2; TW201728461A; TWI599482B; JP2019090058A; KR101893741B1; CN108349228B

Abstract

It provides：The harmonies of the characteristics such as sliding and the transparency is excellent, manufacture when, liquid crystal display device the subsequent handlings such as polarizer manufacturing process in operability it is excellent, scratch is few, for inhibiting the low interference capability of rainbow spot unevenness also can be suitble to the easy-adhesion polyester film used in excellent optical applications.A kind of easy-adhesion polyester film is at least in single side there is the polyester film of coating layer, aforementioned coating layer to contain：Zirconium oxide/titanium dioxide hybrid particles A；Lubricant particle B；With, binder resin, zirconium oxide in aforementioned oxidation zirconium/titanium dioxide hybrid particles A is 10~90 mass % relative to the containing ratio of the gross mass of zirconium oxide and titanium dioxide, and the average grain diameter of aforementioned lubricants particle B is 200nm or more.

Description

Laminated polyester film

Technical field

The present invention relates to the easy-adhesions that the low interference capability for the problem that can be sure to be able to eliminate rainbow spot unevenness, the transparency are excellent Polyester film.More specifically, the easy-adhesion for being related to fine scratch optical applications that are few, being also suitable for fine is poly- Ester film.

Background technology

The stacking used above of display, the ornament materials of touch panel, computer, TV, liquid crystal display device etc. etc. There is the hard coat film of transparent hard conating.In addition, the transparent plastic film as base material, usually can be used transparent polyester film, In order to improve the polyester film of base material and the adaptation of hard conating, mostly setting with easy-adhesion coating layer as they Middle layer.

Aforementioned hard coat film is required to temperature, humidity, the durability of light, the transparency, chemical resistance, wearability, antifouling Property etc..In addition, the surface due to being mostly used for display, ornament materials etc., it is therefore desirable to visual, design.Therefore, it is Dazzle, rainbow shape color etc., have generally carried out following operation caused by reflected light when inhibiting from arbitrary angle： On the upper layer of hard conating, setting is layered on top of each other the anti-reflection layer of the multilayered structure of high refractive index layer and low-index layer.

However, display, ornament materials etc. be on the way, in recent years, it is desirable that further large screen (larger in area) and High precision is accompanied by this, especially increasingly to the requirement level of the inhibition of the rainbow shape color (interference spot) under fluorescent lamp It is high.In addition, for the reproducibility of color of sunshine, 3 type of wavelength of fluorescent lamp become mainstream, it is easier to generate interference spot.In turn, by The requirement that cost is reduced in simplifying for anti-reflection layer is also higher and higher.It is therefore desirable to only with the hard of not additional anti-reflection layer Film inhibits interference spot as possible.

It has been said that the rainbow shape color (interference spot) of hard coat film is the refractive index (such as 1.62 due to the polyester film of base material ~1.65) what the difference of the refractive index (such as 1.49) of the hard conating and by formation such as acrylic resins generated greatly.In order to subtract Refringence between small stacking and the generation for preventing interference spot, disclose following method：It is arranged on the polyester film of base material and applies Layer of cloth is applied in a manner of reducing the refringence of polyester film and coating layer, coating layer and the refringence of hard conating with constituting The resin and height of layer of cloth reflect the content of additive to control the refractive index of coating layer.

In the past, in field of the optics with easy-adhesion film, it is known to following technology：Comprising specific in adhesive layer Particle reduces (referring for example to patent document 1) to rainbow spot unevenness.However, for the above-mentioned prior art, from cementability and rainbow spot From the perspective of unevenness inhibits, it is seen that certain achievement is obtained, but there are problems that causing to be easy scuffing because of sliding difference, In order to improve sliding, exist if other particles are added the transparency reduce etc. can not obtain sliding with it is transparent, be used for Reduce balanced problem of the low interference capability of rainbow spot unevenness.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2007-203712 bulletins

Invention content

Problems to be solved by the invention

The use in the outdoor zone of the mobile devices such as mobile phone, auto navigation, e-book due to the development of mobile technology Expand.In addition, from slimming aspect, above-mentioned mobile device is essentially the display based on liquid crystal display panel.Such neck In domain, such as in the mobile phone equipped with touch panel, as the hard coat film of the surface protection for display, contacted with coated face Two interfaces reflected light caused by interference fringe, icon external member (icon suite) etc. design is implemented to the back side of hard coat film Property use on the way, visual defect caused by interference fringe just gradually becoming apparent from.

However, if it is desired to obtain high low interference capability then largely addition high refraction additive when, the transparency is impaired, generates The situation of low interference capability and the transparency can not be taken into account.In addition, the usage also in the display of fine, therefore, if Want inhibit cut then add lubricant, even if make sliding it is good sometimes if be unable to maintain that the transparency.

In turn, in recent years in order to improve productivity ratio, with the high speed of the post-processings processing such as the stacking of hard conating, cutting processing Change and promote, applies strong friction to coating layer, thickness variation, quality caused by the scratch of previous unquestioned coating layer Variation is increasingly becoming project.In particular, the hardness of the resin used to improve refractive index is higher and crisp, therefore, press down The coating layer of interference spot has been made, more there is the scratch bigger tendency of the coating layer.

Also not to coating layer while being urgently desired to have the inhibition of interference spot as a result, and then under High-speed machining Assign cut, high adhesion with the transparency and with hard conating the easily be bonded polyester film of optics.

The present invention is made as background using the project of the above-mentioned prior art.That is, the object of the present invention is to provide： The harmonies of the characteristics such as sliding and the transparency is excellent, manufacture when, liquid crystal display device the follow-up work such as polarizer manufacturing process Operability in sequence is excellent, scratch is few, for inhibiting the low interference capability of rainbow spot unevenness also can be suitble to make in excellent optical applications Easy-adhesion polyester film.

The solution to the problem

The present inventor has made intensive studies in order to achieve the above objectives, as a result completes the present invention.That is, the present invention includes It constitutes below.

1. a kind of easy-adhesion polyester film is at least to have the polyester film of coating layer, aforementioned coating layer in single side Contain：Zirconium oxide/titanium dioxide hybrid particles A；Lubricant particle B；With, binder resin, aforementioned oxidation zirconium/titanium dioxide is mixed It is 10~90 mass %, aforementioned profit that the zirconium oxide in particle A, which is closed, relative to the containing ratio of the gross mass of zirconium oxide and titanium dioxide The average grain diameter of lubrication prescription particle B is 200nm or more.

2. according to the easy-adhesion polyester film described in the above-mentioned 1st, wherein zirconium oxide/titanium dioxide hybrid particles A's is flat Equal grain size is 5~200nm.

3. according to the easy-adhesion polyester film described in the above-mentioned 1st or the 2nd, wherein lubricant particle B is relative to coating layer Solid constituent containing ratio be 0.1~20 mass %.

4. according to the easy-adhesion polyester film described in above-mentioned 1st~any one of 3rd, wherein zirconium oxide/titanium dioxide Hybrid particles A is 2~50 mass % relative to the containing ratio of the solid constituent of coating layer.

5. a kind of laminated polyester film, the painting of the easy-adhesion polyester film described in above-mentioned 1st~any one of 4th There is 1 in the group being made of hard conating, antiglare layer, anti-glare anti-reflection layer, anti-reflection layer and low reflection layer on layer of cloth Kind or more functional layer.

The effect of invention

According to the present invention it is possible to provide：It can be sure to be able to inhibit low interference capability, the transparency and the sliding of rainbow spot unevenness It is harmonious it is excellent, scratch is few, manufacture when, liquid crystal display device the subsequent handlings such as polarizer manufacturing process in operability it is excellent Optical applications in can be suitble to the easy-adhesion polyester film used.

Specific implementation mode

(polyester film)

The polyester film used as base material in the present invention is the film being made of polyester resin, preferably mainly with poly- to benzene In naphthalate, polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate At least one kind of polyester film for constituent.Alternatively, it is also possible to for by polyester above-mentioned be copolymerized have third element monomers Copolyester formed film.In these polyester films, from balanced aspect of physical property and cost, most preferably poly- pair Ethylene terephthalate film.

