CN103842854B

CN103842854B - Water-dispersed composition and the optical film using the water-dispersed composition

Info

Publication number: CN103842854B
Application number: CN201280048254.XA
Authority: CN
Inventors: 林美笑; 崔城蘭
Original assignee: Kolon Corp
Current assignee: Kolon Corp
Priority date: 2011-09-30
Filing date: 2012-09-27
Publication date: 2018-02-02
Anticipated expiration: 2032-09-27
Also published as: JP2015163712A; CN103842854A; JP2015501230A; TWI527690B; TW201323208A; CN106338782B; JP5864760B2; CN106338782A; JP6133927B2

Abstract

The invention provides a kind of optical film, and it does not have rainbow phenomena and has high transmission rate and low haze.Moreover, it relates to water-dispersed composition and the optical film using the water-dispersed composition.More particularly it relates to can with high index of refraction, overcome rainbow phenomena and in the hot and humid lower water-dispersed composition with excellent adhesiveness, and the optical film of the use water-dispersed composition.

Description

Water-dispersed composition and the optical film using the water-dispersed composition

Technical field

Following disclosure is related to water-dispersed composition and the optical film using the water-dispersed composition.It is more specific and Speech, disclosure below relate to high index of refraction, overcome rainbow phenomena and hot and humid lower with excellent viscous The water-dispersed composition of conjunction property, and the optical film using the water-dispersed composition.It will not be produced in addition, present disclosure is related to Interference fringe phenomenon has high transmission rate and the optical film of low haze simultaneously.

Background technology

Optical film is used as the film of the optical component of display, and it is used as liquid crystal display (LCD) back light unit（BLU）'s Optical material, or as the various displays of protection（Such as LCD, plasma display（PDP）Or touch panel etc.）'s The optical component on surface.In this optical film, it is desirable to the excellent transparency and observability, and using special with excellent machinery The biaxially oriented polyester film of property and electrology characteristic is as basement membrane.

In general, because biaxially oriented polyester film has excellent dimensional stability, caliper uniformity and translucency, institute Various industrial materials and optical material are widely used as with biaxially oriented polyester film.

This biaxially stretched polyester laminated film be used for it is optical in the case of because case hardness is low, and wearability or Resistance to marring deficiency, therefore when the film is used as the optical component of various displays, easily sent out because rubbing or being contacted with object Raw surface damage.Therefore, it is this impaired in order to prevent, hard conating is laminated on the surface of the film, and to improve polyester film（That is base Film）Close adhesion between hard conating, prime coat is formed as intermediate layer.

Prime coat with copolymer polyester resin that polyester film has excellent adhesiveness generally by forming.But it is being used alone In the case of copolymer polyester resin, the cohesive with polyester base film is enough, but using prismatic lens, antireflection layer or When using copolymer polyester resin after the various post-processings processing of hard conating etc., copolymer polyester resin is probably inadequate.In order to Make up the problem, carried out research primer coating layer method come when preparing polyester using with excellent easy bonding Property, pliability and the polyurethane resin of wearability and strong bonding improve bonding force, be thus used in the various fields for requiring bonding In.But when prime coat is made up of polyurethane resin, with outer layer（Such as hard conating etc.）Bonding force it is excellent, but with it is poly- Ester film（It is basement membrane）Bonding force deficiency, so as to which enough bondings with outer layer can not be obtained.

In addition, as one of method of cohesive after evaluation post-processing processing, hot and humid（65 DEG C, 90%）Under comment During valency moisture-proof, the back side of post-processing film is penetrated into due to moisture to cause bonding force to deteriorate, and therefore, carried out to solving The research of the method for the problem.

In order to solve the problem, in Korean Patent No.10-1050216（Patent document 1）In disclose using crosslinking dosage form The method that durability is improved into polymer network.

In addition, in order to improve the close adhesion between basic unit and hard conating and eliminate due between hard conating and polyester film Rainbow phenomena caused by huge refractive index difference, bottom is used as usually using acrylic resin, polyurethane resin and polyester resin etc. The material of enamelled coating.As related invention, in the flat 10-110091 of Japanese Patent Laid-Open No.（Patent document 2）In disclose and make Improve the method with the cohesive of basement membrane with the aqueous dispersions of polyester resin and fluorine compounds.But such as the institute in related invention It has been shown that, resistance to blocking (blocking resistance) is improved to increase glass transition temperature in addition fluorine compounds In the case of, because glass transition temperature（Tg）Quick increase, it is abundant without occurring under heat treatment temperature when preparing film Degraded, this causes subsequent region is cracked or stayed in film, and whiting is produced in film so that the film is uncomfortable Share and make optical film.

In addition, in order to improve the close adhesion between basic unit and hard conating and eliminate due between hard conating and polyester film Rainbow phenomena caused by huge refractive index difference, it is used as intermediate layer usually using acrylic resin or polyurethane resin etc..However, Using only above-mentioned resin formed primer coating in the case of, refractive index is about 1.5, this close to hard conating refractive index, this It is because the general surface refractive index of biaxially oriented polyester film is 1.64 and the general refractive index of hard conating is 1.52.Therefore, It may not eliminate due to optical interference phenomena caused by the huge refractive index difference between hard conating and polyester film, and When the film is used in display member, this rainbow phenomena can cause kopiopia and reduce display visuality.

As the method for overcoming this kopiopia, disclosed in Korea Patent Laid discloses No.10-2011-0034784 By the side of basement membrane coating include refractive index be 1.54 to 1.59 polyurethane binder polyurethane coating composition with Include the acrylic coating composition formation for the acryloid cement that refractive index is 1.4 to 1.5 in the opposite side coating of basement membrane Optical film.In above-mentioned related invention, adjusted by changing the structure of the isocyanates used in polyurethane coating composition Refractive index is saved, so as to overcome rainbow phenomena.

In addition, as the related invention for overcoming rainbow phenomena, a kind of hard apply is disclosed in Korean Patent No.10-0994051 Tunic, it includes the hard conating and hard for this being coated with the hard coating composition comprising the particulate that particle mean size is 1 to 30 μm The pre-hardening thickness of coating, and the refractive index of the minimal reflection wavelength with 500+/- 50 μm and 1.58+/- 0.1.In above-mentioned correlation In technology, refraction is adjusted by adding organic bead selected from silicones bead and acrylic resin bead into hard conating Rate.However, in the case of using organic bead in hard conating, the transparency of hard conating in itself is deteriorated, can so as to reduce Depending on property.

As described above, in order to overcome the rainbow phenomena of hard coating film, coating group of the regulation for hard conating has been developed Compound and organic or inorganic particulate are to adjust the various technologies of refractive index, and because refractive index is according to coating composition and particulate Combination and it is different, carried out find obtain ideal refractive rate combination research.

The content of the invention

One embodiment of the invention, which is related to, provides a kind of water-dispersed composition, and the water-dispersed composition has in high temperature Excellent adhesiveness, high index of refraction and lower glass transition temperatures under high humidity, and be related to and apply the water-dispersed composition Optical film.

In addition, another embodiment of the present invention, which is related to, provides a kind of water-dispersed composition, the water-dispersed composition passes through Increase crosslink density can have excellent cohesive and overcome rainbow phenomena and optical property, and is related to and applies the water The optical film of dispersive composition.

More particularly it relates to carry

It is described for the optical polyester film that can not cracked on the surface when forming film with the prime coat in region Optical film overcomes optical property（Particularly rainbow phenomena etc.）, and with excellent cohesive under hot and humid.

And then the present invention relates to by making polyester resin and inorganic particles be mutually mixed and provide a kind of primer coating composition Thing, the primer coating compositions have polyester film（It is basement membrane）Middle refractive index between the refractive index of hard conating, and It is related to and forms primer coating by the way that the primer coating compositions are coated on the one or both sides of the polyester base film to carry For a kind of optical film, wherein overcoming rainbow phenomena.

Optical film the present invention relates to water-dispersed composition and using the water-dispersed composition.

In a general aspect, there is provided a kind of to be coated on the one of the basement membrane including polyester base film and with coating composition The optical film of primer coating on side or both sides, the coating composition include polyester resin and the refraction of refractive index 1.4 to 1.6 The inorganic particles of rate 1.8 to 2.2, thus with 1.56 to 1.6 total refractive index, the wherein dry coating thickness of primer coating is 50 To 150nm.

The inorganic particles can have 1 to 50nm particle mean size.

The inorganic particles can be the zirconium oxide that surface is modified.

The zirconium oxide that the surface is modified can have acyl group or alkylation group in its surface, and can use Na⁺As counter ion.

The optical film can be further 1.51 to 1.53 comprising refractive index on the one or both sides of primer coating Acrylic resin coating.

The acrylic resin coating can have 1 to 10 μm of dry coating thickness.

In the case where acrylic resin coating is formed only on side, the film can with less than 1.0% mist degree and More than 91% total light transmittance, and in the case where acrylic resin coating is formed on both sides, the film can have 0.5% with Under mist degree and more than 92% total light transmittance.

In another general aspect, there is provided a kind of water-dispersed composition for primer base, the water-dispersed composition Selected from the first water-dispersed composition, the second water-dispersed composition and the 3rd water-dispersed composition, first water-dispersed composition Comprising by linear polymers of 10 to the 75 weight % with two end groups and 25 to 90 weight % with least three end groups The water dispersible polyurethane resin of branched polymer composition, second water-dispersed composition, which includes, passes through 20 to 40 moles of % of polycondensation 2,6- naphthalenedicarboxylic acids, 1 to the 10 mole of % aromatic dicarboxylic acid comprising sulfonate, 1 to 10 mole of % aromatic dicarboxylic acid, 10 to 30 moles of % double [4 (2- hydroxyl-oxethyls) phenyl] fluorenes represented by chemical formula 1 below, 1 to 10 mole of % by following The triglyceride compound and 30 to the 60 moles of % obtained polyester resin of diol compound that chemical formula 2 represents, and described the First and second water-dispersed composition is mixed with each other in three water-dispersed compositions.

[chemical formula 1]

[chemical formula 2]

(in chemical formula 2, R₁To R₃It is each independently selected from hydrogen and (C1-C30) alkane with or without unsaturated hydrocarbons Base.)

The end group of the water dispersible polyurethane resin can be closed partly or entirely with inorganic acid salt.

The water dispersible polyurethane resin can be prepared as follows：By 39 to 45 weight % polyalcohol, 0.3 to 1.2 weight % Trimethylolpropane and 50 to 57 weight % isocyanate compound react with each other it is pre- for NCO to prepare end group Polymers, then the prepolymer and 3 to 4 weight % inorganic acid salt are reacted to close the isocyanates end with ionic group again Base.

The water dispersible polyurethane resin can have 10,000 to 20,000 weight average molecular weight.

First water-dispersed composition can include 5 to 10 weight % water dispersible polyurethane adhesive, 0.1 to 0.5 weight The % wetting agent based on silicones, 0.1 to 0.5 weight % colloidal silica particles, and the water of surplus, the moisture is measured to dissipate Polyurethane binder includes the water dispersible polyurethane resin and water with the solid content with 10 to 30 weight %.

The colloidal silica particles can have 50 to 1000nm particle mean size.

The aromatic dicarboxylic acid can be selected from dimethyl terephthalate (DMT), terephthalic acid (TPA), M-phthalic acid, 1,2- Any in naphthalenedicarboxylic acid, 1,4- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 1,3- pentamethylene dioctyl phthalate and 1,4 cyclohexanedicarboxylic acid Kind or at least two mixture, the aromatic dicarboxylic acid comprising sulfonate can for selected from 2,5- dicarboxyl benzene sulfonic acids Sodium, 5- sulfo-isophthalic acids, 2- sulfo-isophthalic acids, 4- sulfo-isophthalic acids and 4- sulfo groups-naphthalene -2,6- diformazans Any of acid or at least two mixture, and the diol compound can be selected from ethylene glycol, diethylene glycol, three Ethylene glycol, tetraethylene glycol, five ethylene glycol, six ethylene glycol, propane diols (propylene glycol), tripropylene glycol, 1,3- the third two Any of alcohol, 1,3 butylene glycol, propane diols (propane diol), bisphenol-A, bisphenol b or at least two mixture.

The polyester resin can be with 1.58 to 1.64 refractive index and 40 to 60 DEG C of glass transition temperature.

Second water-dispersed composition can include 10 to 40 weight % water dispersible polyester adhesive, 0.1 to 0.5 weight % wetting agent, the silicon dioxide microparticle of 0.1 to 0.5 weight % particle mean size 100 to 200nm are measured with 2 to 10 weight %'s Total solid content, the water dispersible polyester adhesive include the polyester resin and water with the solid content with 10 to 40 weight %.

Second water-dispersed composition can further include hydrophilic organic solvent and surfactant.

3rd water-dispersed composition can include the mixing of 5 to 10 weight % the first and second water-dispersed compositions Thing, 0.1 to the 0.5 weight % wetting agent based on silicones, 0.1 to 0.5 weight % colloidal silica particles, and surplus Water.

The mixture of first and second water-dispersed composition can be the first and second water-dispersed compositions with 1:9 to 5:Mixture of 5 weight than mixing.

The colloidal silica particles can have 50 to 1000nm particle mean size.

3rd water-dispersed composition can have 1.57 to 1.62 refractive index.

In another general aspect, there is provided a kind of optical film, the optical film includes by coating selected from above-mentioned first, the The primer coating that any one of two and the 3rd water-dispersed composition water-dispersed composition is formed.

The dry coating of the primer coating can be 50 to 100nm.

The primer coating can meet following physical property：The swelling ratio measured with equation 1 below is 35 to 100, The gel fraction measured with equation 2 below is 75 to 85, and glass transition temperature is more than 60 DEG C.

[formula 1]

Swelling ratio=（Weight-original weight after holding）/ original weight × 100

（In equation 1, the weight after the holding refers to dry coating film（About 1g）Immerse distilled water（50g）In and 70 The weight that measures after DEG C being kept for 24 hours.）

[formula 2]

Gel fraction=（Dried weight/original weight）×100

（In formula 2, the dried weight refers to dry coating film（About 1g）Immerse distilled water（50g）In, 70 DEG C kept for 24 hours, the weight that measure after then the film after the holding is dried 3 hours at 120 DEG C again.）

Beneficial effect

As described above, the bonding force for being suitable as hard coating film can be had according to the optical film of the present invention and overcome Rainbow phenomena.

In addition, in the case where the optical film also includes hard conating because the optical film with more than 91% it is high total Light transmittance and less than 1% low haze, so as to which the optical film can meet the requirement of excellent optical property.

In addition, excellent moisture-proof can be had according to the water-dispersed composition of the present invention and overcome rainbow phenomena.

And then it can be adjusted according to the optical film of the present invention by adjusting the content ratio of the first and second water-dispersed compositions Refractive index and bonding force are saved, and in the case of by online process applied coating composition, is advantageous to pass through drawing process Adjust coating layer thickness.

In addition, according to the present invention it is possible to refractive index is adjusted, so as to overcome rainbow phenomena.In addition, adding has three The prepolymer of the urethane composition of functional group increases crosslink density, so as to the excellent moisture resistance under hot and humid.

Brief description of the drawings

Fig. 1 is the cross section of the first instantiation of the optical film for showing an exemplary according to the present invention View；

Fig. 2 is that the cross section for the second instantiation for showing optical film in accordance with an exemplary embodiment of the invention regards Figure；

Fig. 3 is that the cross section for the 3rd instantiation for showing optical film in accordance with an exemplary embodiment of the invention regards Figure；

Fig. 4 is that the cross section for the 4th instantiation for showing optical film in accordance with an exemplary embodiment of the invention regards Figure；And

Fig. 5 is the photo of the evaluation criterion for the method for showing the adhesion according to the evaluation present invention.