In addition, it may be multilayer that aforementioned polyester film, which can be single layer,.As long as in addition, playing the effect of the present invention In range, various additives can be contained in polyester resin as needed in these each layers.As additive, such as can lift Go out antioxidant, photostabilizer, antigelling agent, organic wetting agent, antistatic agent, ultra-violet absorber, surfactant etc..

(coating layer)

The easy-adhesion polyester film of the present invention is the painting that easy-adhesion is laminated on the base film of above-mentioned polyester Made of layer of cloth.In coating layer, including：Zirconium oxide/titanium dioxide hybrid particles A (hereinafter, being simply denoted as particle A sometimes)；Profit Lubrication prescription particle B (hereinafter, being simply denoted as particle B sometimes)；With binder resin.

Particle A is zirconium oxide/titanium dioxide hybrid particles.So-called hybrid particles refer in the present invention, zirconium oxide and dioxy Change titanium in single liquid individually to disperse, includes zirconium oxide and titanium dioxide not form Set Status as complex The particle group of the two.Certainly, liquid component is evaporated in drying process, curing process and is disappeared substantially in coating layer.Pass through Coating layer includes such particle A, and sliding and the harmony of the transparency are excellent, it can be ensured that the high transparency and low interference Property.Liquid is easy to form coating layer using aftermentioned so-called online rubbing method, it is therefore preferable that water-based liquid.

It can also include the other compositions in addition to zirconium oxide/titanium dioxide in particle A, can be that inorganic particle also may be used Think organic granular, be not particularly limited, the metals such as silica, titanium dioxide, zirconium oxide, talcum, kaolinite can be enumerated Oxide, calcium carbonate, calcium phosphate, barium sulfate etc. are inactive inorganic particle to polyester.

The gross mass of zirconium oxide and titanium dioxide (is free of the matter of liquid relative to the quality of the particle A as hybrid particles Amount) ratio preferably 70 mass % or more, more preferable 80 mass % or more, further preferred 90 mass % or more.It is of course possible to For 100 mass %.The ratio of the gross mass of zirconium oxide and titanium dioxide in particle A is obtained if it is 70 mass % or more The harmony of sliding and the transparency, is preferred.

Constitute gross mass of the quality relative to zirconium oxide and titanium dioxide of the zirconium oxide of the particle A as hybrid particles Ratio preferably 10 mass % or more, more preferable 20 mass % or more, further preferred 30 mass % or more, particularly preferred 40 matter Measure % or more and then particularly preferred 50 mass % or more, most preferably 55 mass % or more.The quality of zirconium oxide is relative to zirconium oxide When ratio with the gross mass of titanium dioxide is 10 mass % or more, surface roughness will not become too much, the sliding with deflector roll Property become appropriateness, be not easy to scratch.Therefore, mist degree will not be got higher, and hyalinosis is excellent.

Ratio preferably 90 matter of the quality of the zirconium oxide of composition particle A relative to the gross mass of zirconium oxide and titanium dioxide Measure % or less, more preferable 85 mass % or less, further preferred 80 mass % or less, particularly preferred 77 mass % or less.Oxidation The quality of zirconium relative to the gross mass of zirconium oxide and titanium dioxide ratio if it is 90 mass % hereinafter, then surface roughness is not Can become too small, keep appropriate sliding, operability becomes good, be not easy to scratch when rolling out and it is preferred that.

Ratio preferably 10 matter of the quality of the titanium dioxide of composition particle A relative to the gross mass of zirconium oxide and titanium dioxide Measure % or more, more preferable 15 mass % or more and then preferably 20 mass % or more, particularly preferred 23 mass % or more.Titanium dioxide The quality of titanium relative to the gross mass of zirconium oxide and titanium dioxide ratio be 10 mass % or more when, sliding improve, operation Property improve, scratch resistance become it is good and preferred.But gross mass of the quality of titanium dioxide relative to zirconium oxide and titanium dioxide Ratio become larger and mean that the ratio of the quality of zirconium oxide becomes smaller, it is therefore preferable that 90 mass % or less, more preferable 80 mass % with Under so preferably 70 mass % or less, particularly preferred 60 mass % or less and then particularly preferred 50 mass % or less, most preferably 45 mass % or less.

The preferred 5nm or more of average grain diameter of particle A, more preferable 10nm or more, further preferred 15nm or more, particularly preferably 20nm or more.The average grain diameter of particle A be 5nm or more when, be not easy aggregation and it is preferred that.

The preferred 200nm or less of average grain diameter of particle A, more preferable 150nm or less, further preferred 100nm or less, especially It is preferred that 60nm or less.When the average grain diameter of particle A is 200nm or less, the transparency is good and preferred.

Particle B can be enumerated：(1) silica, kaolinite, talcum, precipitated calcium carbonate, powdered whiting, zeolite, oxidation Aluminium, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, satin white, alumina silicate, diatomite, calcium silicates, hydroxide The inorganic particles such as aluminium, hydrated halloysite, magnesium carbonate, magnesium hydroxide, (2) acrylic acid series or metha crylic, vinyl chloride, second Vinyl acetate system, nylon, styrene/acrylic system, phenylethylene/butadiene system, polystyrene/acrylic acid series, polystyrene/different Pentadiene system, polystyrene/isoprene, methyl methacrylate/butyl methacrylate system, melamine series, poly- carbon The organic granulars such as acid esters system, urea system, epoxy, carbamate system, phenol system, diallyl phthalate system, Polyester are The sliding of appropriateness is assigned to coating layer, particularly preferably uses silica.

The preferred 200nm or more of average grain diameter of particle B, more preferable 250nm or more, further preferred 300nm or more, especially It is preferred that 350nm or more.The average grain diameter of particle B be 200nm or more when, be not easy to assemble, it can be ensured that sliding and it is preferred that.

The preferred 2000nm or less of average grain diameter of particle B, more preferable 1500nm, further preferred 1000nm, particularly preferably 700nm.The average grain diameter of particle B be 2000nm or less when, keep the transparency, in addition, particle will not fall off and it is preferred that.

The surface treatment that can carry out particle A and B has as surface preparation：Plasma discharge processing, corona are put Physical surface treatment as electric treatment and the chemical surface treatment of use coupling agent are, it is preferable to use coupling agent.As coupling agent, It is preferable to use organoalkoxy metal compounds (examples：Titanium coupling agent, silane coupling agent).In the case that particle B is silica, Silane coupled processing is particularly effective.It, can be in order to pre- before preparing this layer of coating fluid as the surface conditioning agent of particle B First implement surface treatment and use, or can also add and contain when preparing this layer of coating fluid and then in the form of additive In the layer.It can of course be used for particle A.

As the binder resin for constituting coating layer, it is not particularly limited, makees as long as being the resin for bringing easy-adhesion For the concrete example of polymer, it is (poly- that polyester resin, acrylic resin, carbamate resins, polyethylene-based resin can be enumerated Vinyl alcohol etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxylated cellulose, starch etc..Wherein, from , it is preferable to use polyester resin, acrylic resin, carbamate resins from the perspective of grain holding, adaptation.In addition, examining When considering the amalgamation with polyester film, polyester resin is best.These foregoing adhesives resin combinations can also be used.

Aforementioned polyester resin in coating layer, in all solids ingredient can be 100 mass %, preferably comprise 10 matter Measure % or more and 90 mass % or less.More preferably 20% mass % or more and 80 mass % or less.The content of polyester resin is When 90 mass % or less, keep under high temperature and humidity with the adaptation of hard conating and it is preferred that.On the contrary, content be 10 mass % with When upper, due to other carbamate resins etc. presence and the temperature remains within the normal range, the adaptation with polyester film under high temperature and humidity, It is preferred.

In the present invention, in order to form cross-linked structure in coating layer, coating layer can be formed comprising crosslinking agent.By containing Crosslinking dose, the adaptation under high temperature and humidity can be further increased.As specific crosslinking agent, urea system, epoxy can be enumerated System, melamine series, isocyanates Xi, oxazolines system, carbodiimide system etc..Wherein, high from the ageing stability of masking liquid, high temperature Adaptation improvement effect under wet process is set out, preferably melamine series, isocyanates Xi, oxazolines systems, carbodiimide system Crosslinking agent.In addition, in order to promote cross-linking reaction, catalyst etc. can be used as needed.

As content of the crosslinking agent in coating layer, preferably in all solids ingredient, 5 mass % or more and 50 mass % Below.More preferable 10 mass % or more and 40 mass % or less.If it is 10 mass % or more, the resin of coating layer is kept Intensity, the adaptation under high temperature and humidity is good, if it is 40 mass % hereinafter, then keeping the flexibility of the resin of coating layer, protects Hold the adaptation under room temperature, high temperature and humidity and it is preferred that.

The content of particle A in coating layer preferably 2 mass % or more, more preferable 3 mass % or more, further preferred 4 matter Measure % or more, particularly preferred 5 mass % or more.It, can be higher when the content of particle A in coating layer is 2 mass % or more The refractive index for keeping coating layer, can effectively obtain low interference capability and it is preferred that.

Particle A contents preferably 50 mass % or less in coating layer, more preferable 40 mass % or less, further preferred 30 matter Measure % or less, particularly preferred 20 mass % or less.When particle A contents in coating layer are 50 mass % or less, film property is made in holding And it is preferred that.

Particle B content preferably 0.1 mass % or more, more preferable 0.5 mass % or more in coating layer, further preferred 1 Quality % or more.When particle B content in coating layer is 0.1 mass % or more, keep appropriate sliding and it is preferred that.

Particle B content preferably 20 mass % or less in coating layer, more preferable 15 mass % or less, further preferred 10 matter Measure % or less.When particle B content in coating layer is 20 mass % or less, mist degree is lower kept, is gone out in terms of the transparency Hair is preferred.

Preferably 0.001 μm or more of the film thickness of coating layer, more preferable 0.01 μm or more, further preferred 0.02 μm or more, spy Not preferably 0.05 μm or more.When the film thickness of coating layer is 0.001 μm or more, cementability is good and preferred.

Preferably 2 μm or less of the film thickness of coating layer, more preferable 1 μm or less, further preferred 0.8 μm or less, particularly preferred 0.5 μm or less.The film thickness of coating layer be 2 μm or less when, it is no generation adhesion worry and it is preferred that.

In order to improve the deaeration of levelability, coating fluid when coating, in coating layer, surfactant can also be contained.Table Face activating agent can be cationic system, anionic system, nonionic system etc., preferably silicon-type, acetylenic glycols system or fluorine system table Face activating agent.It is preferred that in the range of the inhibition of the rainbow shape color under not damaging fluorescent lamp, the degree of adaptation, these Surfactant contains in coating layer.

It is the inhibition of the rainbow shape color in the case where not damaging fluorescent lamp, close in order to assign other functionality to coating layer In the range of the degree of conjunction property, various additives can be contained.As aforementioned additive, for example, fluorescent dye, glimmering Optical brightener, plasticizer, ultra-violet absorber, pigment dispersing agent, foam inhibitor, antifoaming agent, preservative etc..

As painting method, the so-called online rubbing method coated simultaneously when polyester base material film film and system can be applied After film polyester base material film separately use coater so-called offline rubbing method, online rubbing method be it is effective and more It is preferred that.

As painting method, for coating solution is thin in polyethylene terephthalate (hereinafter, brief note makees PET) Well known arbitrary method may be used in the method for film.For example, reverse roll coating method, gravure coating process, kiss-coating Method, die coater method, volume brush method, spray coating method, air knife coating method, bar rubbing method, tubular type scraper method, infiltration rubbing method, curtain Curtain rubbing method etc..These methods individually or can also be combined to coat.

In the present invention, as the method that coating layer is arranged on polyester film, following method can be enumerated：It will contain molten Agent, particle, resin coating solution in polyester film and drying.As solvent, can enumerate the organic solvents such as toluene, water, Or the mixed stocker of water and water-soluble organic solvent, it is mixed from environmental problem aspect, preferably individual water or water Closing has the mixing series solvent of water-soluble organic solvent.

The solid component concentration of coating liquid additionally depends on the type of binder resin, type of solvent etc., preferably 2 mass % Above, more preferable 4 mass %.The solid component concentration of coating liquid preferably 35 mass % or less, more preferable 15 mass % or less.

For the drying temperature after coating, also depending on the type of binder resin, the type of solvent, crosslinking agent has Nothing, solid component concentration etc., preferably 80 DEG C or more, preferably 250 DEG C or less.

The surface roughness (Ra) of coating layer and the sliding etc. of painting layer surface have a relationship, preferably 0.01nm or more, more It is preferred that 0.1nm or more, further preferred 0.2nm or more, particularly preferred 0.5nm or more.On the other hand, for the surface of coating layer The upper limit of roughness (Ra), preferably 200nm or less, more preferable 100nm or less, further preferred 80nm or less, particularly preferably 50nm or less.

(manufacture of optics easy-adhesion polyester film)

The optics easy-adhesion polyester film of the present invention can be manufactured according to the manufacturing method of general polyester film. For example, following method：So that polyester resin is melted, be extruded as sheet and shape, the temperature more than glass transition temperature Under degree, after being stretched gained No yield point polyester along longitudinal direction using the speed difference of roller, transversely stretched using stenter, Implement heat treatment.

The polyester film of the present invention can be that single axle drawn membrane may be biaxially oriented film, use twin shaft When oriented film is as protective film before liquid crystal display panel, from pellicular front it is just upper from also have no the color spot of iris, but from Inclined direction observes the color spot of iris sometimes when observing, it is therefore necessary to pay attention to.

The phenomenon is since biaxially oriented film on direction of travel, width direction, thickness direction by having different refractions The indicatrix of rate is formed, and becomes there are retardation that zero (refractive index is ellipse according to the transmission direction of the light inside film Circle is visible with positive round) direction.Therefore, it from the specific direction of inclined direction when liquid crystal display picture, generates and prolongs sometimes Amount is as zero point late, and centered on the point, the color spot of iris is generated with concentric circles.Moreover, by (method is just gone up from pellicular front Line direction) when being set as θ to the angle of position of color spot of visible iris, the birefringence in pellicular front is bigger, which becomes to get over Greatly, it is difficult to see the color spot of iris.In biaxially oriented film, the tendency that angled θ becomes smaller, therefore, as single axle drawn membrane that Sample, it is difficult to see the color spot of iris and it is preferred that.

However, in complete uniaxiality (mono-symmetry) film, it is apparent with the mechanical strength in the direction of differently- oriented directivity straight trip It reduces, it is not preferable.It is currently preferred that being drawn in the range of not generating the color spot of iris substantially or in liquid crystal display In the range of the color spot for not generating iris in viewing angle required by face, there is biaxiality (twin shaft objectivity).

(laminated polyester film)

Invention which are intended primarily for the laminated polyester films of optical applications can pass through the easy-adhesion polyester in the present invention It is arranged by electron beam or ultraviolet hardening acrylic resin or siloxane-based heat-curing resin etc. on the coating layer of film Hard conating of formation etc. is to obtain.

Setting functional layer is also preferred scheme on the coating layer of the easy-adhesion polyester film of the present invention.Functional layer is Refer to, for reflection-proof, inhibits dazzle, inhibition rainbow spot is uneven, inhibits cut etc., in addition to aforementioned hard conating, antiglare layer, anti-glare Anti-reflection layer, anti-reflection layer, low reflection layer and antistatic layer etc. have functional layer.Functional layer can use the art In well known various layers, the kind thereof is not particularly limited.Hereinafter, being illustrated to each functional layer.