[detailed description of main element]

10：Polyester base film

20、20a、20b：Primer coating

30、30a、30b：Hard conating

Embodiment

It will be described in detail first embodiment of the invention.

First embodiment of the invention is related to one kind and includes polyester base film and be coated on the basement membrane with coating composition One or both sides on primer coating optical film, the coating composition include refractive index 1.4 to 1.6 polyester resin and The inorganic particles of refractive index 1.8 to 2.2 and thus have 1.56 to 1.6 total refractive index, wherein the primer coating is dry-coated Thickness degree is 50 to 150nm.

In first embodiment of the invention, the inorganic particles can have 1 to 50nm particle mean size.

In first embodiment of the invention, the inorganic particles can be the zirconium oxide that surface is modified.

In first embodiment of the invention, zirconium oxide that the surface is modified can have in its surface acyl group or Alkylation group, and Na can be used⁺As counter ion.

In first embodiment of the invention, the coating composition can include 5 to 30 weight % refractive index 1.4 The wetting agent of polyester resin, 0.1 to 0.4 weight %, the dioxy of 0.1 to 0.5 weight % particle mean size 100 to 200nm to 1.6 SiClx and 0.5 to 30 weight the % weight of solid content 5 to 40 % moisture dissipate inorganic particles, and the total solid content of said composition Can be 2 to 10 weight %.

In first embodiment of the invention, the optical film can be further contained in the side or two of primer coating The acrylic resin coating of the refractive index 1.51 to 1.53 formed on side.

In first embodiment of the invention, the dry coating thickness of the acrylic resin coating is 1 to 10 μm.

It is described in the case where acrylic resin coating is formed only on side in first embodiment of the invention Film can have less than 1.0% mist degree and more than 91% total light transmittance, and formed in acrylic resin coating on both sides In the case of, the film can have less than 0.5% mist degree and more than 92% total light transmittance.

The present inventor is by having found that following facts completes first embodiment of the invention.In order that obtain priming paint The refractive index of coating has 1.64（It is polyester film（Basement membrane）Refractive index）With 1.52（It is the refractive index of hard conating）In Between be worth, the organic bond of coating composition including refractive index 1.4 to 1.6 and the inorganic particles of refractive index 1.8 to 2.2 and by In the case that this is conditioned so as to have 1.56 to 1.6, more preferably 1.58 total refractive index and be applied, the refraction of primer coating Rate is similar to the refractive index of basement membrane, so as to overcome rainbow phenomena.

In addition, the present inventor is by having found that following facts completes first embodiment of the invention.Using Below particle mean size 50nm, more specifically in the case of 1 to 50nm inorganic particles, after polyester film is manufactured, when one When hard conating is formed on side, optical film can meet following physical property：Total light transmittance be more than 91%, and mist degree be 1% with Under, and when hard conating is being formed on both sides simultaneously, optical film can meet following physical property：Total light transmittance is more than 92%, And mist degree is less than 0.5%, it means that optical property is further overcome.

More specifically, by finding that following facts completes first embodiment of the invention.Made using polyester resin For organic bond, using zirconia sol as inorganic particles, the zirconium oxide that is modified especially with surface, so as to gram The coalescence of clothes and adhesive, and the storage-life of coating composition can be improved, so as to make it suitable for manufacturing the work of polyester film Skill, the technique are continuous processing.

First embodiment of the invention is described with reference to the accompanying drawings.First instantiation of first embodiment of the invention It is related to a kind of polyester film for optical applications, as shown in figure 1, the polyester film includes polyester base film 10 and applied with coating composition Primer coating 20 of the cloth on the side of the polyester base film 10, the coating composition include the polyester of refractive index 1.4 to 1.6 Resin and the inorganic particles of refractive index 1.8 to 2.2 and thus have 1.56 to 1.6 total refractive index.

Second instantiation of first embodiment of the invention is related to a kind of polyester film for optical applications, such as Fig. 2 Shown, the polyester film includes polyester base film 10 and the priming paint being coated on coating composition on the both sides of the polyester base film 10 applies Layer 20a and 20b, the coating composition include refractive index 1.4 to 1.6 polyester resin and refractive index 1.8 to 2.2 it is inorganic micro- Grain and thus have 1.56 to 1.6 total refractive index.

3rd instantiation of first embodiment of the invention is related to a kind of polyester film for optical applications, such as Fig. 3 Priming paint painting shown, that the polyester film includes polyester base film 10, is coated on coating composition on the side of the polyester base film 10 Layer 20 and acrylic resin coating 30, the coating composition include the polyester resin and refractive index 1.8 of refractive index 1.4 to 1.6 To 2.2 inorganic particles thus there is 1.56 to 1.6 total refractive index.

4th instantiation of first embodiment of the invention is related to a kind of polyester film for optical applications, such as Fig. 4 Priming paint painting shown, that the polyester film includes polyester base film 10, is coated on coating composition on the both sides of the polyester base film 10 Layer 20a and 20b and acrylic resin coating 30a and 30b, the coating composition include the polyester resin of refractive index 1.4 to 1.6 Thus there is 1.56 to 1.6 total refractive index with the inorganic particles of refractive index 1.8 to 2.2.

But show that these examples are in order to which the first embodiment is described in detail, but the present invention is not limited to these.

Hereinafter, first embodiment of the invention will be described in further detail.

In view of light transmittance, the basement membrane preferably used in first embodiment of the invention is polyester film, more specifically, For polyethylene terephthalate film.As this polyethylene terephthalate film, preferably using poly- pair stretched PET film, and can use be stretched uniaxially or biaxially polyethylene terephthalate film.It is used The thickness of basement membrane can be 25 to 250 μm, but be not restricted to that this.

In first embodiment of the invention, the primer coating is made up of coating composition, the coating composition The inorganic particles of polyester resin and refractive index 1.8 to 2.2 comprising refractive index 1.4 to 1.6, thus with 1.56 to 1.6 it is total Refractive index.In 1.56 to 1.6 ranges of indices of refraction, the primer coating can use the moisture prepared to dissipate emulsion coating, make Other additives are used during standby water dispersion emulsion, therefore the water dispersion emulsion has the refractive index similar to polyester base film.

More specifically, the polyester resin can preferably have 1.4 to 1.6 refractive index.By using the polyester Resin can increase the bonding force with basement membrane, and the dosage of inorganic particles can be reduced, and it is possible thereby to reduce cost, because The refractive index of polyester resin is higher than other resin combinations, and is produced in recycling in the technical process for manufacturing the film Bad products when, reduce the deterioration of the color change and physical property of section, so as to reduce film cost.

In addition, the inorganic particles can have 1.8 to 2.2 refractive index.For example, the inorganic particles can be ZnO, TiO₂、CeO₂、SnO₂And ZrO₂In one kind or at least two, but be not restricted to that these.Preferably, zirconium oxide can be used （ZrO₂）., can be with excellent in view of overcoming and the coalescence of polyester resin (it is adhesive resin) and increasing the stability of composition The zirconium oxide that choosing is modified using surface.The zirconium oxide that the surface is modified can have acyl group or alkylation base in its surface Group, and can preferably use Na⁺As counter ion.The acyl group includes acetyl group, propiono, malonyl and benzoyl Deng.

The method for preparing the zirconium oxide that the surface is modified is as follows.By zirconates（Basic zirconium chloride etc.）With alkali（Such as hydroxide Sodium, potassium hydroxide or ammoniacal liquor etc.）Reacted in water at a temperature of 10 to 50 DEG C, to obtain the slurry of zirconia particles, and will The slurry filtration simultaneously washs.Then, 1 to 3 mole of organic acid is added based on 1 mole of zirconium oxide thereto（Such as carboxylic acid, hydroxyl Yl carboxylic acid, formic acid or acetic acid etc.）, and be heat-treated under the water temperature more than 170 DEG C.

The counter ion is not limited to Na⁺, but because the ionogen of the polyester binder as primary binder is NaSO₃, in order to keep ionic equilibrium, it is preferable to use Na⁺.When adding other ionogens, polyester binder can be produced Coalescence.

The zirconia particles being modified using the surface are so that increase composition stability, and gather in manufacture Ethylene glycol terephthalate（PET）The technique of film（It is continuous processing）During can obtain have stablize physical property Online coating（ILC）Film.In addition, the inorganic particles can have 1 to 50nm particle mean size.It is it is highly preferred that described inorganic Particulate can have 1 to 10nm particle mean size.In the case where the size of the inorganic particles is less than 1nm, further speed up Coalescence, so that it is likely to reduced the storage period of composition, and in the case where size is more than 50nm, optical film may be increased Optical property, particularly mist degree.

Used it is highly preferred that the inorganic particles can dissipate collosol state with the weight of solid content 5 to 40 % moisture, and In the case, pH can be 7 to 9, more preferably 8 to 8.5.When solid content is below 5 weight %, it may be difficult to add enough The inorganic particles of amount, and when solid content is more than 40 weight %, there may be coalescence in particulate inorganic material itself.

First embodiment of the invention is characterised by, using comprising polyester resin and inorganic particles so as to 1.56 To the coating composition of 1.6 total refractive index.In the case where refractive index is less than 1.56, between coating composition and basement membrane Refractive index difference is big so that rainbow phenomena becomes serious, and because the content of high refractive particles needs to be higher than the scope of the present invention To increase refractive index, the generation of the spot in appearance of coat can be increased when manufacturing the film, and due to manufacturing cost increase, drop Low commercialized possibility.In addition, in the case where refractive index is higher than 1.6, the refractive index between coating composition and hard conating Difference is big, so as to which rainbow phenomena becomes serious.

In first embodiment of the invention, for primer coating coating composition can be moisture dissipate or water-based group Compound, it includes polyester resin, wetting agent, the silica of particle mean size 100 to 200nm, and the weight of solid content 5 to 40 % Moisture dissipate inorganic particles.

It is highly preferred that the coating composition for primer coating can including 5 to 30 weight % refractive index 1.4 to 1.6 polyester resin, 0.1 to 0.4 weight % wetting agent, 0.1 to 0.5 weight % particle mean size 100 to 200nm titanium dioxide Silicon and 0.5 to 30 weight the % weight of solid content 5 to 40 % moisture dissipate inorganic particles with always containing admittedly with 2 to 10 weight % Amount.

As the coating method for being used to form the coating composition of primer coating, can use in oriented polyester film The online rubbing method of said composition is coated with technical process on the surface, the offline coating after the film is manufactured can also be used Method.Both approaches can use.

Preferably, online rubbing method can be used, because be coated and film forming simultaneously, can reduce and be manufactured into This, and the thickness of coating can be changed by draw ratio.

In first embodiment of the invention, when needed, it may further include in the side of primer coating or two The acrylic resin coating formed on side, the acrylic resin coating have 1.50 to 1.54, preferably 1.51 to 1.53 folding Penetrate rate.In addition, the acrylic resin coating can have 1 to 10 μm of thickness.

The acrylic resin coating can be made up of any component, as long as the component can form hard conating.More specifically Ground, as commercial examples, Z-711 products (AIKACo.) can be used, but be not restricted to that this.

In the present invention, primer coating is formed to meet the requirement of the refractive index of the present invention and thickness so that optical film can To meet following physical property：When forming acrylic resin coating on side, mist degree is less than 1.0, and total light transmission Rate is more than 91%, and when forming acrylate resin layer on both sides simultaneously, mist degree is less than 0.5, and total light transmittance is More than 92%.

Hereinafter, the detailed description of first embodiment of the invention will be provided by embodiment.But the present invention is not limited to The following examples.

The method of the measurement physical property shown in embodiment and comparing embodiment below is as follows.

1）The measurement of total light transmittance

The total light transmittance of whole film uses haze meter（Nippon Denshoku300A）Measurement.

2）The measurement of refractive index

2-1）Measurement for the refractive index of the polyester resin of primer coating

Water dispersible polyester resin combination is applied on polycarbonate membrane and dried.Then, at room temperature using refraction Instrument（Abbe refractometer, ATAGOCo., DR-M2 ,@550）Measure its refractive index.

2-2）The measurement of the refractive index of inorganic particles

Liquid inorganic particulate is added to by the water-based of refractive index 1.52 with 10 weight %, up to 10 to 50 weight % scope In resin, it is applied on polycarbonate membrane, and dries.Then, at room temperature using refractometer（Abbe refractometer, ATAGO Co., DR-M2 ,@550）Measure its refractive index.

The result of measurement is drawn into curve, and predicted based on fraction of particle and the hypothesis that refractive index is proportional to one another when inorganic Material has refractive index during 100% content.

3）The measurement 1 of rainbow phenomena degree

After according to embodiment and comparing embodiment manufacture optical film, hard conating is carried out on one side thereof（Refractive index 1.52） Processing, and opposite side blacking.Then, it is confirmed whether to produce rainbow phenomena with bore hole.In darkroom mesh is carried out under three wavelength lamps Survey.

Evaluation criterion is as follows.

Well：There is not rainbow phenomena, and color impression is uniform.

It is medium：It is faint rainbow phenomena occur, and color impression is uniform.

Difference：There is rainbow phenomena strongly, and color impression is strong.

4）The measurement 2 of rainbow phenomena degree

After according to embodiment and comparing embodiment manufacture optical film, hard conating is carried out on one side thereof（Refractive index 1.52） Processing, and opposite side blacking.Then the reflection graphic patterns in visible-range are measured using UV- visible (CARY5000).

Well：Ripple amplitude 500 to 600nm reduces the ripple amplitude compared with the ripple amplitude of other wave-length coverages Less than 1%.

It is medium：Ripple amplitude 500 to 600nm reduces the ripple amplitude compared with the ripple amplitude of other wave-length coverages Less than 3%.

Difference：The wave-length coverage of ripple amplitude reduction is not or the wavelength in the absence of ripple amplitude reduction 500 to 600nm Scope.

5）With the measurement of the bonding force of hard conating（American Society Testing and Materials's standard（ASTM）B905）

After according to embodiment and comparing embodiment manufacture optical film, in the side that the film is coated with the coating composition Upper carry out hard conating process, then measures bonding force at room temperature.Hot water treatment at high temperature（100 DEG C, 10min）Afterwards, evaluate Bonding force between hard conating and online coating.

In grid the situation of remaining 100% film, the situation of remaining 95% film, the situation of remaining 85 to 95% films, residue 65 to The situation and residue 65% of 85% film are be evaluated as 5 points, 4 points, 3 points, 2 points and 0 point respectively with the situation of lower film.

6）The measurement of dry coating thickness

On full wafer film, 5 are marked with 1m interval on the direction of (machine direction) is transversely to the machine direction Point, then using ESEM（SEM, Hitachi S-4300）Measure its cross section.In addition, the region marked is with 50000x Multiplying power amplification, measure the thickness at 30 points, and calculate its average value in this region.

7）The measurement of granularity

1% fluid sample is injected into UPA-UT151（NikkisoCo.）, granularity is measured, and provide its average value.

Embodiment 1

The preparation of coating composition 1

By 20 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 4 weight % particle mean size 6nm and the zirconium oxide of refractive index 2.1 Colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water, and stir 3 hours, thus prepare the weight % of total solid content 5.5 polyester coating combination Thing.The refractive index of the coating composition is 1.58.