For example, well known hard conating can be used in the formation of hard conating, it is not particularly limited, can uses：By dry Dry, hot, chemical reaction or any one of irradiating electron beam, radiation, ultraviolet light are to polymerization and/or the resinification of reaction Close object.As such curable resin, melamine series, acrylic acid series, silicon-type, polyethenol series can be enumerated and consolidated The property changed resin, from obtaining high case hardness or optical design aspect, the preferably acrylic acid series of photo-curable type cures Property resin.As such acrylic acid series curable resin, multifunctional (methyl) acrylate system monomer, acrylic acid can be used Ester system oligomer, as the example of acrylic ester oligomer, can enumerate polyester acrylate system, epoxy acrylate system, Urethane acrylate system, polyether acrylate system, polybutadiene acrylic acid ester system, organic silicon acrylic ester system etc..It is logical Hybrid reaction diluent, Photoepolymerizationinitiater initiater, sensitizer etc. in these acrylic acid series curable resins are crossed, so as to obtain It is used to form the coating composition of aforementioned optical functional layer.

Above-mentioned hard conating can have the anti-dazzle function (anti-dazzle function) of making extraneous light scatter.Anti-dazzle function is (anti-dazzle Light function) it is obtained by forming bumps on the surface of hard conating.At this point, the mist degree of film ideally preferably 0~50%, it is more excellent Select 0~40%, particularly preferred 0~30%.Certain 0% is ideal, can be 0.2% or more, or 0.5% therefore More than.

Therefore, the purposes of film of the invention can be suitable for the main entirety for spreading film for optical use, can be suitble to For prismatic lens piece, AR (antireflection) film, hard coat film, diffuser plate, broken prevent the optics such as the LCD such as film, tablet TV, CRT Use the basis film of component, the front panel used positioned at plasma scope as component near-infrared absorbing optical filter, Transparent conducting films such as touch panel, electroluminescent etc..

As be used to form above-mentioned hard conating by the cured acrylic resin of electron beam or ultraviolet light, in more detail For, the acrylic resin of the functional group with acrylic ester can be used, can be used for example：Contain lower molecular weight Polyester resin, polyether resin, acrylic resin, epoxy resin, carbamate resins, alkyd resin, spiral shell acetal resin, The oligomer of (methyl) acrylate of polyfunctional compounds such as polybutadiene, polymercaptan polyenoid resin, polyalcohol etc. or Prepolymer and (methyl) ethyl acrylate as reactive diluent, (methyl) ethylhexyl acrylate, styrene, methylbenzene The monofunctional monomers such as ethylene, n-vinyl pyrrolidone and polyfunctional monomer, such as trimethylolpropane tris (methyl) propylene Acid esters, hexylene glycol (methyl) acrylate, tripropylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6-HD two (methyl) acrylic acid The acrylic resin of ester, neopentyl glycol two (methyl) acrylate etc..

Wherein, in the case of electron beam or ultraviolet curing resin, it can be mixed in aforementioned resin and be used as photopolymerization The acetophenones of initiator, benzophenone, rice Chi benzoylbenzoic acids ester, α-amyl oxime ester, tetra methylthiuram list thioether, Thioxanthene ketone class, the n-butylamine as photosensitizer, triethylamine, three-normal-butyl phosphines etc. and use.

In addition, silicon-type (siloxane-based) heat-curing resin can by under acid or base catalyst, by organosilicon Hydride compounds individually or two or more is mixed and be hydrolyzed with condensation reaction and manufacture.In particular, the case where low reflection is used Under, when a kind or more fluorosilane compounds being mixed and being hydrolyzed with condensation reaction, in low-refraction, improve stain resistance Etc. it is better.

(manufacture of laminated polyester film)

For the manufacturing method of the laminated polyester film in the present invention, illustrated by taking easy-adhesion polyester film as an example, Certainly it is not limited to this.

Aforementioned electronic beam or ultraviolet hardening acrylic acid are coated in the coating level of aforementioned easy-adhesion polyester film Resinoid or siloxane-based heat-curing resin.In the case that coating layer is set to two sides, it is coated at least one coating level. Coating fluid is not necessarily to particularly diluted, needs to be diluted with organic solvent according to the viscosity of coating fluid, wettability, painting film thickness etc. There is no special problem.For coating layer, after being coated with aforementioned coating liquid on aforementioned film, after making it dry as needed, according to The condition of cure of coating fluid, carries out electron beam or ultraviolet light irradiation and heating forms hard conating to make coating layer cure.

In the present invention, preferably 1~15 μm of the thickness of hard conating.When the thickness of hard conating is 1 μm or more, effectively performance pair As the chemical resistance of hard conating, wearability, soil resistance etc. effect and it is preferred that.On the other hand, thickness is 15 μm or less When, keep the flexibility of hard conating, no worry for generating cracking etc. and it is preferred that.

As scratch resistance, when coated side preferably being made to be worn away with black lining paper, with the unconspicuous situation of visual cut.Preceding commentary If cut unobvious in valence, deflector roll by when be not easy to scratch, be preferred from the viewpoint of operability is equal.

The lower limit of confficient of static friction (μ s) preferably 0.3 when being 0.3 or more, the problem of no excessive slip, therefore, is manufacturing In process, rolls change with the roller etc. of hard chrome plating and be easy.Keep operability, adhesion resistance and it is preferred that.Confficient of static friction (μ s) it is upper Limit preferably 0.5, be 0.5 or less when, when rolling without to as contact opposing face film cause cut worry and it is preferred that.

The lower limit of the coefficient of kinetic friction (μ d) preferably 0.4 when being 0.4 or more, the problem of no excessive slip, therefore, is manufacturing In process, rolls change with the roller etc. of hard chrome plating and be easy.Keep operability, adhesion resistance and it is preferred that.The coefficient of kinetic friction (μ d) it is upper Limit preferably 0.6, be 0.6 or less when, when rolling without to as contact opposing face film cause cut worry and it is preferred that.

The polyester film of the present invention is used mainly as the easy adhering film of optics, it is therefore preferable that having the high transparency. The lower limit of mist degree is preferably 0%, more more preferable closer to 0%.The upper limit of mist degree preferably 2%, when being 2% or less, light is saturating Penetrate that rate is good, can obtain distinct image in liquid crystal display device and it is preferred that.The mist degree of polyester film for example can be according to after The method stated and measure.

By using the evaluation of aftermentioned measuring method, lower limit is preferred for the coating layer of adhesive layer and the adaptation of hard conating 80%, the upper limit preferably 100%.When being 80% or more, it may be said that be the state of the abundant adaptation for keeping coating layer and hard conating.

For the adaptation under the conditions of the high temperature and humidity of the adhesive layer and hard conating evaluated according to aftermentioned method, lower limit It is preferred that 10%, the upper limit preferably 100% of high temperature and humidity adaptation.When being 10% or more, substantially meet under the conditions of high temperature and humidity The adaptation of adhesive layer and hard conating, the passability in post-processing process substantially meet.More preferable 50% or more.

Be formed with hard conating polarizing film protection polyester film can not be confirmed preferably by aftermentioned evaluation method it is dry Spot is related to, if can not confirm interference spot using the evaluation method, the visuality of liquid crystal image device becomes good and preferred.

The easy-adhesion polyester film of the present invention can be used for various uses, the polarisation being preferred in liquid crystal display device The manufacturing process of plate uses particularly preferable as the protective film for the polarizing film for constituting polarizer.In general, polarizing film is mostly poly- Vinyl alcohol system uses polyvinyl alcohol system, is wherein added crosslinking dose as needed for the easy-adhesion polyester film of the present invention Deng bonding agent be bonded on polarizing film.At this point, the present invention easy-adhesion polyester film coating layer be not more preferably with partially The piece that shakes bonding side face and towards its opposing face use.It is preferred that the present invention easy-adhesion polyester film and polarizing film Be laminated on the surface of bonding it is described in such as International Publication No. 2012/105607, comprising polyester based resin, polyethenol series The adhesive layer of resin and crosslinking agent.

Embodiment

Then, using embodiment, comparative example and reference example, the present invention is described in detail, but the present invention does not limit certainly In embodiment below.In addition, the evaluation method used in the present invention is as described below.

(1) average grain diameter

(measuring method for utilizing scanning electron microscope)

The measurement of the average grain diameter of above-mentioned particle can be carried out by following methods.It is micro- for particle scanning electron Mirror (SEM) shoots photo, becomes the multiplying power of 2~5mm with the size of minimum particle 1, measures 300~500 particles most Major diameter (farthest away from 2 points between distance), using its average value as average grain diameter.Present in coating layer in the present invention The average grain diameter of grain can be measured by the assay method.

(dynamic light scattering method)

The average grain diameter of particle can also be found out when manufacturing particle, film by dynamic scattering method.Colloidal sol is used and is divided Dispersion media dilutes, using the parameter of decentralized medium, with submicron particles analyzer N4PLUS (Beckman Coulter corporations) It is measured, is calculated with the Cumulant Method Using, to obtain average grain diameter.The particle observed in colloidal sol with dynamic light scattering method is averaged Grain size observes the average grain diameter of these aggregated particles when having the mutual aggregation of particle.

(2) refractive index of particle

The detecting refractive index of particle can be carried out by following methods.After so that inorganic particle is dried with 150 DEG C, with mortar powder It is broken, by gained powder infusion after solvent 1 (solvent of low-refraction also than particle), by (the high refractive index also than particle of solvent 2 Solvent) it bit by bit adds until the basic bleach of particle.Use Abbe refractometer (ATAGO CO., LTD. Abbe refractometers Meter) measure the refractive index of the liquid.Measurement carries out under 23 DEG C, D rays (wavelength 589nm).Above-mentioned solvent 1 is selected with solvent 2 The solvent that can be mixed each other, according to refractive index, for example, 1,1,1,3,3,3-hexafluoro-2-propanol, 2- propyl alcohol, chloroform, Carbon tetrachloride, toluene, glycerine equal solvent.

(3) mist degree of easy-adhesion polyester film

The mist degree of easy-adhesion polyester film is according to JIS K 7136：2000, using nephelometer (Japan electricity color system, NDH2000 it) measures.

(4) adaptation

It is formed in the adhesive layer of the polyester film obtained in embodiment described in the project that aforementioned hard conating is formed Hard conating.For being formed with the easy bonding polyester film of hard conating, the record of the 8.5.1 according to JIS-K5400-1990 is asked Go out the adaptation of hard conating and base film.

Specifically, using the cutter guide of clearance gap 2mm, hard conating is penetrated through, is assigned on hard conating face and reaches base 100 latticed notch of material film.Then, by cellophane tape (Nichiban systems, No. 405；24mm wide) it is adhered to net The cut sides of trellis, are wiped with rubber, it is made to adhere to completely.Later, cellophane tape is vertically folded into polarizing film from hard conating The hard conating face of protective film is removed, visually to count the grid folded the hard conating face of polarizer protection film from hard conating and removed Quantity, the adaptation of hard conating and base film is found out by following formula.It should be noted that the case where being partially stripped in grid Also it is counted as the grid removed.

Adaptation (%)={ 1- (quantity/100 for the grid removed) } × 100

(5) humidity resistance

To be formed with the polarizing film protection laminate film of aforementioned hard conating in hot and humid groove, in 85 DEG C, 85RH% In the environment of place 500 hours, then, remove hard conating and fold polarizer protection film, place 12 hours at room temperature.Later, Using the adaptation for finding out hard conating and base film with aforementioned same method, as humidity resistance.

(6) confficient of static friction, the coefficient of kinetic friction (μ s, μ d)

The friction coefficient of the polyester film obtained in embodiment is according to JIS K7125-1999 plastic films and piece friction system Number test method is measured using Tensilon (Toyo Baldwin, RTM-100).

(7) interference fringe improvement property (rainbow shape color)

The optics obtained in embodiments forms hard conating in the adhesive layer of easy bonding polyester film.It will be formed with The optics of hard conating is cut into the area of 10cm (thin-film width direction) × 15cm (film length direction) with easy bonding polyester film, Sample film is made.In gained sample film and (the day east electrician strain formula of stickup black glossy adhesive tape on the opposing face of hard conating face Commercial firm's system, vinyl tape No21；It is black).It is using the hard coating surface of the sample film as above, 3 type of wavelength daylight are white Color (National Palook, F.L 15EX-N 15W) is used as light source, from the tiltedly upper position pass with visually most strong visible reflectance It is observed under system (40~60cm of distance, 15~45 ° of angle apart from light source).

With following benchmark by the result divided rank to be visually observed.It should be noted that observation is to be proficient in the evaluation 5 progress, using most grades as opinion rating.It is assumed that become in 2 grades with point in the case of, using being divided into 3 The center of grade.For example, respectively ◎ and zero be each 2 and △ be 1 in the case of use the zero, ◎ to be for 1 and zero and △ Used in the case of each 2 zero, ◎ and △ for each 2 and zero be 1 in the case of use zero.

◎：From institute it is angled from be showed no rainbow shape color

○：Pass through the slightly visible rainbow shape color of a certain angle

△：Slightly observe rainbow shape color

×：Observe clearly rainbow shape color

(8) scratch resistance of coating layer

On rubfastness test machine (Daiei science essence device make made, RT-200) with 3cm (thin-film width direction) × 20cm (film length direction) installs optics easy-adhesion polyester film, in the payload header with counterweight (300g) The contact site of (2cmx2cm, 200g) and sample film use black lining paper (80 μm of thickness, 0.03 μ of arithmetic mean surface roughness M), with reciprocal 3 times of 1 reciprocal 20 seconds speed in the distance of 10cm.The sample film obtained by mounting on black lining paper, with visually true Whether recognize has scuffing.

○：Scuffing can not be confirmed on black lining paper or slight scuffing can confirm that according to position

△：It can confirm that slight scuffing on the whole on black lining paper

×：Scuffing can be clearly confirmed on black lining paper

(9) glass transition temperature

Made using differential scanning calorimetry (DSC) (Seiko Instruments systems, DSC6200) according to JIS K7121-1987 Resin sample 10mg is heated up in 25~300 DEG C of temperature range with 20 DEG C/min, and the extrapolation vitrifying obtained by DSC curve is turned Become start temperature as glass transition temperature.

(10) number-average molecular weight

Resin 0.03g is dissolved in tetrahydrofuran 10ml, uses GPC-LALLS device low angle light light-scattering photometers LS- 8000 (TOSOH Co., Ltd's system, tetrahydrofuran solvent, controls：Polystyrene), use 30 DEG C of column temperature, flow 1ml/ minutes, column (Showa Denko K. K shodex KF-802,804,806) measure number-average molecular weight.

(11) resin forms

Resin is dissolved in deuterochloroform, uses Valian Corporation magnetic nuclear resonance analyzers (NMR) Gemini-200 carries out 1H-NMR analyses, integrates ratio by it, determines mole % ratios of each composition.

(12) surface roughness (Ra)

Based on JIS-B0601-2001, Ra is measured with SURFCOM (registered trademark) 304B (Tokyo Seimitsu Co., Ltd's system). It should be noted that determination condition is in 0.08 μm of sampling (cut off), 2 μm of contact pilotage radius, the long 0.8mm of measurement, finding speed Lower progress in 0.03mm/ seconds.

(polymerization of polyester resin)

In the stainless steel autoclave for having blender, thermometer and partial reflux formula condenser, terephthaldehyde is put into 194.2 mass parts of dimethyl phthalate, 184.5 mass parts of dimethyl isophthalate, Sodium Dimethyl Isophthalate-5-sulfonate 14.8 Mass parts, 0.2 mass parts of 233.5 mass parts of diethylene glycol, 136.6 mass parts of ethylene glycol and tetra-n-butyl titanate esters, from At a temperature of 160 DEG C to 220 DEG C ester exchange reaction was carried out with 4 hours.Then, 255 DEG C are warming up to, reaction system is slowly depressurized Afterwards, so that it is reacted under the decompression of 30Pa 30 minutes 1 hour, obtain copolymer polyester resin (I).Gained copolymer polyester resin (I) It is pale yellow transparent.Measure the reduced viscosity of copolymer polyester resin (I), result 0.70dl/g.Vitrifying based on DSC turns Temperature is 40 DEG C, number-average molecular weight 20000.