The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Manufactured polyethylene terephthalate piece is stretched 3.5 times on longitudinal direction and is cooled to room temperature.Then, with bar type rubbing method Coating composition 1 is coated on the both sides of described, is warming up to 110 to 150 DEG C with 1 DEG C per second of speed, and pass through preheating With drying by coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, it is heat-treated at 235 DEG C in 5 grades of stenters, 200 DEG C by heat-treating film, so that its heat cure, thus manufacture includes for relaxation 10% on longitudinal direction (longitudinal) and horizontal direction The primer coating formed on both sides as shown in Figure 2 and the biaxially-stretched film with 188 μ m thicks.

In the primer coating, the thickness of first coating is 90nm, and the thickness of second coating is 90nm, and its refractive index For 1.58.

The physical property of the optical film of above-mentioned manufacture is shown in table 1 below.

[embodiment 2]

The preparation of coating composition 2

By 17 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 4 weight % particle mean size 6nm and the zirconium oxide of refractive index 2.1 Colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water, and stir 3 hours, thus prepare the weight % of total solid content 5 polyester coating combination Thing.The refractive index of the coating composition is 1.59.

Double spread polyester film is manufactured with identical method in embodiment 1.In the primer coating, first coating Thickness is 80nm, and the thickness of second coating is 80nm, and its refractive index is 1.59.

[embodiment 3]

The preparation of coating composition 3

By 22 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 4 weight % particle mean size 6nm and the zirconium oxide of refractive index 2.1 Colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water, and stir 3 hours, thus prepare the weight % of total solid content 6 polyester coating combination Thing.The refractive index of the coating composition is 1.57.

Double spread polyester film is manufactured with identical method in embodiment 1.In the primer coating, first coating Thickness is 104nm, and the thickness of second coating is 104nm, and its refractive index is 1.57.The optical film of above-mentioned manufacture it is physical Matter is shown in table 1 below.

[embodiment 4]

The preparation of coating composition 4

By 10 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 2.6 weight % particle mean size 6nm and the oxidation of refractive index 2.1 Zirconium colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm colloidal silica particles are added to the water, and stir 3 hours, thus prepare the weight % of total solid content 3 polyester coating Composition.The refractive index of the coating composition is 1.6.

Double spread polyester film is manufactured with identical method in embodiment 1.In the primer coating, first coating Thickness is 62nm, and the thickness of second coating is 62nm, and its refractive index is 1.6.The physical property of the optical film of above-mentioned manufacture Display is in table 1 below.

[embodiment 5]

One side coats the manufacture of polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type The coating composition 1 prepared in embodiment 1 is coated on the side of described by cloth method, is warming up to 1 DEG C per second of speed 110 to 150 DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, at 235 DEG C in 5 grades of drawings It is heat-treated in width machine, heat-treating film is relaxed 10% so that its heat cure, is thus manufactured in machine and transverse direction at 200 DEG C Coat on one side thereof and there is the biaxially-stretched film of 188 μ m thicks.The thickness of primer coating is 92nm, and its refractive index is 1.58。

[embodiment 6]

One side coats the manufacture of polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type The coating composition 2 prepared in example 2 is coated on the side of described by cloth method, is warming up to 1 DEG C per second of speed 110 to 150 DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, at 235 DEG C in 5 grades of drawings It is heat-treated in width machine, heat-treating film is relaxed 10% so that its heat cure, is thus manufactured in machine and transverse direction at 200 DEG C Coat on one side thereof and there is the biaxially-stretched film of 188 μ m thicks.The thickness of primer coating is 85nm, and its refractive index is 1.59。

[embodiment 7]

The preparation of coating composition 5

By 20 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 8 weight % particle mean size 65nm and the zirconium oxide of refractive index 2.1 Colloidal sol（CIKCo., ZWR E-15）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles, and stirs Mix 3 hours, thus prepare the weight % of total solid content 5.5 polyester coating composition.The refractive index of the coating composition is 1.58.

Double spread polyester film is manufactured with identical method in embodiment 1.In primer coating, the thickness of first coating Spend for 89nm, the thickness of second coating is 89nm, and its refractive index is 1.58.The physical property of the optical film of above-mentioned manufacture shows Show in table 1 below.

[embodiment 8]

The preparation of coating composition 6

By 20 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 8 weight % particle mean size 50nm and the zirconium oxide of refractive index 2.1 Colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water, and stir 3 hours, thus prepare the weight % of total solid content 5.5 polyester coating combination Thing.The refractive index of the coating composition is 1.58.

[embodiment 9]

The preparation of coating composition 6

By 22 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 3 weight % particle mean size 6nm and the zirconium oxide of refractive index 2.1 Colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water, and stir 3 hours, thus prepare the weight % of total solid content 6 polyester coating combination Thing.The refractive index of the coating composition is 1.56.

Double spread polyester film is manufactured with identical method in embodiment 1.In primer coating, the thickness of first coating Spend for 95nm, the thickness of second coating is 95nm, and its refractive index is 1.56.The physical property of the optical film of above-mentioned manufacture shows Show in table 1 below.

[embodiment 10]

With method in the same manner as in Example 1 double spread polyester is manufactured using the coating composition 1 prepared in embodiment 1 Film.In primer coating, the thickness of first coating is 50nm, and the thickness of second coating is 50nm, and its refractive index is 1.58. The physical property of the optical film of above-mentioned manufacture is shown in table 1 below.

[embodiment 11]

With method in the same manner as in Example 1 double spread polyester is manufactured using the coating composition 1 prepared in embodiment 1 Film.In primer coating, the thickness of first coating is 70nm, and the thickness of second coating is 70nm, and its refractive index is 1.58. The physical property of the optical film of above-mentioned manufacture is shown in table 1 below.

[embodiment 12]

With method in the same manner as in Example 1 double spread polyester is manufactured using the coating composition 1 prepared in embodiment 1 Film.In primer coating, the thickness of first coating is 120nm, and the thickness of second coating is 120nm, and its refractive index is 1.58.The physical property of the optical film of above-mentioned manufacture is shown in table 1 below.

[embodiment 13]

With method in the same manner as in Example 1 double spread polyester is manufactured using the coating composition 1 prepared in embodiment 1 Film.In primer coating, the thickness of first coating is 150nm, and the thickness of second coating is 150nm, and its refractive index is 1.58.The physical property of the optical film of above-mentioned manufacture is shown in table 1 below.

[comparing embodiment 1]

The preparation of coating composition 7

By 8 weight % aqueous acrylic adhesives（Refractive index 1.44）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 5 weight % particle mean size 6nm and the zirconium oxide of refractive index 2.1 Colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water, and stir 3 hours, thus prepare the weight % of total solid content 5 acrylic coating combination Thing.The refractive index of the coating composition is 1.53.

[comparing embodiment 2]

The preparation of coating composition 8

By 6 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones（Dow Corning Corp., polyester-silicone copolymers）, 1.6 weight % particle mean size 6nm and the zirconia sol of refractive index 2.1 （Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm glue Body silicon dioxide microparticle is added to the water, and stirs 3 hours, thus prepares the weight % of total solid content 2 polyester coating composition.Should The refractive index of coating composition is 1.57.

[comparing embodiment 3]

The preparation of coating composition 9

By 20 weight % waterborne polyester adhesive（Refractive index 1.54）, 0.3 weight % the wetting agent based on silicones （Dow Corning Corp., polyester-silicone copolymers）, 8 weight % particle mean size 6nm and the zirconium oxide of refractive index 2.1 Colloidal sol（Its solid content with 30 weight % is simultaneously surface-treated with sodium citrate）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water, and stir 3 hours, thus prepare the weight % of total solid content 6.5 polyester coating combination Thing.The refractive index of the coating composition is 1.62.

[table 1]

As shown in table 1, it is found that according to the total light transmittance of the polyester film for being coated with primer coating composition of the present invention （TT）For 90.1 to 91.7%, and its mist degree is 0.73 to 1.74.It can be found that the size in particulate as in Example 7 is In the case of 65nm, mist degree somewhat increases.

[embodiment 14 to 22]

Hard conating is formed on the primer coating of the film manufactured in embodiment 1 to 8.

In the case, the hard conating is by acrylic resin（AIKA Co., Z-711）It is made, and such as institute in table 2 below Show and adjust its refractive index and thickness.

The physical property of the optical film of above-mentioned manufacture is shown in table 2 below.

[comparing embodiment 4 to 6]

Hard conating is formed on the primer coating of the film manufactured in comparing embodiment 1 to 3.

In the case, the hard conating is by acrylic resin（AIKA Co., KY-11）It is made, and such as institute in table 2 below Show and adjust its refractive index and thickness.

[table 2]

As shown in table 2, the comparing embodiment 4 of the scope of the invention is exceeded in refractive index（Comparing embodiment 1）In the case of, There is wave pattern in 300nm, and in comparing embodiment 6（Comparing embodiment 3）In the case of, there is ripple in 800nm Pattern.Thus, it can be understood that deteriorate optical property and generate rainbow phenomena.Furthermore, it is possible to find, in primer coating Coating layer thickness exceed the scope of the invention comparing embodiment 5（Comparing embodiment 2）In the case of, there is ripple in 300nm Pattern.

Then, second embodiment of the invention will be described.

The inventors discovered that there are at least three isocyanate functional groups using（It is end group and closing end group）Water In the case that dispersed polyurethane resin forms coating, moisture-proof is improved under hot and humid very harsh conditions in post processing Property, so as to improve and optic polymer basement membrane（Such as prism film etc.）Cohesive, this completes the present invention second be real Apply scheme.

Second embodiment of the invention is related to the polyurethane coating composition for including water dispersible polyurethane resin（Hereinafter referred to as For " the first water-dispersed composition "）, the water dispersible polyurethane resin has the linear poly- of two end groups by 10 to 75 weight %'s The composition of the branched polymer with least three end groups of compound and 25 to 90 weight %.

Moreover, it relates to a kind of optical film, the optical film include polyester base film and by the side of the basement membrane or The prime coat that polyurethane coating composition is formed is coated with both sides, the polyurethane coating composition is included by 10 to 75 weight % Linear polymer with two end groups and 25 to 90 weight % the composition of the branched polymer with least three end groups water Dispersed polyurethane resin.

In a second embodiment of the present invention, the end group can be blocked different including partly or entirely with inorganic acid salt Cyanate group is with excellent water dispersible.

It is preferable to use the water dispersible polyurethane tree prepared with the following method in a second embodiment of the present invention Fat：By the isocyanation esterification of 39 to 45 weight % polyalcohol, 0.3 to 1.2 weight % trimethylolpropane and 50 to 57 weight % Compound is reacted with each other to prepare the prepolymer that end group is NCO, then again by the inorganic of the prepolymer and 3 to 4 weight % Hydrochlorate is reacted to close the terminal isocyanate groups with ionic group.

The water dispersible polyurethane resin with 10,000 to 20,000 weight average molecular weight can preferably be used.

In a second embodiment of the present invention, moisture of the polyurethane coating composition including 5 to 10 weight % dissipates poly- Urethane adhesive, 0.1 to the 0.5 weight % wetting agent based on silicones, 0.1 to 0.5 weight % colloidal silica particles, With the water of surplus, the water dispersible polyurethane adhesive includes the water dispersible polyurethane resin and water with 10 to 30 weights Measure % solid content.

In a second embodiment of the present invention, the colloidal silica with 50 to 1000nm particle mean size can be used Silicon particle.

In a second embodiment of the present invention, the dry coating thickness of the primer coating can be 50 to 100nm.

Following physical property can be met according to the optical film of second embodiment of the invention：Surveyed according to equation 1 below The swelling ratio of amount is 35 to 100, and the gel fraction according to equation 2 below measurement is 75 to 85, and glass transition temperature is More than 60 DEG C.As long as because meeting above-mentioned physical property, optical film would not be swelled, thus the optical film can in basement membrane and There is excellent bonding force between primer coating and show excellent bonding force when being laminated the post processing of functional layer.It that is to say Say, the primer coating also has excellent bonding force under hot and humid.

[formula 1]

（In equation 1, the weight after holding is referred to dry coating film（About 1g）Immerse distilled water（50g）In and at 70 DEG C The weight measured after being kept for 24 hours.）

[formula 2]

Gel fraction=（Dried weight/original weight）×100

（In formula 2, dried weight is referred to dry coating film（About 1g）Immerse distilled water（50g）In, in 70 DEG C of guarantors Hold 24 hours, then again by the film after the holding in 120 DEG C of weight measured after drying 3 hours.）

Hereinafter, second embodiment of the invention will be described in further detail.

As the basement membrane used in second embodiment of the invention, due to excellent light transmittance, it is preferable to use poly- Ester film, more specifically, polyethylene terephthalate or poly (ethylene naphthalate) film, and the basement membrane can wrap Include additive or particulate.As this polyethylene terephthalate film, preferably using the poly terephthalic acid second stretched Diol ester film, and can use be stretched uniaxially or biaxially polyethylene terephthalate film.The thickness of basement membrane used Can be 50 to 250 μm, but be not restricted to that this.

In a second embodiment of the present invention, the prime coat tool formed on the one or both sides of optic polymer basement membrane There are excellent cohesive and easily viscosity, that is, allow the property bonded with other substrates.

As prime coat, the polyurethane coating composition for including water dispersible polyurethane resin can be used.The moisture dissipates Polyurethane resin includes：With at least three for the isocyanate functional group of end group branched polymer, and the isocyanic acid Ester group partly or entirely uses inorganic acid salt（More specifically, for example, sulfate inorganic salts）End-blocking；It is and different with two The linear polymer of cyanate functional group, and the isocyanate groups partly or entirely use inorganic acid salt（More specifically, Such as the inorganic salts of sulfate）End-blocking.

The water dispersible polyurethane resin can be by 10 to 75 weight the % linear polymer and 25 to 90 weight % The branched polymer composition.In the case where the content of branched polymer is less than 25 weight %, it may not be possible to meet institute of the present invention It is required that swelling ratio and gel fraction, and be likely difficult to obtain in the hot and humid lower film with excellent adhesiveness.In addition, In the case where the content of branched polymer is more than 90 weight %, because excessive gelation causes the quick increase of viscosity, Ke Nengnan To prepare water-dispersed composition, and the appearance that can be produced such as crackle when with the surface of said composition coated film lacks Fall into.In the present invention, branched polymer refers to the resin with least three isocyanate functional groups.

In a second embodiment of the present invention, it is contemplated that regulation coating layer thickness, preferably described water dispersible polyurethane bonding Agent includes water dispersible polyurethane resin and water is using the solid content with 10 to 30 weight % and its content is whole polyurethane composition 5 to 10 weight % of thing.When the content of the water dispersible polyurethane adhesive is less than 5 weight %, coating performance is excellent, but can Can be difficult to bond, and when content is more than 10 weight %, cohesive is excellent, but be likely difficult to realize coating outward appearance and The transparency.

As the method for preparing the water dispersible polyurethane resin, for example, can preferably with the following method：By 39 to 45 The isocyanate compound of weight % polyalcohol, 0.3 to 1.2 weight % trimethylolpropane and 50 to 57 weight % is anti-each other Should come prepare end group be NCO prepolymer, then again by the prepolymer and 3 to 4 weight % inorganic acid salt reaction with The terminal isocyanate groups are closed to prepare water dispersant type polyaminoester resin with the ionic group of sulfate, but methods described is not It is limited to this.