The composition of copolymer polyester resin (I) is as described below.

Dicarboxylic acid component：49 moles of % of terephthalic acid (TPA), 48 moles of % of M-phthalic acid, M-phthalic acid 5- sodium 3 rub You are %

Diol component：60 moles of 40 moles of % of ethylene glycol, diethylene glycol %

(manufacture of polyester water dispersion)

Copolymer polyester resin (I) 30 mass parts, second are added in the reactor for having blender, thermometer and reflux 15 mass parts of glycol-n-butyl ether are heated with 110 DEG C, are stirred, resin is made to dissolve.After resin is completely dissolved, by 55 matter of water Amount part is stirred and is slowly added in polyester liquid.After addition, agitated liquid is simultaneously cooled to room temperature, and makes 28.2 matter of solid constituent Measure the milky polyester water dispersion (I α) of %.

(manufacture of polyurethane aqueous dispersion body)

In the four-hole boiling flask for having blender, coil condenser, nitrogen ingress pipe, silica dehydrator pipe and thermometer, throw Enter 43.75 mass parts of 4,4- dicyclohexyl methyl hydride diisocyanates, 12.85 mass parts of dimethylolpropionic acid, number-average molecular weight 2000 153.41 mass parts of polyhexamethylene carbonate diol, 0.03 mass parts of dibutyl tin laurate and as solvent 84.00 mass parts of acetone, in a nitrogen atmosphere, with 75 DEG C stir 3 hours, confirm reaction solution reach defined amine equivalent.It connects It, after which is cooled to 40 DEG C, adds 8.77 mass parts of triethylamine, obtain polyurethane prepolymer solution.Then, having In the reaction vessel of the homogenous disperse device of standby energy high-speed stirred, water 450g is added, is adjusted to 25 DEG C, while with 2000 minutes^-1It carries out It is water-dispersed to be stirred side addition polyurethane prepolymer solution progress.Later, under reduced pressure, a part for acetone and water is gone It removes, to prepare the water soluble polyurethane resin solution (II) of 37 mass % of solid constituent.The glass of gained polyurethane resin (II) Glass transition temperature is -30 DEG C.

(polymerization of blocked polyisocyanates system crosslinking agent)

In the flask for having blender, thermometer, reflux condensing tube, put into using hexamethylene diisocyanate as raw material The polyisocyanate compound (Asahi Kasei Chemicals systems, Duranate TPA) with isocyanurate structure 100 mass parts, 55 mass parts of propylene glycol monomethyl ether, 30 mass of polyethylene glycol monomethyl ether (average molecular weight 750) Part, in a nitrogen atmosphere, kept for 4 hours with 70 DEG C.Later, reacting liquid temperature is reduced to 50 DEG C, 47 matter of methyl ethyl ketoxime is added dropwise Measure part.The infrared spectrum for measuring reaction solution confirms that the absorption of isocyanate group disappears, obtains the sealing end of 75 mass % of solid constituent Polyisocyanates aqueous dispersions (III).

The polymerization of (oxazoline crosslinkers)

In the flask for having thermometer, nitrogen ingress pipe, reflux condenser, dropping funel and blender, conduct is put into 58 mass parts of ion exchange water of aqueous medium and the mixture of 58 mass parts of isopropanol and polymerization initiator (2,2 '-azos pair (2- amidine propanes) dihydrochloride) 4 mass parts.On the other hand, it in dropping funel, puts into as the poly- of Ju You oxazolinyls Conjunction property 16 mass parts of 2- isopropenyl -2- oxazolines of unsaturated monomer, methoxy polyethylene glycol acrylate (ethylene glycol it is flat Equal 9 moles of addition molal quantity, the villages Xin Zhong chemistry system) 32 mass parts of 32 mass parts and methyl methacrylate mixture, Under nitrogen atmosphere, it was added dropwise with 1 hour with 70 DEG C.After completion of dropwise addition, reaction solution is stirred 9 hours, it is cooling, to obtain solid The water-soluble resin (IV) of the Ju You oxazolinyls of 40 mass % of constituent concentration.

(polymerization of carbodiimide system crosslinking agent)

In the flask for having blender, thermometer, reflux condensing tube, 168 mass of hexamethylene diisocyanate is put into Part and polyethylene glycol monomethyl ether (M400, average molecular weight 400) 220 mass parts are stirred 1 hour with 120 DEG C, and then are added 4, 4 '-dicyclohexyl methyl hydride diisocyanate, 26 mass parts and 3- methyl-1s-phenyl -2- phosphorus-as carbodiimidization catalyst 3.8 mass parts of 1- oxides (being 2 mass % relative to whole isocyanates), 5 are stirred under stream of nitrogen gas, with 185 DEG C in turn Hour.The infrared spectrum of reaction solution is measured, confirms 2200~2300cm of wavelength^-1Absorption disappear.60 DEG C are naturally cooled to, is added 567 mass parts of ion exchange water obtain the carbodiimide water-soluble resin (V) of 40 mass % of solid constituent.

(epoxy crosslinking agent)

As epoxy crosslinking agent, Nagase ChemteX Corporation Denacol EX-521 (solids are used Constituent concentration 100%) (epoxy crosslinking agent (VI)).

(melamine series crosslinking agent)

As melamine series crosslinking agent, Dainippon Ink Chemicals Beccamine M-3 (solid component concentration 60%) are used (melamine series crosslinking agent (VII)).

(zirconia particles)

In 3 liters of glass container, pure water 2283.6g and oxalic acid dihydrate 403.4g is put into, is heated to 40 DEG C, system Standby 10.72 mass % oxalic acid aqueous solutions.It is slowly added aqueous zirconyl carbonate powder (ZrOCO when stirring the aqueous solution₃、AMR International Corp. systems are scaled ZrO₂Contain 39.76 mass %) 495.8g, mixing 30 minutes after, with 90 DEG C into Row heats for 30 minutes.Then, 25.0 mass % tetramethylammonium hydroxide aqueous solutions were slowly added with 1 hour (rubs chemical industry more Co. Ltd. system) 1747.2g.It is pulp-like in the moment mixed liquor, with ZrO₂Conversion contains 4.0 mass %.The slurry is moved Enter stainless steel autoclave container, with 145 DEG C of progress, 5 hours hydro-thermal process.The non-peptization object of product after the hydro-thermal process disappears It loses and complete solation.Gained colloidal sol contains as ZrO₂4.0 mass %, pH6.8, the average grain based on dynamic light scattering method Diameter is 19nm.In addition, being adjusted colloidal sol to ZrO with pure water₂2.0 mass % of concentration is simultaneously measured, and gained transmissivity is 88%.Pass through Transmission electron microscope observes particle, as a result the essentially ZrO of 7nm or so₂The aggregated particle of primary particle.For carry out on State ZrO obtained from hydro-thermal process₂The zirconia sol 4000g of 4.0 mass % of concentration, using ultrafiltration apparatus, while being slowly added Pure water side is cleaned and is concentrated, and ZrO is obtained₂Concentration 13.1 mass %, pH4.9, ZrO₂Transmissivity when 13.1 mass % of concentration 76% zirconia sol 953g.

The ZrO obtained from carrying out above-mentioned cleaning and concentration₂It is added in the zirconia sol 300g of 13.1 mass % of concentration After 20 mass % aqueous citric acid solutions 3.93g and 25 mass % tetramethylammonium hydroxide aqueous solutions 11.0g, and then use ultrafiltration apparatus It is concentrated, as a result obtains ZrO₂The zirconia sol 129g of the high concentration of 30.5 mass % of concentration.For the gained high concentration Zirconia sol, pH9.3, average grain diameter based on dynamic light scattering method are 19nm.In addition, the sediment of the zirconia sol It disappears, stablizes 1 month or more under conditions of 50 DEG C.