In addition, when the weight average molecular weight of the water dispersible polyurethane resin is in the range of 10000 to 20000, it is described poly- Urethane resin may not gelation but be dispersed in water, and can obtain lower there are excellent physical properties hot and humid Film.

Weight average molecular weight can use gel permeation chromatography（GPC）The light scattering of-multi-angle（MALS）System（WyattCo.） Measurement, and the configuration of MALS systems is as follows.

The configuration of MALS systems

-GPC：Water1525 binary HPLC pumps

- RI detectors：Optilab rex

-MALS：Wyatt Dawn8+

- chromatographic column：PLgel5μm Mixed-C(7.5mmΦ×300mm)×2(Polymer Laboratories)

- mobile phase：DMF(50mM LiCl)

- flow velocity：0.5mL/min

- temperature：50℃

- sample size：0.5%, 500 μ l

As polyalcohol, the polyalcohol based on polyester or the polyalcohol based on polyethers can be used, and preferably use base In the polyalcohol of polyester.Polyalcohol based on polyester can be by by carboxylic acid, decanedioic acid or acid anhydrides and polyalcohol （polyhydric alcohol）React the polyalcohol prepared.The species of polyalcohol is not limited, and it is preferably equal using weight The PEPA of molecular weight 600 to 3000.The content of polyalcohol can be 39 to 45 weight %.In content less than 39 weight %'s In the case of, molecular weight diminishes so that prime coat becomes really up to the mark, and is likely difficult to stretch, so as to which appearance of coat may be bad. In the case that content is more than 45 weight %, online coating（ILC）Layer becomes too soft, so as to deteriorate isolation performance.

Trimethylolpropane is used to prepare the prepolymer with three functional groups, and the content of trimethylolpropane used Can be 0.3 to 1.2 weight %.In the case where content is less than 0.3 weight %, crosslink density can reduce and can reduce resist blocking and that Property, and in the case where content is higher than 1.2 weight %, crosslink density is too high, deteriorates tensile property, so as to which appearance of coat may It is bad, and bonding force can deteriorate.

Isocyanate compound is not limited, but can preferably use hexamethylene diisocyanate.When isocyanates chemical combination When the content of thing is 50 to 57 weight %, the prepolymer with three functional groups can be prepared.

As inorganic acid salt it is preferable to use niter cake, and its content can be 3 to 4 weight %.

Wetting agent based on silicones can also be included according to the polyurethane coating composition of second embodiment of the invention With colloidal silica particles as additive, to be advantageous in the epilamellar coating performance of optic polymer and on prime coat Resistance to hot-working.

The content of the wetting agent based on silicones can be 0.1 to 0.5 weight %, and colloidal silica particles Content can be 0.1 to 0.5 weight %.In addition, the particle mean size of the colloidal silica particles can be 50 to 1000nm.

In a second embodiment of the present invention, the dry coating thickness of the primer coating can be 50 to 100nm.As Coating method, the online rubbing method for being coated with said composition on the surface in the technical process of oriented polyester film can be used, The offline rubbing method after the film is manufactured can be used.Both approaches can use.Preferably, online coating can be used Method, because be coated and film forming simultaneously, manufacturing cost can be reduced, and the thickness that draw ratio changes coating can be passed through Degree.

Hereinafter, the detailed description of second embodiment of the invention will be provided by embodiment.But the present invention is not limited to The following examples.

With following measuring method physical properties.

1st, using polyurethane coating composition film physical property measurement

By water dispersible polyurethane adhesive（15g）It is put into diameter 80mm and height 15mm bulge, and at 65 DEG C Dry 72 hours and dried 3 hours at 120 DEG C.By the dry coating（1g）Immerse distilled water（50g）In and 70 DEG C holding After 24 hours, take out the film after keeping and measure its swelling ratio.Film after holding is dried 3 hours at 120 DEG C, Ran Houji Its weight is recorded, thus measures gel fraction.

1）Swelling ratio：By dry coating（1g）Immerse distilled water（50g）In and 70 DEG C keep 24 hours after, take out Film after holding simultaneously records its swelling ratio.

2）Gel fraction：Film after holding is dried 3 hours at 120 DEG C, then records its weight.

Gel fraction=（Dried weight/original weight）×100

3）Tg measurement：Use the differential scanning calorimetry (DSC) of two circulation patterns（DSC, PerkinElmer DSC7）Measure glass Glass transition temperature（Tg）.Under the following conditions Tg is measured using 10 to 11mg dry coating and PerKinElmer DSC7.

First circulation=0~200 DEG C, 200 DEG C/min, the residence time -3min//200 DEG C~-40 DEG C, 200 DEG C/min, stop M- 5min when staying

Second circulation=- 40 DEG C~200 DEG C, 20 DEG C/min

2nd, the method for the adhesive of the double-deck coating polyester film of evaluation

Using thermal gradient test instrument（TOYOSEIKI）Under 0.4MPa pressure condition by film under 5 preset temperatures Pressure removes pressing plate, and verify degree of compression (pressed degree) after 1 minute.The difference of degree of compression is evaluated according to Fig. 5.

- the evaluation under constant humidity degree：In thermostatic constant wet chamber（20~25 DEG C, 40~50RH%）In tested.

- the evaluation under increased humidity：Tested under the humidity using the 100%RH of ultrasonic humidifier.

[preparing embodiment 1]

The preparation of water dispersible polyurethane adhesive 1

Prepare the water dispersible polyurethane of the branched polymer with 25 weight % in theory.

In the polyethylene glycol adipate glycol by making 40 weight %（polyethylene adipate diol）、0.3 Weight % trimethylolpropane and 56.7 weight % hexamethylene diisocyanate react with each other preparation, and there is isocyanate functional group to make After the prepolymer of end group, by making to be used as ionic group for the isocyanates of prepolymer end functional group and 3 weight % The polyurethane that prepared by niter cake reaction have ionic group and weight average molecular weight is 10,700.By by the above-mentioned of 20 weight % The they of preparation prepares the weight % of solid content 20 water dispersible polyurethane adhesive 1 in 80 weight % water.

[preparing embodiment 2]

The preparation of water dispersible polyurethane adhesive 2

Prepare the water dispersible polyurethane of the branched polymer with 50 weight % in theory.

In the polyethylene glycol adipate glycol by making 40 weight %, 0.6 weight % trimethylolpropane and 55.9 weights Amount % hexamethylene diisocyanate react with each other preparation have isocyanate functional group as the prepolymer of end group after, by make for Prepared by the isocyanates of prepolymer end functional group and 3.5 weight % the niter cake reaction as ionic group have ion Group and the polyurethane that weight average molecular weight is 14,400.By by the they of 20 weight % above-mentioned preparation in 80 weight % Water in prepare the weight % of solid content 20 water dispersible polyurethane.

[preparing embodiment 3]

The preparation of water dispersible polyurethane adhesive 3

Prepare the water dispersible polyurethane of the branched polymer with 90 weight % in theory.

In the polyethylene glycol adipate glycol by making 40 weight %, 1.2 weight % trimethylolpropane and 54.8 weights Amount % hexamethylene diisocyanate react with each other preparation have isocyanate functional group as the prepolymer of end group after, by make for Prepared by the isocyanates of prepolymer end functional group and 4.0 weight % the niter cake reaction as ionic group have ion Group and the polyurethane that weight average molecular weight is 19,000.By by the they of 20 weight % above-mentioned preparation in 80 weight % Water in prepare the weight % of solid content 20 water dispersible polyurethane.

[embodiment 23]

Prepare the polyurethane coating composition 1 with excellent crosslink density

By the 5 weight % water dispersible polyurethane adhesive prepared in embodiment 1 is prepared, 0.3 weight % based on silicon tree The wetting agent of fat（Dow Corning Corp., polyester-silicone copolymers）With 0.3 weight % particle mean size 140nm glue Body silicon dioxide microparticle is added to the water and stirred 2 hours, thus prepares polyurethane coating composition 1.

The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Polyurethane coating composition 1 is coated on the both sides of described by bar type rubbing method, with 1 DEG C per second of speed be warming up to 110 to 150 DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, at 230 DEG C in 5 grades of stenters It is heat-treated, the heat-treating film is relaxed 10% so that its heat cure, is thus manufactured in the longitudinal and transverse direction at 200 DEG C Coat on both sides and there is the biaxially-stretched film of 188 μ m thicks.In the polyurethane coating, the dry thickness of first coating is 80nm, and the dry thickness of second coating is 80nm.

[embodiment 24]

Prepare the polyurethane coating composition 2 with excellent crosslink density

By the 5 weight % water dispersible polyurethane adhesive prepared in embodiment 2 is prepared, 0.3 weight % based on silicon tree The wetting agent of fat（Dow Corning Corp., polyester-silicone copolymers）With 0.3 weight % particle mean size 140nm glue Body silicon dioxide microparticle is added to the water and stirred 2 hours, thus prepares polyurethane coating composition 2.

The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Polyurethane coating composition 2 is coated on the both sides of described by bar type rubbing method, with 1 DEG C per second of speed be warming up to 110 to 150 DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, at 230 DEG C in 5 grades of stenters It is heat-treated, heat-treating film is relaxed 10% so that its heat cure, is thus manufactured in the longitudinal and transverse direction at 200 DEG C Coated on its both sides and there is the biaxially-stretched film of 188 μ m thicks.In the polyurethane coating, the dry thickness of first coating is 80nm, and the dry thickness of second coating is 80nm.

[embodiment 25]

Prepare the polyurethane coating composition 3 with excellent crosslink density

By the 5 weight % water dispersible polyurethane adhesive prepared in embodiment 3 is prepared, 0.3 weight % based on silicon tree The wetting agent of fat（Dow Corning Corp., polyester-silicone copolymers）With 0.3 weight % particle mean size 140nm glue Body silicon dioxide microparticle is added to the water and stirred 2 hours, thus prepares polyurethane coating composition 3.

The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Polyurethane coating composition 3 is coated on the both sides of described by bar type rubbing method, with 1 DEG C per second of speed be warming up to 110 to 150 DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, at 230 DEG C in 5 grades of stenters It is heat-treated, heat-treating film is relaxed 10% so that its heat cure, is thus manufactured in the longitudinal and transverse direction at 200 DEG C Coated on its both sides and there is the biaxially-stretched film of 188 μ m thicks.In the polyurethane coating, the dry thickness of first coating is 80nm, and the dry thickness of second coating is 80nm.

[comparing embodiment 7]

The preparation of urethane composition

By 5 weight % aqueous polyurethane adhesive（Solid content, Liang Ge functional groups and 8000 weight with 20 weight % are equal The aqueous polyurethane adhesive of molecular weight, Dai-ichi Kygyo Seiyaku Co., UREKO H-3）, 0.3 weight % based on The wetting agent of silicones（Dow Corning Corp., polyester-silicone copolymers）With 0.3 weight % particle mean size 140nm Colloidal silica particles be added to the water and stir 2 hours, thus prepare the urethane composition in comparing embodiment 7.

By with embodiment 23 identical method using said composition manufacture double spread polyester film.

Measurement is water-based poly- in the water dispersible polyurethane adhesive and comparing embodiment 7 prepared in preparing embodiment 1 to 3 The physical property of urethane adhesive is simultaneously shown in table 3.

[table 3]

	Swelling ratio	Gel fraction	Tg(℃)
				Prepare embodiment 1	99.8	81.5	61.3
Prepare embodiment 2	61.5	79.2	61.4
				Prepare embodiment 3	36.5	82.1	627
Comparing embodiment 7	It is solvable	It is solvable	36

Measurement is according to embodiment 23 to 25 and the physical property of the film of comparing embodiment 7 and is shown in table 4 and 5.

[table 4] evaluates adhesion degree under constant humidity degree

	80℃	90℃	100℃	110℃	120℃
						Embodiment 23	○	○	△	X	X
Embodiment 24	◎	○	○	△	△
						Embodiment 25	◎	◎	◎	◎	◎
Comparing embodiment 7	○	X	X	X	X

[table 5] evaluates adhesion degree under increased humidity

	70℃	80℃	90℃	100℃	110℃
						Embodiment 23	△	△	X	X	X
Embodiment 24	○	△	X	X	X
						Embodiment 25	◎	◎	◎	○	△
Comparing embodiment 7	X	X	X	X	X

As shown in table 4 and 5, it is found that according to an embodiment of the invention 23, under constant humidity degree 100 DEG C with On temperature under adhesive deteriorate, but in embodiment 24 and 25, adhesion is all at a temperature of up to 120 DEG C under constant humidity degree It is excellent.

Under increased humidity, it is found that adhesion is all excellent at a temperature of up to 80 DEG C in embodiment 23 and 24 Different, and adhesion is excellent at a temperature of up to 110 DEG C in embodiment 25.

In view of these as a result, it can be appreciated that by adjusting in the water dispersible polyurethane adhesive used in prime coat The number of end group can manufacture in the hot and humid lower film with excellent physical properties.

Hereinafter, it will be described in detail third embodiment of the invention.

Third embodiment of the invention is related to polyester coating composition and the polyester film using the polyester coating composition.

More specifically, third embodiment of the invention is related to the polyester coating composition comprising polyester resin（Below Referred to as " the second water-dispersed composition "）, the polyester resin obtains as follows：20 to 40 moles of % of polycondensation 2,6- naphthalenedicarboxylic acids, 1 Aromatic dicarboxylic acid to 10 moles of %, 1 to the 10 mole of % aromatic dicarboxylic acid comprising sulfonate, 10 to 30 moles of % by Double [4 (2- hydroxyl-oxethyls) phenyl] fluorenes, 30 to the 60 moles of % diol compound and 1 to 10 that chemical formula 1 below represents rub Your the % triglyceride compound represented by chemical formula 2 below.

[chemical formula 1]

[chemical formula 2]

（In chemical formula 2, R₁To R₃It is each independently selected from hydrogen and (C1-C30) alkyl with or without unsaturated hydrocarbons.

The present inventor, which is studied, can have excellent adhesion with polyester base film with introducing and control interference figure to produce Prime coat.It is identical serial polyester resin emulsion that the present inventor, which is used with basement membrane, to increase and the polyester film for basement membrane Bonding force, and it is more than 1.58 to attempt to prepare refractive index, it is highly preferred that the polyester emulsion of refractive index 1.58 to 1.64 is to control The generation of interference figure.

The inventors discovered that by being used as carboxyl acid component using the compound with aromatic structure in synthesizing polyester resin It can increase refractive index with diol component.More specifically, the inventors discovered that, double [4 (2- hydroxyls of chemical formula 1 are being added Ethyoxyl) phenyl] refractive index is added in the case of fluorenes.Although above-mentioned aromatic compounds can increase refractive index, simultaneously Add the glass transition temperature of resin.Therefore, when preparing water dispersion emulsion using the compound and manufacturing the film In the case of using the water dispersion emulsion, stretching and will not carry out enough degradeds under heat treatment temperature, so as in the film Surface crack or formed wherein a region and cause white opacity.

Therefore, the present inventor is studied to solve these problems, and by finding that following truth completes the present invention's 3rd embodiment.And it is highly preferred that carry out the feelings of synthesizing polyester resin in the triglyceride compound shown in addition chemical formula 2 Under condition, branched structure is formd to reduce glass transition temperature.When using the compound in the range of 1 to 10 mole of % When, the polyester resin with 1.58 to 1.64 high index of refraction and 40 to 60 DEG C of glass transition temperature can be synthesized.Then, The water dispersion emulsion of primer coating is ready for use on using the polyester resin, and bottom is formed using the emulsion when manufacturing the film Lacquer coat, so as to manufacture the polyester film with excellent optical.