(titanium dioxide granule)

It will be with TiO₂The benchmark meter that converts includes 7.75 mass % titanium tetrachlorides (Osaka Titanium Technology Co., Ltd. systems) titanium tetrachloride aqueous solution 12.09kg and ammonium hydroxide (Ube Industries, Ltd's system) comprising 15 mass % ammonia 4.69kg is mixed, and prepares the stock white feed liquid of pH9.5.Then, it by after the slurries filtration, is cleaned with pure water, obtains solid constituent Content is the aqueous titanium acidleach cake 9.87kg of 10 mass %.Then, it is added comprising 35 mass % hydrogen peroxide in the filter cake After aquae hydrogenii dioxidi (Mitsubishi Gas Chemical Co., Ltd's system) 11.28kg and pure water 20.00kg, with 80 DEG C of temperature, stirring Lower heating 1 hour, and then pure water 57.52kg is added, it obtains with TiO₂Conversion benchmark meter includes the mistake of 1 mass % peroxidating metatitanic acids Titanium oxide aqueous acid 98.67kg.The titanium peroxide aqueous acid is transparent yellowish-brown, and pH is 8.5.

Then, mixed-cation exchanger resin (Mitsubishi Chemical's strain formula meeting in aforementioned titanium peroxide aqueous acid 98.67kg Society's system) 4.70kg is slowly added under stiring with SnO thereto₂The benchmark meter that converts includes 1 mass % potassium stannate (Showa chemical industry Co. Ltd. system) stannic acid aqueous solutions of potassium 12.33kg.Then, after the cation exchange resin separation of potassium ion etc. having been put into, It is put into autoclave (pressure-resistant Xiao Zi Industrial Co., Ltd system, 120L), is heated 18 hours with 165 DEG C of temperature.

Then, after gained mixed aqueous solution being cooled to room temperature, with ultra-filtration membrane device (Asahi Kasei Corporation's system, ACV- 3010) it concentrates, it is 10 mass %, water-dispersed molten comprising titanium system particle (hereinafter referred to as " P-1 ") to obtain solid component content Glue 9.90kg.Solids contained in the obtained colloidal sol is measured in aforementioned manners, and result is the crystal with rutile-type Structure, the titanium system particle (primary particle) that is formed by the composite oxides comprising titanium and tin.In turn, it measures in the titanium system particle The content of contained metal component, as a result in terms of the oxide of each metal component conversion benchmark, for TiO₂87.2 mass %, SnO₂ 11.0 mass % and K₂1.8 mass % of O.In addition, the pH of the mixed aqueous solution is 10.0.In turn, aforementioned includes titanium system particle Colloidal sol water-dispersed be transparent milky, the average grain diameter of aforementioned titanium system particle is 35nm contained in the colloidal sol water-dispersed, And then the distribution frequency of the big particle of the grain size with 100nm or more is 0%.In turn, the refractive index of gained titanium system particle can To be considered as 2.42.

(zirconium oxide/titanium dioxide hybrid particles)

The zirconia particles obtained among the above and titanium dioxide granule are mixed with respective ratio, to be made solid at Divide zirconium oxide/titanium dioxide hybrid particles of 13 mass % of concentration.

(formation of hard conating)

Using #10 bars, the hard conating formation of following compositions is gathered with what coating solution manufactured in aftermentioned embodiment The one side Nian Jie with polarizing film of ester film is to be dried 1 minute with 70 DEG C on the face of opposite side, solvent is removed.Then, it uses High-pressure sodium lamp irradiates 300mJ/cm to the film for being coated with hard conating²Ultraviolet light, obtain the inclined of the hard conating with 5 μm of thickness Shake piece protective film.

Hard conating formation coating fluid

65.00 mass % of methyl ethyl ketone

27.20 mass % of dipentaerythritol hexaacrylate

(villages Xin Zhong chemistry A-DPH)

6.80 mass % of polyethylene diacrylate

(villages Xin Zhong chemistry A-400)

1.00 mass % of Photoepolymerizationinitiater initiater

(Ciba Specialty Chemicals Co.Ltd. Irgacure 184)

(embodiment 1)

(modulation of coating fluid)

Modulate the coating fluid of following compositions.

34.94 mass parts of water

30.00 mass parts of isopropanol

7.24 mass parts of particle A-1

(zirconium oxide of average grain diameter 23nm/titanium dioxide hybrid particles,

Zirconium oxide quality relative to 75 mass % of zirconium oxide/titanium dioxide gross mass,

13 mass % of solid component concentration)

0.90 mass parts of particle B-1

(silicon dioxide gel, the 40 mass % of solid component concentration of average grain diameter 450nm)

Polyester water dispersion (I α) 17.92 mass parts

(28.2 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 2.90 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.26 mass parts of dispersing aid

(manufacture of easy-adhesion polyester film)

By the inherent viscosity (solvent as film raw material polymer：Phenol/tetrachloroethanes=60/40) be 0.62dl/g, And the PET resin pellet for containing substantially no particle is dried 6 hours under the decompression of 133Pa with 135 DEG C.Later, it supplies to crowded Go out machine, using about 280 DEG C of melting extrusions as sheet, keeps its quenching close in the rotation cooling metallic roll that surface temperature remains 20 DEG C Solidification is closed, non-stretched PET sheet is obtained.

By the non-stretched PET sheet with by heating roller group and infrared heater be heated to 100 DEG C, later with there is circumference The roller group of speed difference stretches 3.5 times along its length, obtains being uniaxially stretched PET film.

Then, 15 seconds dry with 80 DEG C after above-mentioned coating fluid being coated on the single side of PET film with roller coating method.It needs Illustrate, 0.12g/m is become with the coating weight after the drying after finally stretching²Mode be adjusted.Then, stenter is used 4.0 times are stretched in the width direction with 150 DEG C, in the state of fixing the length of the width direction of film, are heated with 230 DEG C 0.5 second, and then the relaxation processes 10 seconds of 3% width direction are carried out with 230 DEG C, obtain the easy-adhesion polyester of 38 μm of thickness Film.

(embodiment 2)

Instead of the particle A-1 of coating fluid, it is changed to gross mass of the quality of zirconium oxide relative to zirconium oxide and titanium dioxide Ratio be 50 mass % particle A-2 in addition to this obtain easy-adhesion polyester film similarly to Example 1.

(embodiment 3)

Instead of the particle A-1 of coating fluid, it is changed to gross mass of the quality of zirconium oxide relative to zirconium oxide and titanium dioxide Ratio be 25 mass % particle A-3 in addition to this obtain easy-adhesion polyester film similarly to Example 1.

(embodiment 4)

Instead of the coating fluid modulated, used in embodiment 1, modulate, using the coating fluid of following compositions, in addition to this, with Embodiment 1 gets similarly easy-adhesion polyester film.

37.23 mass parts of water

30.00 mass parts of isopropanol

3.79 mass parts of particle A-1

13 mass % of solid component concentration)

0.95 mass parts of particle B-1

Polyester water dispersion (I α) 18.77 mass parts

(28.2 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 3.03 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.27 mass parts of dispersing aid

(embodiment 5)

32.85 mass parts of water

30.00 mass parts of isopropanol

10.39 mass parts of particle A-1

13 mass % of solid component concentration)

0.87 mass parts of particle B-1

Polyester water dispersion (I α) 17.15 mass parts

(28.2 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 2.80 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.25 mass parts of dispersing aid

(embodiment 6)

39.17 mass parts of water

30.00 mass parts of isopropanol

7.24 mass parts of particle A-1

13 mass % of solid component concentration)

0.90 mass parts of particle B-1

13.70 mass parts of polyurethane aqueous dispersion body (II)

(37 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 2.90 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.26 mass parts of dispersing aid

(embodiment 7)

34.94 mass parts of water

30.00 mass parts of isopropanol

7.24 mass parts of particle A-1

13 mass % of solid component concentration)

0.90 mass parts of particle B-1

Polyester water dispersion (I α) 13.27 mass parts

(28.2 mass % of solid component concentration)

4.98 mass parts of polyurethane aqueous dispersion body (II)

(37 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 2.90 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.26 mass parts of dispersing aid

(embodiment 8)

Blocked isocyanate system crosslinking agent (III) of coating fluid is changed to the water-soluble resin of Ju You oxazolinyls (IV), and its content is adjusted, in addition to this, obtains easy-adhesion polyester film similarly to Example 1.