More specifically, in third embodiment of the invention, the aromatic dicarboxylic acid can be selected to benzene two Formic acid dimethyl ester, terephthalic acid (TPA), M-phthalic acid, 1,2- naphthalenedicarboxylic acids, 1,4- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 1,3- Any of pentamethylene dioctyl phthalate and 1,4 cyclohexanedicarboxylic acid or at least two mixture.

The aromatic dicarboxylic acid comprising sulfonate can be selected from 2,5- dicarboxyls benzene sulfonic acid sodium salt, 5- sulfo groups isophthalic two Any of formic acid, 2- sulfoisophthalic acids, 4- sulfoisophthalic acids and 4- sulfo groups-naphthalene -2,6- dioctyl phthalate or at least Two kinds of mixture.

The diol compound can be selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, five ethylene glycol, six Any of ethylene glycol, propane diols, tripropylene glycol, 1,3- propane diols, 1,3 butylene glycol, propane diols, bisphenol-A and bisphenol b etc. Or at least two mixture.

In addition, in third embodiment of the invention, the polyester can meet following physical property：Refractive index is 1.58 to 1.64, and glass transition temperature is 40 to 60 DEG C.

In third embodiment of the invention, the polyester coating composition can include water dispersible polyester adhesive, The water dispersible polyester adhesive includes polyester resin and water with the solid content with 10 to 40 weight %.

More specifically, in third embodiment of the invention, the polyester coating composition can include 10 to 40 Weight % water dispersible polyester adhesive, 0.1 to 0.5 weight % wetting agent, 0.1 to 1.0 weight % granularity 100 are to 200nm's Silica with the total solid content with 2 to 10 weight %, the water dispersible polyester adhesive include polyester resin and water with 10 to 40 weight % solid content.

Hydrophilic organic solvent can also be included according to the water-dispersed composition of third embodiment of the invention as needed And surfactant.

In addition, according to the third embodiment of the invention, the scope of the present invention includes：Comprising with the water-dispersed composition The polyester film of the primer coating of coating, more specifically, this is coated on comprising polyester base film and with the polyester coating composition The polyester film of primer coating on the one or both sides of polyester base film.

Hereinafter, the various configurations of third embodiment of the invention be will be described in detail.

In third embodiment of the invention, the water-dispersed composition can with 1.58 to 1.64 refractive index and 40 to 60 DEG C of glass transition temperature.In the case where refractive index is less than 1.58 or higher than 1.64, coating composition and hard painting Refractive index difference between layer is big, so as to because there may be rainbow phenomena so that said composition is not suitable for optical film. In addition, in the case where glass transition temperature is higher than 60 DEG C, will not be carried out enough with during process of thermal treatment stretching Degraded, so as to produce blushing.

In order to meet above-mentioned refractive index and glass transition temperature requirement, included and passed through according to the polymer blend of the present invention The polyester resin that polycondensation acid composition and diol component obtain, wherein the sour composition includes 20 to 40 moles of % 2,6- naphthalenes two The aromatic dicarboxylic acid of formic acid, 1 to the 10 mole of % aromatic dicarboxylic acid comprising sulfonate and 1 to 10 mole of %, and described two Double [4 (2- hydroxyl-oxethyls) phenyl] fluorenes represented by chemical formula 1 below of first alkoxide component including 10 to 30 moles of %, 1 to 10 are rubbed That % triglyceride compound represented by chemical formula 2 below and 30 to 60 moles of % diol compound.

[chemical formula 1]

[chemical formula 2]

In third embodiment of the invention, the NDA of the acid constituents is a kind of dicarboxylic acid component, such as There are two aromatic rings shown in chemical formula 3 below, which thereby enhance refractive index.

[chemical formula 3]

The content of used 2,6- naphthalenedicarboxylic acids can be preferably 20 to 40 moles of %.In the content less than 20 moles of %'s In the case of, it may be difficult to so that polyester resin has high index of refraction, and in the case of higher than 40 moles % of the content, Ke Nengnan So that said composition to be dispersed in water.

In addition, the aromatic dicarboxylic acid comprising sulfonate is used to ensure the dispersibility in water, and can be Selected from 2,5- dicarboxyls benzene sulfonic acid sodium salt, 5- sulfoisophthalic acids, sulfoisophthalic acid, 4- sulfoisophthalic acids and 4- sulphurs Any of base-naphthalene -2,6- dioctyl phthalate etc. or at least two mixture, but not limited to this.It is highly preferred that it can use The 2,5- dicarboxyl benzene sulfonic acid sodium salts represented by chemical formula 4.The content of aromatic dicarboxylic acid comprising sulfonate used can be with excellent Elect 1 to 10 mole of % as, and in the case of less than 1 mole % of the content, water dispersible may deteriorate, and be higher than in content In the case of 10 moles of %, hydrophily becomes too much so that process performance may deteriorate or may produce the adhesion of film.

[chemical formula 4]

In addition, the aromatic dicarboxylic acid refers to the aromatic dicarboxylic acid except including NDA and sulfonate Outside other dicarboxylic acid components, and can be selected from dimethyl terephthalate (DMT), terephthalic acid (TPA), M-phthalic acid, 1, Appointing in 2- naphthalenedicarboxylic acids, 1,4- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 1,3- pentamethylene dioctyl phthalate and 1,4 cyclohexanedicarboxylic acid It is a kind of or at least two mixture, but not limited to this.The content of aromatic dicarboxylic acid used can be preferably 1 to 10 Mole %, and in the case of less than 1 mole % of the content, hence it may becomes difficult to increase refractive index, and in content higher than 10 moles of %'s In the case of, it may be difficult to said composition is dispersed in water, b values may increase, and due to the aromatic component when manufacturing film Increase bonding force may be caused to reduce.

In the diol component of third embodiment of the invention, double [4 (2- hydroxyl-oxethyls) of chemical formula 1 below Phenyl] fluorenes is used to increase refractive index and have high transparency, and its content can be preferably 10 to 30 moles of %.Contain at this In the case of less than 10 moles % of amount, it may be difficult to increase refractive index, and in the case of higher than 30 moles % of the content, Ke Nengnan So that said composition to be dispersed in water.

[chemical formula 1]

In addition, the use of the triglyceride compound represented by chemical formula 2 below it is somebody's turn to do after coating in stretching to overcome The defects of being cracked in the technical process of film with non-through melting forming region excessively, and in order to uniform film and refraction Rate, and in order to reduce with refractive index increase and increased glass transition temperature, the triglyceride compound is for drawing Enter the collateral chain with long-chain.The content of used triglyceride compound can be 1 to 10 mole of %.Rubbed in content less than 1 In the case of your %, transition temperature（Tg）It will not be decreased sufficiently, and in the case of higher than 10 moles % of content, refractive index may Reduce and there may be the adhesion of film.

[chemical formula 2]

（In chemical formula 2, R₁To R₃It is each independently selected from hydrogen and (C1-C30) alkane with or without unsaturated hydrocarbons Base.）

The diol compound can be, for example, selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, five second In glycol, six ethylene glycol, propane diols, tripropylene glycol, 1,3- propane diols, 1,3 butylene glycol, propane diols, bisphenol-A and bisphenol b etc. It is any or at least two mixture, but not limited to this.The content of used diol compound can be 30 to 60 Mole %.In the case of less than 30 moles % of content, esterification may be insufficient, and in situation of the content higher than 60 moles of % Under, it is possible to create the adhesion of film, heat resistance may deteriorate, and refractive index may reduce.

According to the polyester resin obtained by polycondensation said components of third embodiment of the invention can have 0.1 to 1.0, more preferably 0.1 to 1.6 inherent viscosity.Within the above range, the polyester emulsion can be by the way that the polyester resin be divided Dissipate or be dissolved in water or aqueous solvent and prepare.

The polyester resin obtained according to third embodiment of the invention can pass through the synthesizing polyester in association area It is prepared by the method for resin.For example, in the absence of a solvent, the NDA including 20 to 40 moles of %, 1 to 10 are rubbed The sour composition of your % aromatic dicarboxylic acid comprising sulfonate and 1 to 10 mole of % aromatic dicarboxylic acid and rubbed including 10 to 30 The glycol of your % double [4 (2- hydroxyl-oxethyls) phenyl] fluorenes, 1 to 10 mole of % triglyceride compound and 30 to 60 moles of % The diol component of compound is mixed with each other, and the mixture is put into reactor, then carries out esterification by heating, together When remove caused by water byproduct or methanol.Then, it is anti-by reducing the pressure in reactor while raising temperature progress polycondensation Should, while reclaim accessory substance diol component.

In this case, it is possible to using the catalyst for promoting polycondensation reaction, for example, catalyst for esterification reaction, ester exchange are anti- Catalyst or polycondensation catalyst etc. are answered, and various additives can be added, such as stabilizer or inorganic particles etc..

In third embodiment of the invention, the coating composition for forming primer coating can be dissipated for moisture or water Property composition, it includes polyester resin, wetting agent, the silica of particle mean size 100 to 200nm, and the weight of solid content 5 to 40 The moisture for measuring % dissipates inorganic particles.

More specifically, polyester coating composition according to the third embodiment of the invention can include 10 to 40 weights The % polyester resin, 0.1 to 0.5 weight % wetting agent, 0.1 to 1.0 weight % particle mean size 100 are measured to the two of 200nm Silica, and it is fabricated such that the total solid content of said composition is 2 to 10 weight %.In view of adjusting coating layer thickness, preferably It is that solid content is in the range of 2 to 10 weight %.

The polyester coating composition can also include hydrophilic organic solvent and surfactant to improve when needed Dispersion stabilization.

As hydrophilic organic solvent, using dioxane, acetone, tetrahydrofuran and MEK etc., and surface-active is used as Agent, using anion or nonionic surface active agent, so that dispersion stabilization can be improved.Preferably, it is used hydrophilic The content of property organic solvent and surfactant is 0.1 to 5 weight %.

As the coating method for being used to form the polyester coating composition of primer coating, can use in stretched polyester The online rubbing method of said composition is coated with the technical process of film on the surface, the offline painting after the film is manufactured can also be used Cloth method.Both approaches can use.

According to the third embodiment of the invention, comprising by being coated with the polyester coating on the one or both sides of basement membrane The polyester film for the primer coating that composition is formed is intended to be included within the scope of the present invention.Here, implement as in the present invention the 3rd The basement membrane used in scheme, due to excellent translucency, it is preferable to use polyester film, more specifically, poly terephthalic acid Glycol ester.As this polyethylene terephthalate film, preferably using the polyethylene terephthalate stretched Film, and can use be stretched uniaxially or biaxially polyethylene terephthalate film.

The thickness of the basement membrane can be 25 to 188 μm, but be not restricted to that this.

Hereinafter, the detailed description of third embodiment of the invention will be provided by embodiment.But the present invention is not limited to The following examples.

The method of the physical properties shown in embodiment and comparing embodiment below is as follows.

1）The measurement of total light transmittance

2）The measurement of refractive index

One composition is applied on polycarbonate membrane and dried.Then, at room temperature using refractometer（Abbe reflects Instrument, ATAGOCo., DR-M2 ,@550）Measure its refractive index.

3）The measurement 1 of rainbow phenomena degree

After according to embodiment and comparing embodiment manufacture optical film, hard conating is carried out on one side thereof（Refractive index 1.52） Processing, and opposite side blacking.Then, it is confirmed whether to produce rainbow with bore hole.Estimated in darkroom under three wavelength lamps.

Evaluation criterion is as follows.

Well：There is not rainbow phenomena, and color impression is uniform.

4）The measurement 2 of rainbow phenomena degree

5）Appearance of coat

The film is watched when light transmission is passed through film under three wavelength lamps.

The seemingly transparent situation of transmitted light is shown as ◎, and transmitted light seems to be muddy situation and is defined as bleaching.

6）Glass transition temperature

Use the DSC of two circulation patterns（PerkinElmer DSC7）Measure glass transition temperature.

TG is measured using 10mg dry coating and PerKinElmer DSC7.

First circulation=0~200 DEG C, 200 DEG C/min, residence time 3min, 200 DEG C~-40 DEG C, 200 DEG C/min, stop Time 5min

Second circulation=- 40 DEG C~200 DEG C, 20 DEG C/min

7）Mist degree

Use NDH-5000（Nippon Denshoku Co.）Measure mist degree.

10 samples are taken out with 0.5m interval from full wafer film（5cm x5cm）, and its mist degree is measured, it is flat so as to show Average.

8）The measurement of the coating layer thickness of drying layer

On full wafer film, 5 points are marked with 1m interval on the direction being transversely to the machine direction, then using SEM （Hitachi S-4300）Measure its cross section.In addition, the region marked is amplified with 50000x multiplying power, measure in the region In thickness at 30 points, and calculate its average value.

[embodiment 26]

1）The preparation of polyester coating composition 1

Under condition of no solvent, by 40 moles of NDA（26 moles of %）, 5 moles of 2,5- dicarboxyls benzene sulfonic acid sodium salt （3.3 moles of %), 5 moles of dimethyl terephthalic acid（3.3 moles of %）, double [4 (2- hydroxyl-oxethyls) phenyl] 20 moles of fluorenes （13.3 mole %）, triglycerides（Kao Corp., name of product：85P）10 moles（6.6 moles of %）With 70 moles of ethylene glycol （46.4 mole %）It is mixed with each other and is put into reactor, by the way that temperature is warming up to 250 DEG C of progress from 170 DEG C with 1 DEG C per minute Esterification, while remove water byproduct or methanol.Then, by being decompressed to 1mmHg in the reactor, while 260 are warming up to DEG C polycondensation reaction is carried out, while reclaim accessory substance glycol, thus prepare the polyester resin of inherent viscosity 0.5.

75 weight % water is added in 25 weight % prepared polyester resin and emulsified, thus prepare 25 weight %'s Waterborne polyester adhesive.The refractive index of prepared waterborne polyester adhesive is 1.60.

By 20 weight % waterborne polyester adhesive, 0.3 weight % silicone wetting agent（Dow Corning Corp., gather Ester-silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and stirs 3 Hour, thus prepare the weight % of solid content 5.5 primer coating compositions 1.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Primer coating compositions 1 are coated on the both sides of described by cloth method, and 110 to 150 DEG C are warming up to 1 DEG C per second of speed, and By preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, hot place is carried out in 5 grades of stenters at 235 DEG C Reason, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in its both sides in 200 DEG C of films by heat treatment The upper biaxially-stretched film for coating and there are 188 μ m thicks.In the polyester primer coating, the dry coating thickness of first coating is 100nm, and the dry coating thickness of second coating is 100nm.The physical property of optical film obtained above is shown in table 6 below In.

[embodiment 27]

1）The preparation of polyester coating composition 2

Under condition of no solvent, by 40 moles of NDA（26 moles of %）, 5 moles of 2,5- dicarboxyls benzene sulfonic acid sodium salt （3.3 moles of %), 5 moles of dimethyl terephthalic acid（3.3 moles of %）, double [4 (2- hydroxyl-oxethyls) phenyl] 30 moles of fluorenes（20 Mole %）, triglycerides（Kao Corp., name of product：85P）10 moles（6.6 moles of %）With 60 moles of ethylene glycol（40 rub You are %）It is mixed with each other and is put into reactor, by the way that temperature is warming up into 250 DEG C from 170 DEG C with 1 DEG C per minute be esterified instead Should, while remove water byproduct or methanol.Then, by being decompressed to 1mmHg in the reactor, while 260 DEG C of progress are warming up to Polycondensation reaction, while accessory substance glycol is reclaimed, thus prepare the polyester resin of inherent viscosity 0.6.

75 weight % water is added in 25 weight % prepared polyester resin and emulsified, thus prepare 25 weight %'s Waterborne polyester adhesive.The refractive index of prepared waterborne polyester adhesive is 1.62.

By 20 weight % waterborne polyester adhesive, 0.3 weight % silicone wetting agent（Dow Corning Corp., gather Ester-silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and stirs 3 Hour, thus prepare the weight % of solid content 5.5 primer coating compositions 2.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Primer coating compositions 2 are coated on the both sides of described by cloth method, and 110 to 150 DEG C are warming up to 1 DEG C per second of speed, and By preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, hot place is carried out in 5 grades of stenters at 235 DEG C Reason, heat-treating film is relaxed 10% so that its heat cure, is thus manufactured on both sides in the longitudinal and transverse direction at 200 DEG C Coat and there is the biaxially-stretched film of 188 μ m thicks.In the polyester primer coating, the dry coating thickness of first coating is 100nm, and the dry coating thickness of second coating is 100nm.The physical property of optical film obtained above is shown in table 6 below In.

[embodiment 28]

1）The preparation of polyester coating composition 3

Under condition of no solvent, by 40 moles of NDA（26 moles of %）, 5 moles of 2,5- dicarboxyls benzene sulfonic acid sodium salt （3.3 moles of %), 5 moles of dimethyl terephthalic acid（3.3 moles of %）, double [4 (2- hydroxyl-oxethyls) phenyl] 10 moles of fluorenes （6.66 mole %）, triglycerides（Kao Corp., name of product：85P）10 moles（6.6 moles of %）With 80 moles of ethylene glycol （53.33 mole %）It is mixed with each other and is put into reactor, is entered by the way that temperature is warming up into 250 DEG C from 170 DEG C with 1 DEG C per minute Row esterification, while remove water byproduct or methanol.Then, by being decompressed to 1mmHg in the reactor, it is warming up to simultaneously 260 DEG C of progress polycondensation reactions, while accessory substance glycol is reclaimed, thus prepare the polyester resin of inherent viscosity 0.5.

75 weight % water is added in 25 weight % prepared polyester resin and emulsified, thus prepare 25 weight %'s Waterborne polyester adhesive.The refractive index of prepared waterborne polyester adhesive is 1.58.

By 20 weight % waterborne polyester adhesive, 0.3 weight % silicone wetting agent（Dow Corning Corp., gather Ester-silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and stirs 3 Hour, thus prepare the weight % of solid content 5.5 primer coating compositions 3.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Primer coating compositions 3 are coated on the both sides of described by cloth method, and 110 to 150 DEG C are warming up to 1 DEG C per second of speed, and By preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, hot place is carried out in 5 grades of stenters at 235 DEG C Reason, heat-treating film is relaxed 10% so that its heat cure, is thus manufactured on both sides in the longitudinal and transverse direction at 200 DEG C Coat and there is the biaxially-stretched film of 188 μ m thicks.In the polyester primer coating, the dry coating thickness of first coating is 100nm, and the dry coating thickness of second coating is 100nm.The physical property of optical film obtained above is shown in table 6 below In.

[embodiment 29]

2）One side coats the manufacture of polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Coating composition 1 is coated on the side of described by cloth method, is warming up to 110 to 150 DEG C with 1 DEG C per second of speed, and pass through Preheat and dry coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, it is heat-treated at 235 DEG C in 5 grades of stenters, Heat-treating film is relaxed 10% so that its heat cure, thus manufacture is comprising on one side thereof in the longitudinal and transverse direction at 200 DEG C The primer coating of formation and the biaxially-stretched film with 188 μ m thicks.The dry coating thickness of the polyester primer coating is 100nm.The physical property of optical film obtained above is shown in table 6 below.

[embodiment 30]

2）One side coats the manufacture of polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Coating composition 2 is coated on the side of described by cloth method, is warming up to 110 to 150 DEG C with 1 DEG C per second of speed, and pass through Preheat and dry coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, it is heat-treated at 235 DEG C in 5 grades of stenters, Heat-treating film is relaxed 10% so that its heat cure, thus manufacture is comprising on one side thereof in the longitudinal and transverse direction at 200 DEG C The primer coating of formation and the biaxially-stretched film with 188 μ m thicks.The dry coating thickness of the polyester primer coating is 100nm.The physical property of optical film obtained above is shown in table 6 below.

[embodiment 31]

2）One side coats the manufacture of polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Coating composition 3 is coated on the side of described by cloth method, is warming up to 110 to 150 DEG C with 1 DEG C per second of speed, and pass through Preheat and dry coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, it is heat-treated at 235 DEG C in 5 grades of stenters, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, thus manufacture are included in its side in 200 DEG C of films by heat treatment The primer coating of upper formation and the biaxially-stretched film with 188 μ m thicks.The dry coating thickness of the polyester primer coating is 100nm.The physical property of optical film obtained above is shown in table 6 below.

[comparing embodiment 8]

1）The preparation of polyester coating composition 4

Under condition of no solvent, by 40 moles of NDA（26 moles of %）, 5 moles of 2,5- dicarboxyls benzene sulfonic acid sodium salt （3.3 moles of %), 5 moles of dimethyl terephthalic acid（3.3 moles of %）, double [4 (2- hydroxyl-oxethyls) phenyl] 30 moles of fluorenes（20 Mole %）With 70 moles of ethylene glycol（46.66 mole %）Be mixed with each other and be put into reactor, by with 1 DEG C per minute by temperature 250 DEG C of progress esterifications are warming up to from 170 DEG C, while remove water byproduct or methanol.Then, by depressurizing in the reactor To 1mmHg, while 260 DEG C of progress polycondensation reactions are warming up to, while reclaim accessory substance glycol, thus prepare inherent viscosity 0.5 Polyester resin.

By 20 weight % waterborne polyester adhesive, 0.3 weight % silicone wetting agent（Dow Corning Corp., gather Ester-silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and stirs 3 Hour, thus prepare the weight % of solid content 5.5 primer coating compositions 4.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Primer coating compositions 4 are coated on the both sides of described by cloth method, and 110 to 150 DEG C are warming up to 1 DEG C per second of speed, and By preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, hot place is carried out in 5 grades of stenters at 235 DEG C Reason, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in its both sides in 200 DEG C of films by heat treatment The upper biaxially-stretched film for coating and there are 188 μ m thicks.In the polyester primer coating, the dry coating thickness of first coating is 100nm, and the dry coating thickness of second coating is 100nm.The physical property of optical film obtained above is shown in table 6 below In.

[comparing embodiment 9]

1）The preparation of polyester coating composition 5

Under condition of no solvent, by 40 moles of NDA（26 moles of %）, 5 moles of 2,5- dicarboxyls benzene sulfonic acid sodium salt （3.3 moles of %), 5 moles of dimethyl terephthalic acid（3.3 moles of %）, double [4 (2- hydroxyl-oxethyls) phenyl] 20 moles of fluorenes （13.33 mole %）With 80 moles of ethylene glycol（53.33 mole %）It is mixed with each other and is put into reactor, by with 1 DEG C per minute Temperature is warming up to 250 DEG C of progress esterifications from 170 DEG C, while removes water byproduct or methanol.Then, by reactor In be decompressed to 1mmHg, while be warming up to 260 DEG C of progress polycondensation reactions, while reclaim accessory substance glycol, thus prepare inherent viscosity 0.4 polyester resin.

By 20 weight % waterborne polyester adhesive, 0.3 weight % silicone wetting agent（Dow Corning Corp., gather Ester-silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and stirs 3 Hour, thus prepare the weight % of solid content 5.5 primer coating compositions 5.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Primer coating compositions 5 are coated on the both sides of described by cloth method, and 110 to 150 DEG C are warming up to 1 DEG C per second of speed, and By preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, hot place is carried out in 5 grades of stenters at 235 DEG C Reason, heat-treating film is relaxed 10% so that its heat cure, is thus manufactured on both sides in the longitudinal and transverse direction at 200 DEG C It is coated with and there is the biaxially-stretched film of 188 μ m thicks.In the polyester primer coating, the dry coating thickness of first coating is 100nm, and the dry coating thickness of second coating is 100nm.The physical property of optical film obtained above is shown in table 6 below In.

[comparing embodiment 10]

1）The preparation of polyester coating composition 6

Under condition of no solvent, by 40 moles of NDA（26 moles of %）, 5 moles of 2,5- dicarboxyls benzene sulfonic acid sodium salt （3.3 moles of %), 5 moles of dimethyl terephthalic acid（3.3 moles of %）With ethylene glycol and butanediol with 1:The mixture of 1 ratio 100 moles（66.66 mole %）It is mixed with each other and is put into reactor, by is warming up to temperature from 170 DEG C with 1 DEG C per minute 250 DEG C of progress esterifications, while remove water byproduct or methanol.Then, by being decompressed to 1mmHg in the reactor, simultaneously 260 DEG C of progress polycondensation reactions are warming up to, while reclaim accessory substance glycol, thus prepare the polyester resin of inherent viscosity 0.4.

75 weight % water is added in 25 weight % prepared polyester resin and emulsified, thus prepare 25 weight %'s Waterborne polyester adhesive.The refractive index of prepared waterborne polyester adhesive is 1.54.

By 20 weight % waterborne polyester adhesive, 0.3 weight % silicone wetting agent（Dow Corning Corp., gather Ester-silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and stirs 3 Hour, thus prepare the weight % of solid content 5.5 primer coating compositions 6.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature, thus manufacture the polyethylene terephthalate piece of 2000 μm of thickness.80 DEG C Longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, applied with bar type Primer coating compositions 6 are coated on the both sides of described by cloth method, and 110 to 150 DEG C are warming up to 1 DEG C per second of speed, and By preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, hot place is carried out in 5 grades of stenters at 235 DEG C Reason, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in its both sides in 200 DEG C of films by heat treatment The upper biaxially-stretched film for being coated with and there are 188 μ m thicks.In the polyester primer coating, the dry coating thickness of first coating is 100nm, and the dry coating thickness of second coating is 100nm.The physical property of optical film obtained above is shown in table 6 below In.

The physical property of manufactured film is shown in table 6 below.

[table 6]

As shown in table 6, it is found that according to the polyester binder resins of the present invention with 1.58 to 1.62 high refraction Rate and 43 to 55 DEG C of lower glass transition temperatures.

It is, therefore, to be understood that the light transmittance of manufactured film is high, mist degree is low, excellent appearance, when forming film without white Muddiness produces, and without rainbow phenomena is produced, so as to which the film is adapted for use as optical film.

Below, it will be described in detail fourth embodiment of the invention.

Fourth embodiment of the invention is related to a kind of water-dispersed composition, and it includes the first water-dispersed composition and second The mixture of water-dispersed composition,

Wherein, first water-dispersed composition includes water dispersible polyurethane resin, the water dispersible polyurethane resin by The linear polymer with two end groups of 10 to 75 weight and 25 to the 90 weight % branched polymeric with least three end groups Thing forms, and

Second water-dispersed composition includes the polyester resin obtained by the following composition of polycondensation：20 to 40 moles of %'s The aromatic dicarboxylic acid of NDA, 1 to the 10 mole of % aromatic dicarboxylic acid comprising sulfonate and 1 to 10 mole of %, 10 to 30 moles of % double [4 (2- hydroxyl-oxethyls) phenyl] fluorenes represented by chemical formula 1 below, 1 to 10 mole of % by following The triglyceride compound and 30 to 60 moles of % diol compound that chemical formula 2 represents.

[chemical formula 1]

[chemical formula 2]

In addition, can be including 5 to 10 weight % according to the water-dispersed composition of four embodiment of the invention first and the The mixture of two water-dispersed compositions, 0.1 to the 0.5 weight % wetting agent based on silicones, 0.1 to 0.5 weight % colloid Silicon dioxide microparticle, and the water of surplus.

In addition, in the water-dispersed composition of four embodiment of the invention, first and second water-dispersed composition Mixture can be the first and second water-dispersed compositions with 1:9 to 5:Mixture of 5 weight than mixing.

In addition, in the water-dispersed composition of four embodiment of the invention, the first water-dispersed composition can include water Dispersed polyurethane resin and water are with the solid content with 10 to 30 weight %.

In addition, in the water-dispersed composition of four embodiment of the invention, the linear polymerization of the first water-dispersed composition Thing has the end group partly or entirely closed with inorganic acid salt.

In the water-dispersed composition of four embodiment of the invention, the moisture of first water-dispersed composition dissipates poly- ammonia Ester resin can be prepared as follows：By 39 to 45 weight % polyalcohol, 0.3 to 1.2 weight % trimethylolpropane and 50 to 57 Weight % isocyanate compound is reacted with each other to prepare the prepolymer that end group is NCO, then again by the prepolymer Reacted with 3 to 4 weight % inorganic acid salt to close the terminal isocyanate groups with ionic group.

In addition, in the water-dispersed composition of four embodiment of the invention, the water dispersible polyurethane resin can have There is 10,000 to 20,000 weight average molecular weight.

In addition, in the water-dispersed composition of four embodiment of the invention, the second water-dispersed composition can include poly- Ester resin and water are with the solid content with 10 to 40 weight %.

In addition, in the water-dispersed composition of four embodiment of the invention, the aromatic dicarboxylic acid can be selected from Dimethyl terephthalate (DMT), terephthalic acid (TPA), M-phthalic acid, 1,2- naphthalenedicarboxylic acids, 1,4- naphthalenedicarboxylic acids, 1,5- naphthalene diformazans Any of acid, 1,2- naphthalenedicarboxylic acids, 1,3- pentamethylene dioctyl phthalate and 1,4 cyclohexanedicarboxylic acid compound or at least two The mixture of compound, the aromatic dicarboxylic acid comprising sulfonate can be selected from 2,5- dicarboxyls benzene sulfonic acid sodium salt, 5- sulphurs Appointing in base-M-phthalic acid, 2- sulfo-isophthalic acids, 4- sulfo-isophthalic acids and 4- sulfo groups-naphthalene -2,6- dioctyl phthalate The mixture of a kind of compound or at least two compounds, and the diol compound can be, for example, selected from ethylene glycol, Diethylene glycol, triethylene glycol, tetraethylene glycol, five ethylene glycol, six ethylene glycol, propane diols, tripropylene glycol, 1,3- propane diols, 1,3- The mixture of any of butanediol, propane diols, bisphenol-A, bisphenol b compound or at least two compounds.

In addition, in the water-dispersed composition of four embodiment of the invention, the polyester of second water-dispersed composition Resin can be with 1.58 to 1.64 refractive index and 40 to 60 DEG C of glass transition temperature.

In addition, in the water-dispersed composition of four embodiment of the invention, the colloidal silica particles can have There is 50 to 1000nm granularity.

In addition, the water-dispersed composition of four embodiment of the invention can have 1.57 to 1.62 refractive index.

In addition, in four embodiment of the invention, the primer coating formed by being coated with the water dispersed combination is included Optical film is included within the scope of the present invention.

The optical film of four embodiment of the invention can include polyester base film and by the one or both sides of the basement membrane The primer coating that the upper coating water-dispersed composition is formed.