(embodiment 9)

Blocked isocyanate system crosslinking agent (III) of coating fluid is changed to carbodiimide water-soluble resin (V), and is adjusted In addition to this its content obtains easy-adhesion polyester film similarly to Example 1.

(embodiment 10)

Blocked isocyanate system crosslinking agent (III) of coating fluid is changed to melamine series crosslinking agent (VII), and is adjusted In addition to this its content obtains easy-adhesion polyester film similarly to Example 1.

(embodiment 11)

Blocked isocyanate system crosslinking agent (III) of coating fluid is changed to epoxy crosslinking agent (VI), and adjusts it and contains Amount, in addition to this, obtains easy-adhesion polyester film similarly to Example 1.

(embodiment 12)

Instead of the particle A-1 of coating fluid, it is changed to the particle A-4 that average grain diameter is 40nm, in addition to this, with embodiment 1 Get similarly easy-adhesion polyester film.

(embodiment 13)

Instead of the particle A-1 of coating fluid, it is changed to the particle A-5 that average grain diameter is 30nm, in addition to this, with embodiment 1 Get similarly easy-adhesion polyester film.

(embodiment 14)

The film thickness of coating layer is changed to 0.05 μm, in addition to this, obtains easy-adhesion polyester similarly to Example 1 Film.

(embodiment 15)

The film thickness of coating layer is changed to 0.075 μm, in addition to this, obtains easy-adhesion polyester similarly to Example 1 Film.

(embodiment 16)

The film thickness of coating layer is changed to 0.125 μm, in addition to this, obtains easy-adhesion polyester similarly to Example 1 Film.

(embodiment 17)

35.40 mass parts of water

30.00 mass parts of isopropanol

7.26 mass parts of particle A-1

13 mass % of solid component concentration)

0.36 mass parts of particle B-1

Polyester water dispersion (I α) 17.98 mass parts

(28.2 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 2.90 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.26 mass parts of dispersing aid

(embodiment 18)

34.48 weight portion of water

30.00 mass parts of isopropanol

7.22 mass parts of particle A-1

13 mass % of solid component concentration)

1.44 mass parts of particle B-1

Polyester water dispersion (I α) 17.88 mass parts

(28.2 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 2.90 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.26 mass parts of dispersing aid

(comparative example 1)

Instead of the particle A-1 of coating fluid, it is changed to the independent particle A-6 of non-mixed zirconium oxide without containing titanium dioxide, is removed Except this, easy-adhesion polyester film is obtained similarly to Example 1.

(comparative example 2)

Instead of the particle A-1 of coating fluid, it is changed to the independent particle A-7 of non-mixed TiO 2 series without containing zirconium oxide, Consider solid component concentration and adjust quality %, in addition to this, obtains easy-adhesion polyester film similarly to Example 1.

(comparative example 3)

35.71 mass parts of water

30.00 mass parts of isopropanol

7.27 mass parts of particle A-1

13 mass % of solid component concentration)

Polyester water dispersion (I α) 28.58 mass parts

(28.2 mass % of solid component concentration)

Blocked isocyanate system crosslinking agent (III) 1.38 mass parts

(75 mass % of solid component concentration)

0.30 mass parts of surfactant

(fluorine system, 10 mass % of solid component concentration)

3.00 mass parts of high boiling solvent

0.26 mass parts of dispersing aid

[table 1]

* 1：The data of the non-mixed independent particle of zirconium oxide

* 2：The data of the non-mixed independent particle of titanium dioxide

For the easy-adhesion polyester film obtained by each embodiment, scratch resistance is good, confficient of static friction, dynamic friction Coefficient also appropriateness, the transparency, adaptation, humidity resistance, low interference capability each assessment item in obtain satisfactory result. In contrast, for the easy-adhesion polyester film obtained by comparing example 1, zirconium oxide is free of in the particle A in coating layer, because This, cannot be satisfied in terms of humidity resistance.In addition, for the easy-adhesion polyester film obtained by comparing example 2, in coating layer Particle A in therefore cannot be satisfied in terms of scratch resistance without titanium dioxide.Moreover, example 3 by comparing is obtained Easy-adhesion polyester film, without the lubricant particle B in coating layer, therefore, friction coefficient is big.

(embodiment 19)

The easy-adhesion for being obtained the antiglare layer formation of following compositions in embodiment 1 with coating solution using #5 bars It is 1 minute dry with 70 DEG C on the coating layer of polyester film, solvent is removed.Then, for being coated with the film of antiglare layer, make With high voltage mercury lamp radiation 300mJ/cm²Ultraviolet light, obtain the laminated polyester film with the antiglare layer of 5 μm of thickness.It is assigned The preferred laminated polyester film of anti-glare is given.

Antiglare layer formation coating fluid

34 mass parts of toluene

50 mass parts of pentaerythritol triacrylate

Silica (1 μm of average grain diameter) 12 mass parts

1 mass parts of organosilicon (levelling agent)

1 mass parts of Photoepolymerizationinitiater initiater

(Ciba Specialty Chemicals Co.Ltd. Irgacure 184)

(embodiment 20)

The middle index layer formation of following compositions obtained with coating solution in embodiment 1 using bar coater easy to stick On the coating layer of connecing property polyester film, after being dried 1 minute with 70 DEG C, high voltage mercury lamp radiation 400mJ/cm is used²Ultraviolet light, obtain To 5 μm of middle index layer of dry film thickness.Then, using bar coater, using method same as middle index layer, by following groups At high refractive index layer formation be formed in and be formed by middle index layer with coating fluid, and then using same as middle index layer Method be formed on the low-index layer formation coating fluids of following compositions, obtain the stacking polyester for being laminated with anti-reflection layer Film.Obtain the preferred laminated polyester film with antireflection.

Middle index layer, which is formed, uses coating fluid (refractive index 1.52)

70 mass parts of dipentaerythritol hexaacrylate

Bis- (3- acryloxy -2- hydroxy propyloxy groups) hexanes of 1,6-

30 mass parts

4 mass parts of Photoepolymerizationinitiater initiater

(Ciba Specialty Chemicals Co., Ltd. system, Irgacure 184)

100 mass parts of isopropanol

High refractive index layer, which is formed, uses coating fluid (refractive index 1.64)

ITO particles (0.07 μm of average grain diameter) 85 mass parts

15 mass parts of tetramethylol methane triacrylate

Photoepolymerizationinitiater initiater (KAYACURE BMS, Japanese chemical drug system) 5 mass parts

900 mass parts of butyl alcohol

Low-index layer, which is formed, uses coating fluid (refractive index 1.42)

Bis- acryloxy -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- of 1,10-, ten hexafluoro decane, 70 mass parts

10 mass parts of dipentaerythritol hexaacrylate

60 mass parts of aerosil particles (XBA-ST, Nissan Chemical system)

Claims

1. a kind of easy-adhesion polyester film is at least in single side there is the polyester film of coating layer, the coating layer to contain： Zirconium oxide/titanium dioxide hybrid particles A；Lubricant particle B；With, binder resin, the zirconium oxide/titanium dioxide mixing Grain A in zirconium oxide relative to zirconium oxide and titanium dioxide gross mass containing ratio be 10~90 mass %, the lubricant The average grain diameter of particle B is 200nm or more.

2. easy-adhesion polyester film according to claim 1, wherein zirconium oxide/titanium dioxide hybrid particles A's is averaged Grain size is 5~200nm.

3. easy-adhesion polyester film according to claim 1 or 2, wherein lubricant particle B consolidates relative to coating layer The containing ratio of body ingredient is 0.1~20 mass %.

4. easy-adhesion polyester film described in any one of claim 1 to 3, wherein zirconium oxide/titanium dioxide mixing Particle A is 2~50 mass % relative to the containing ratio of the solid constituent of coating layer.

5. a kind of laminated polyester film, in the coating layer of easy-adhesion polyester film according to any one of claims 1 to 4 Upper a kind in the group being made of hard conating, antiglare layer, anti-glare anti-reflection layer, anti-reflection layer and low reflection layer with On functional layer.