In the optical film of four embodiment of the invention, the dry coating thickness of the primer coating can be 50 to 100nm。

Below, it will be described in detail fourth embodiment of the invention.

The present inventor, which is studied, can have excellent bonding force with polyester base film with introducing and control interference figure to produce Raw prime coat.It is identical serial polyester resin emulsion that the present inventor, which is used with basement membrane, to increase and the polyester film for basement membrane Bonding force, and attempt to prepare polyester emulsion that refractive index is 1.57 to 1.62 to control the generation of interference figure.

The inventors discovered that there are at least three isocyanate functional groups using（It is end group, and end group gold Belong to ion closing）Water dispersible polyurethane resin form said composition in the case of, it is possible to reduce rainbow phenomena and in high temperature height Moisture-proof is improved under wet very harsh conditions, so as to be improved and optic polymer basement membrane in post processing（Such as hard conating Film etc.）Cohesive, this completes fourth embodiment of the invention.

Hereinafter, the various configurations of fourth embodiment of the invention be will be described in detail.

Fourth embodiment of the invention is related to water-dispersed composition, and the water-dispersed composition, which includes, to be used to adjust refraction First water-dispersed composition of rate and under hot and humid very harsh conditions improve moisture-proof with excellent adhesion Second water-dispersed composition of property.

More specifically, the one side of four embodiment of the invention is related to a kind of water-dispersed composition, and it includes The mixture of one water-dispersed composition and the second water-dispersed composition,

Wherein, first water-dispersed composition includes water dispersible polyurethane resin, the water dispersible polyurethane resin by 10 to 75 weight % linear polymer with two end groups and 25 to 90 weight %'s is branched poly- with least three end groups Compound forms, and

[chemical formula 1]

[chemical formula 2]

More specifically, in fourth embodiment of the invention, the water-dispersed composition can also include silicones Wetting agent and colloidal silica particles are as additive to be advantageous in the epilamellar coating performance of optic polymer and the bottom of at Resistance to hot-working on enamelled coating.

More specifically, in this aspect of four embodiment of the invention, the water-dispersed composition can include 5 to The mixture of 10 weight % the first and second water-dispersed compositions, 0.1 to the 0.5 weight % wetting agent based on silicones, 0.1 To 0.5 weight % colloidal silica particles, and the water of surplus.

In this aspect of four embodiment of the invention, the water-dispersed composition can also include hydrophilic when needed Property organic solvent and surfactant are to increase dispersion stabilization.

As hydrophilic organic solvent, using dioxane, acetone, tetrahydrofuran and MEK etc., and surface-active is used as Agent, using anion surfactant or nonionic surface active agent, so that dispersion stabilization can be improved.It is preferred that Ground, the content of hydrophilic organic solvent and surfactant used is 0.1 to 5 weight %.

In addition, in the embodiment of four embodiment of the invention, the mixing of first and second water-dispersed composition Thing can be the first and second water-dispersed compositions with 1:9 to 5:Mixture of 5 weight than mixing.With being used independently first Compared with the situation of the second water-dispersed composition, in the case where being used in mixed way the first and second water-dispersed compositions, Ke Yirong Change places and adjust cohesive and refractive index and the optical property such as rainbow phenomena can be overcome.In the first water-dispersed composition Mixed weight ratio be less than 1 in the case of, the effect for improving cohesive may be small, and in the mixing weight of the first water-dispersed composition In the case that amount is than being more than 5, overcoming the effect of rainbow phenomena may be lowered.

In whole water-dispersed composition, the content of the mixture of used first and second water-dispersed composition can be with For 5 to 10 weight %.When the content is less than 5 weight %, coating performance is excellent, but is likely difficult to realize bonding, and works as content During more than 10 weight %, cohesive is excellent, but is likely difficult to realize the outward appearance and the transparency of coating.

The content of the wetting agent based on silicones can be 0.1 to 0.5 weight %, and colloidal silica particles Content can be 0.1 to 0.5 weight %.In addition, the particle mean size of the colloidal silica particles can be 50 to 1000nm. In the case where granularity is less than 50nm, it may be difficult to play a part of antiblocking agent, and in the case where granularity is more than 1000nm, Mist degree may be increased, so as to which optical property may deteriorate.

In the aspect of four embodiment of the invention, the first water-dispersed composition can include water dispersible polyurethane Resin, the water dispersible polyurethane resin by 10 to 75 weight % the linear polymer and 25 to 90 weight % with two end groups Branched polymer with least three end groups and water composition, with the solid content with 10 to 30 weight %.The linear polymerization Thing refers to linear polyester resin, and the branched polymer refers to branched polyurethanes resin.

The water dispersible polyurethane resin includes：It is the branched polymeric of the isocyanate functional group of end group with least three Thing, and the isocyanate groups partly or entirely use inorganic acid salt（More specifically, for example, sulfate inorganic salts）Envelope End；And the linear polymer with two isocyanate functional groups, and the isocyanate groups partly or entirely use nothing Machine hydrochlorate（More specifically, for example, sulfate inorganic salts）End-blocking.

The water dispersible polyurethane resin can be by 10 to 75 weight the % linear polymer and 25 to 90 weight % The branched polymer composition.Branched polymer content be less than 25 weight % in the case of, it may not be possible to meet swelling ratio and Gel fraction, and be likely difficult to obtain in the hot and humid lower film with excellent adhesiveness.In addition, in branched polymer In the case that content is more than 90 weight %, because excessive gelation causes the quick increase of viscosity, it may be difficult to prepare water discrete sets Compound, and the surface appearance defects such as crackle can be produced when with the surface of said composition coated film.In the present invention, Branched polymer refers to the resin with least three isocyanate functional groups.

In fourth embodiment of the invention, when water dispersible polyurethane adhesive includes water dispersible polyurethane resin and water During with solid content with 10 to 30 weight %, the adhesive can be easily mixed, and said composition is being applied to basement membrane The thickness of dry coating film was easily adjusted when upper.

As the method for preparing the water dispersible polyurethane resin, for example, can preferably with the following method：By 39 to 45 The isocyanate compound of weight % polyalcohol, 0.3 to 1.2 weight % trimethylolpropane and 50 to 57 weight % is anti-each other Should come prepare end group be terminal isocyanate groups prepolymer, then again by the prepolymer and 3 to 4 weight % inorganic acid salt reaction, To close the terminal isocyanate groups with the ionic group of sulfate to prepare the water dispersant type polyaminoester resin, but it is described Method not limited to this.In the case of using the above method, it can prepare and be mixed with linear polyester resin and branched polyurethanes The water dispersible polyurethane resin of resin, and especially it is possible to prepare the linear polymer and 25 to 90 weights by 10 to 75 weight % Measure the water dispersible polyurethane resin of % branched polymer composition.

When the weight average molecular weight of the water dispersible polyurethane resin is in the range of 10,000 to 20,000, the polyurethane Resin may not gelation but be dispersed in water, and can obtain hot and humid lower with excellent physical properties Film.

The weight average molecular weight can use GPC- multi-angle light scattering（MALS）System（WyattCo.）Measurement, and The configuration of MALS systems is as follows.

The configuration of MALS systems

-GPC：Water1525 binary HPLC pumps

- RI detectors：Optilab rex

-MALS：Wyatt Dawn8+

- mobile phase：DMF(50mM LiCl)

- flow velocity：0.5mL/min

- temperature：50℃

- sample size：0.5%, 500 μ l

As polyalcohol, the polyalcohol based on polyester or the polyalcohol based on polyethers can be used, and preferably use base In the polyalcohol of polyester.Polyalcohol based on polyester can be by prepared by carboxylic acid, decanedioic acid or acid anhydrides and polyol reaction Polyalcohol.The species of polyalcohol is not limited, and preferably uses the PEPA of weight average molecular weight 600 to 3000. The content of polyalcohol can be 39 to 45 weight %.In the case where content is less than 39 weight %, molecular weight diminishes so that prime coat Become really up to the mark, and be likely difficult to stretch, so as to which appearance of coat may be bad.In the case where content is more than 45 weight %, online Coating（ILC）Layer becomes too soft so that may deteriorate isolation performance.

Trimethylolpropane is used to prepare the prepolymer with three functional groups, and trimethylolpropane used Content can be 0.3 to 1.2 weight %.In the case where content is less than 0.3 weight %, crosslink density can be reduced and can reduced Resistance to blocking, and in the case where content is higher than 1.2 weight %, crosslink density is too high, deteriorates tensile property, so as to outside coating Seeing may be bad, and bonding force can deteriorate.

In the one side of four embodiment of the invention, second water-dispersed composition has high index of refraction and low glass Glass transition temperature, so as to not cracked when after manufacturing the film in stretched film or region.Especially, the second water dispersed combination Thing is used to overcome the optical property such as rainbow phenomena, in the case where using polyester film as basement membrane, preferably with 1.58 To 1.64 refractive index and 40 to 60 DEG C of glass transition temperature.When refractive index within the above range when, the second water discrete sets Refractive index difference between compound and the polyester film for being basement membrane is small, so as to produce rainbow phenomena.In addition, in glass transition In the case that temperature is in the range of 40 to 60 DEG C, when manufacturing polyester film by on-line machining, when described in coating before the stretching During water-dispersed composition, stretching and can sufficiently degraded in heat treatment process, so as to which change will not be produced in film In vain.

In order to meet the requirement of above-mentioned refractive index and glass transition temperature, the second water-dispersed composition includes passing through polycondensation The polyester resin that acid constituents and diol component obtain, wherein NDA of the acid constituents including 20 to 40 moles of %, 1 to the 10 mole of % aromatic dicarboxylic acid comprising sulfonate and 1 to 10 mole of % aromatic dicarboxylic acid, and the dihydric alcohol group Point include 10 to 30 moles of % pair [4 (2- hydroxyl-oxethyls) phenyl] fluorenes represented by chemical formula 1 below, 1 to 10 mole of % The triglyceride compound and 30 to 60 moles of % diol compound represented by chemical formula 2 below.

[chemical formula 1]

[chemical formula 2]

The aromatic dicarboxylic acid can be selected from dimethyl terephthalate (DMT), terephthalic acid (TPA), M-phthalic acid, 1,2- Any in naphthalenedicarboxylic acid, 1,4- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 1,3- pentamethylene dioctyl phthalate and 1,4 cyclohexanedicarboxylic acid Kind or at least two mixture.

The diol compound can be selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, five ethylene glycol, six Any of ethylene glycol, propane diols, tripropylene glycol, 1,3- propane diols, 1,3 butylene glycol, propane diols, bisphenol-A, bisphenol b or At least two mixture.

In addition, in fourth embodiment of the invention, the polyester resin can meet following physical property：Refraction Rate is 1.58 to 1.64, and glass transition temperature is 40 to 60 DEG C.

In fourth embodiment of the invention, second water-dispersed composition can include water dispersible polyester and bond Agent, the water dispersible polyester adhesive include the polyester resin and water with the solid content with 10 to 40 weight %.

In third embodiment of the invention, the NDA of the acid constituents is a kind of dicarboxylic acid component, such as There are two aromatic rings shown in chemical formula 3 below, thereby increase refractive index.

[chemical formula 3]

The content of 2,6- naphthalenedicarboxylic acids can be preferably 20 to 40 moles of %.In the case of less than 20 moles % of the content, It is likely difficult to so that polyester resin has a high index of refraction, and in the case of higher than 40 moles % of the content, it may be difficult to by the group Compound is dispersed in water.

In addition, the aromatic dicarboxylic acid comprising sulfonate is used to ensure the dispersibility in water, and can be Selected from 2,5- dicarboxyls benzene sulfonic acid sodium salt, 5- sulfoisophthalic acids, sulfoisophthalic acid and 4- sulfo groups-naphthalene -2,6- dioctyl phthalate Deng any of or at least two mixture.It is highly preferred that 2, the 5- dicarboxyl benzene sulphurs represented by chemical formula 4 can be used Sour sodium.The content of aromatic dicarboxylic acid comprising sulfonate used can be preferably 1 to 10 mole of %, and low in the content In the case of 1 mole of %, water dispersible may deteriorate, and in the case of higher than 10 moles % of content, hydrophily became Greatly, so as to which process performance may deteriorate or may produce the adhesion of film.

[chemical formula 4]

In addition, the aromatic dicarboxylic acid refers to the aromatic dicarboxylic acid except including NDA and sulfonate Outside other dicarboxylic acid components, and can be selected from dimethyl terephthalate (DMT), terephthalic acid (TPA), M-phthalic acid, 1, Appointing in 2- naphthalenedicarboxylic acids, 1,4- naphthalenedicarboxylic acids, 1,5- naphthalenedicarboxylic acids, 1,3- pentamethylene dioctyl phthalate and 1,4 cyclohexanedicarboxylic acid It is a kind of or at least two mixture, but not limited to this.The content of aromatic dicarboxylic acid used can be preferably 1 to 10 Mole %, and in the case of less than 1 mole % of the content, hence it may becomes difficult to increase refractive index, and in content higher than 10 moles of %'s In the case of, it may be difficult to said composition is dispersed in water, and b values may increase and due to the aromatics group when manufacturing film The increase divided may cause bonding force to reduce.

In the diol component of fourth embodiment of the invention, double [4 (2- hydroxyl-oxethyls) of chemical formula 1 below Phenyl] fluorenes is used to increase refractive index and have high transparency, and its content can be preferably 10 to 30 moles of %.Contain at this In the case of less than 10 moles % of amount, it may be difficult to increase refractive index, and in the case of higher than 30 moles % of the content, Ke Nengnan So that said composition to be dispersed in water.

[chemical formula 1]

In addition, the use of the triglyceride compound represented by chemical formula 2 below it is somebody's turn to do after coating in stretching to overcome The defects of being cracked in the technical process of film with non-through melting forming region excessively, and in order to uniform film and folding Penetrate rate, and in order to reduce with refractive index increase and increased glass transition temperature, the triglyceride compound are used for Introduce the collateral chain with long-chain.The content of used triglyceride compound can be 1 to 10 mole of %.It is less than 1 in content In the case of mole %, transition temperature（Tg）It is not decreased sufficiently, and in the case of higher than 10 moles % of content, refractive index can It can reduce and there may be the adhesion of film.

[chemical formula 2]

According to the polyester resin obtained by polycondensation said components of four embodiment of the invention can have 0.1 to 1.0, more preferably 0.1 to 1.6 inherent viscosity.Within the above range, the polyester emulsion can be by the way that the polyester resin be divided Dissipate or be dissolved in water or aqueous solvent and prepare.

The polyester resin obtained according to four embodiment of the invention can pass through the synthesizing polyester in association area It is prepared by the method for resin.For example, in the absence of a solvent, the NDA including 20 to 40 moles of %, 1 to 10 are rubbed The acid constituents of your % aromatic dicarboxylic acid comprising sulfonate and 1 to 10 mole of % aromatic dicarboxylic acid and rubbed including 10 to 30 The glycol of your % double [4 (2- hydroxyl-oxethyls) phenyl] fluorenes, 1 to 10 mole of % triglyceride compound and 30 to 60 moles of % The diol component of compound is mixed with each other, and the mixture is put into reactor, then carries out esterification by heating, together When remove caused by water byproduct or methanol.Then, it is anti-by reducing the pressure in reactor while raising temperature progress polycondensation Should, while reclaim accessory substance diol component.

In the water-dispersed composition of four embodiment of the invention, the mixture of the first and second water-dispersed compositions can With with 1.57 to 1.62 refractive index.When refractive index within the above range when, be applied to by said composition on polyester base film When can overcome rainbow phenomena and optical property.

In addition, the another aspect of four embodiment of the invention is related to comprising by being coated with water-dispersed composition formation The optical film of primer coating.

The optical film of the aspect of four embodiment of the invention can include polyester base film and by the basement membrane The primer coating that the water-dispersed composition is formed is coated with one or both sides.The dry coating thickness of the primer coating can be 50 to 100nm.

, can be with excellent due to excellent light transmittance in the optical film according to the aspect of four embodiment of the invention Choosing uses polyester film（More specifically, polyethylene terephthalate or poly (ethylene naphthalate) film）As basement membrane, And the basement membrane can include additive or particulate.As this polyethylene terephthalate film, preferably using stretching The polyethylene terephthalate film crossed, and can use be stretched uniaxially or biaxially polyethylene terephthalate Film.The thickness of basement membrane used can be 50 to 250 μm, but be not restricted to that this.

In the optical film according to the aspect of four embodiment of the invention, in the side of optic polymer basement membrane or The prime coat formed on both sides has excellent cohesive and easily viscosity, that is, allows the property bonded with other substrates.

In the optical film according to the aspect of four embodiment of the invention, the dry coating thickness of the primer coating Can be 50 to 100nm.As coating method, it can use and be coated with the group on the surface in the technical process of oriented polyester film The online rubbing method of compound, the offline rubbing method after the film is manufactured can also be used.Both approaches can use.It is preferred that Ground, online rubbing method can be used, because be coated and film forming simultaneously, manufacturing cost can be reduced, and can lead to Thickness of the overstretching than changing coating.

In the optical film according to the aspect of four embodiment of the invention, the primer coating can meet following Physical property：With equation 1 below measure swelling ratio be 35 to 100, with equation 2 below measure gel fraction for 75 to 85, and refractive index is 1.54 to 1.62.

[formula 1]

（In equation 1, the weight after holding refers to dry coating film（About 1g）Immerse distilled water（50g）In and 70 DEG C guarantor The weight measured after holding 24 hours.）

[formula 2]

Gel fraction=（Dried weight/original weight）×100

（In formula 2, dried weight refers to dry coating film（About 1g）Immerse distilled water（50g）In, in 70 DEG C of holdings 24 hours, then again by the film after the holding in 120 DEG C of weight measured after drying 3 hours.）

Hereinafter, the detailed description of four embodiment of the invention will be provided by embodiment.But the present invention is not limited to The following examples.

With following measuring method physical properties.

1st, the measurement of the physical property of film

By the mixture of the first and second water-dispersed compositions（15g）It is put into diameter 80mm and height 15mm bulge In, and dry 72 hours at 65 DEG C and dried 3 hours at 120 DEG C.By dry coating（1g）Immerse distilled water（50g）In simultaneously After 70 DEG C are kept for 24 hours, take out the film after keeping and measure its swelling ratio.Film after holding is dried 3 at 120 DEG C Hour, its weight is then measured, thus calculated for gel fraction.

1）Swelling ratio：By dry coating（1g）Immerse distilled water（50g）In and 70 DEG C keep 24 hours after, take out protect Film after holding simultaneously records its swelling ratio.

Gel fraction=（Dried weight/original weight）×100

Second circulation=- 40 DEG C~200 DEG C, 20 DEG C/min

2）The measurement of refractive index

The mixture of first and second water-dispersed compositions is applied on polycarbonate membrane, then dried.Then, in room Temperature is lower to use refractometer（Abbe refractometer, ATAGOCo., DR-M2 ,@550）Measure its refractive index.

3）The measurement of total light transmittance

The total light transmittance of whole film uses haze meter（Nippon Denshoku Co.NDH-5000）Measurement.

4）The measurement 1 of rainbow phenomena degree

Water-dispersed composition according to embodiment and comparing embodiment is being applied to polyester base film with 200nm thickness （The polyethylene terephthalate film that 188 μm of thickness）Side on manufacture optical film after, carry out hard conating on one side thereof （Refractive index 1.52）Processing, and opposite side blacking.Then, it is confirmed whether to produce rainbow with bore hole.In three wavelength lamps in darkroom Under estimated.

Evaluation criterion is as follows.

Well：There is not rainbow phenomena, and color impression is uniform.

5）The measurement 2 of rainbow phenomena degree

Water-dispersed composition according to embodiment and comparing embodiment is being applied to polyester base film with 200nm thickness （The polyethylene terephthalate film that 188 μm of thickness）Side on manufacture optical film after, carry out hard conating on one side thereof （Refractive index 1.52）Processing, and opposite side blacking.Then measured using UV- visible (CARY5000) anti-in visible-range Penetrate pattern.

6th, appearance of coat

When the film of the with good grounds embodiment of observation band and the water-dispersed composition of comparing embodiment, while in three wavelength lamps Under make light transmission by they,

7th, the evaluation of bonding force（ASTM B905）

In manufacture according to after the optical film of embodiment and comparing embodiment, hard coating composition is applied to the coating On the side of composition coating.Then, bonding force at room temperature is evaluated by the following method：Examined using cross cutting type adhesion Survey instrument（cross hatch cutter）(YCC-230) rule with being spaced on 1cm X1cm film for 1mm, bonding force is surveyed Try（Nichban No.405）It is adhered thereto, and peels off the adherent zone from it three times.In hot and humid lower evaluation bonding During power, the bonding force between hard conating and online coating is carrying out hot water treatment（100 DEG C, 10min）Carry out in aforementioned manners afterwards Evaluation.

8th, the measurement of the coating layer thickness of dried layer

In full wafer with the film being coated with according to the water-dispersed composition of embodiment and comparing embodiment, what is be transversely to the machine direction 5 points are marked with 1m interval on the TD of direction, then using SEM（Hitachi S-4300）Measure its cross section.In addition, marked The region gone out is amplified with 50000x multiplying power, measures the thickness at 30 points, and calculate its average value in this region.

9th, mist degree

Use NDH-5000（Nippon Denshoku Co.）Measure mist degree.

[preparing embodiment 4]

The preparation of first water-dispersed composition

Prepare has the water dispersible polyurethane of 50 weight % branched polymers in theory.

In the polyethylene glycol adipate glycol by making 40 weight %, 0.6 weight % trimethylolpropane and 55.9 weights Amount % hexamethylene diisocyanate react with each other preparation have isocyanate functional group as the prepolymer of end group after, by make for The isocyanates of prepolymer end functional group and 3.5 weight the % niter cake as ionic group react, and preparation has ion Group and the polyurethane that weight average molecular weight is 14,400.

By the way that the they of 20 weight % above-mentioned preparation is prepared into the weight %'s of solid content 20 in 80 weight % water First water-dispersed composition.

[preparing embodiment 5]

The preparation of second water-dispersed composition

Under condition of no solvent, by 40 moles of NDA（26 moles of %）, 5 moles of 2,5- dicarboxyls benzene sulfonic acid sodium salt （3.3 moles of %), 5 moles of dimethyl terephthalic acid（3.3 moles of %）, double [4 (2- hydroxyl-oxethyls) phenyl] 20 moles of fluorenes （13.3 mole %）, triglycerides（Kao Corp., name of product：85P）10 moles（6.6 moles of %）With 70 moles of ethylene glycol （46.4 mole %）It is mixed with each other and is put into reactor, is entered by the way that temperature is warming up into 250 DEG C from 170 DEG C with 1 DEG C per minute Row esterification, while remove water byproduct or methanol.Then, by being decompressed to 1mmHg in the reactor, it is warming up to simultaneously 260 DEG C of progress polycondensation reactions, while accessory substance glycol is reclaimed, thus prepare the polyester resin of inherent viscosity 1.0.

By the polyester dispersion of 20 weight % above-mentioned preparation is prepared to the weight % of solid content 20 in 80 weight % water Two water-dispersed compositions.

[embodiment 32]

1）The preparation of water-dispersed composition 1：With 1:9 weight is than the first and second water-dispersed compositions of mixing.

By 0.6 weight % the first water-dispersed composition prepared in embodiment 4 is prepared, 5.4 weight % prepare it is real Apply the second water-dispersed composition prepared in example 5,0.3 weight % silicone wetting agent（Dow Corning Corp., polyester- Silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and to stir 2 small When, thus prepare water-dispersed composition 1.

In the case, the first and second water-dispersed compositions are with 1:9 weight measures the physics of film than mixing Property.As a result it is shown in following table 7.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Water-dispersed composition 1 is coated on the both sides of described by bar type rubbing method, and 110 to 150 are warming up to 1 DEG C per second of speed DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, enter at 230 DEG C in 5 grades of stenters Row heat treatment, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in 200 DEG C of films by heat treatment Coated on its both sides and there is the biaxially-stretched film of 188 μ m thicks.The primer coating prepared with the water-dispersed composition 1 is done Coating layer thickness can be 100nm.

The physical property of manufactured optical film is shown in table 8 below.

[embodiment 33]

1）The preparation of water-dispersed composition 2：With 2:8 weight is than the first and second water-dispersed compositions of mixing.

By 1.2 weight % the first water-dispersed composition prepared in embodiment 4 is prepared, 4.8 weight % prepare it is real Apply the second water-dispersed composition prepared in example 5,0.3 weight % silicone wetting agent（Dow Corning Corp., polyester- Silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and to stir 2 small When, thus prepare water-dispersed composition 2.

In the case, the first and second water-dispersed compositions are with 2:8 weight measures the physics of film than mixing Property.As a result it is shown in following table 7.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Water-dispersed composition 2 is coated on the both sides of described by bar type rubbing method, and 110 to 150 are warming up to 1 DEG C per second of speed DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, enter at 230 DEG C in 5 grades of stenters Row heat treatment, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in 200 DEG C of films by heat treatment Coated on its both sides and there is the biaxially-stretched film of 188 μ m thicks.The primer coating prepared with the water-dispersed composition 2 is done Coating layer thickness can be 100nm.

The physical property of manufactured optical film is shown in table 8 below.

[embodiment 34]

1）The preparation of water-dispersed composition 3：With 3:7 weight is than the first and second water-dispersed compositions of mixing.

By 1.8 weight % the first water-dispersed composition prepared in embodiment 4 is prepared, 4.2 weight % prepare it is real Apply the second water-dispersed composition prepared in example 5,0.3 weight % silicone wetting agent（Dow Corning Corp., polyester- Silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and to stir 2 small When, thus prepare water-dispersed composition 3.

In the case, the first and second water-dispersed compositions are with 3:7 weight measures the physics of film than mixing Property.As a result it is shown in following table 7.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Water-dispersed composition 3 is coated on the both sides of described by bar type rubbing method, and 110 to 150 are warming up to 1 DEG C per second of speed DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, enter at 230 DEG C in 5 grades of stenters Row heat treatment, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in 200 DEG C of films by heat treatment Coated on its both sides and there is the biaxially-stretched film of 188 μ m thicks.The primer coating prepared with the water-dispersed composition 3 is done Coating layer thickness can be 100nm.

The physical property of manufactured optical film is shown in table 8 below.

[embodiment 35]

1）The preparation of water-dispersed composition 4：With 4:6 weight is than the first and second water-dispersed compositions of mixing.

By 2.4 weight % the first water-dispersed composition prepared in embodiment 4 is prepared, 3.6 weight % prepare it is real Apply the second water-dispersed composition prepared in example 5,0.3 weight % silicone wetting agent（Dow Corning Corp., polyester- Silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and to stir 2 small When, thus prepare water-dispersed composition 4.

In the case, the first and second water-dispersed compositions are with 4:6 weight measures the physics of film than mixing Property.As a result it is shown in following table 7.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Water-dispersed composition 4 is coated on the both sides of described by bar type rubbing method, and 110 to 150 are warming up to 1 DEG C per second of speed DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, enter at 230 DEG C in 5 grades of stenters Row heat treatment, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in 200 DEG C of films by heat treatment Coated on its both sides and there is the biaxially-stretched film of 188 μ m thicks.The primer coating prepared with the water-dispersed composition 4 is done Coating layer thickness can be 100nm.

The physical property of manufactured optical film is shown in table 8 below.

[embodiment 36]

1）The preparation of water-dispersed composition 5：With 5:5 weight is than the first and second water-dispersed compositions of mixing.

By 3.0 weight % the first water-dispersed composition prepared in embodiment 4 is prepared, 3.0 weight % prepare it is real Apply the second water-dispersed composition prepared in example 5,0.3 weight % silicone wetting agent（Dow Corning Corp., polyester- Silicone copolymers）It is added to the water with 0.3 weight % particle mean size 140nm colloidal silica particles and to stir 2 small When, thus prepare water-dispersed composition 5.

In the case, the first and second water-dispersed compositions are with 5:5 weight measures the physics of film than mixing Property.As a result it is shown in following table 7.

2）The manufacture of dual coating polyester film

Anhydrous poliester chip is being put into extruder and after melting extrusion, is using surface temperature 20 DEG C of curtain coating drum fast cooling temperature simultaneously hardens, and thus manufactures the polyethylene terephthalate piece of 2000 μm of thickness. 80 DEG C in longitudinal direction（MD）On manufactured polyethylene terephthalate piece stretched 3.5 times and be cooled to room temperature.Then, use Water-dispersed composition 5 is coated on the both sides of described by bar type rubbing method, and 110 to 150 are warming up to 1 DEG C per second of speed DEG C, and by preheating and drying coated sheets in transverse direction（TD）Upper 3.5 times of stretching.Then, enter at 230 DEG C in 5 grades of stenters Row heat treatment, 10% is relaxed in the longitudinal and transverse direction so that its heat cure, is thus manufactured in 200 DEG C of films by heat treatment Coated on its both sides and there is the biaxially-stretched film of 188 μ m thicks.The primer coating prepared with the water-dispersed composition 5 is done Coating layer thickness can be 100nm.

The physical property of manufactured optical film is shown in table 8 below.

[table 7]

	Swelling ratio	Gel fraction	Tg(℃)	Refractive index
					Embodiment 32	98.2	81.4	36	1.594
Embodiment 33	96.0	79.2	42	1.588
					Embodiment 34	92.4	76.5	46	1.582
Embodiment 35	90.3	76.0	46	1.576
					Embodiment 36	88.7	77.2	48	1.57

As shown in table 7, it is found that forming film using water-dispersed composition according to an embodiment of the invention In the case of, the film has more than 1.57 high index of refraction, less than 48 DEG C of lower glass transition temperatures, and excellent moisture-proof Property.

[table 8]

As shown in Figure 8, it was demonstrated that, on using the both sides of water-dispersed composition according to embodiments of the present invention in polyester film all Formed coating in the case of, the film can with more than 93% excellent total light transmittance, low haze and excellent appearance of coat with And excellent bonding force, and rainbow phenomena therein can be overcome.

Claims

1. a kind of optical film, it includes polyester base film and the bottom being coated with coating composition on the one or both sides of the basement membrane Lacquer coat, the coating composition includes the polyester resin of refractive index 1.4 to 1.6, the surface of refractive index 1.8 to 2.2 is modified Thus zirconia sol and particle mean size 100 have 1.56 to 1.6 total refractive index to 200nm silica, wherein institute The dry coating thickness for stating primer coating is 50 to 150nm, the particle mean size of the zirconia sol that the surface is modified for 1 to 50nm, the surface of the zirconia sol use modified with organic acids.

2. optical film according to claim 1, wherein, the zirconia sol that the surface is modified has acyl in its surface Base or alkylation group, and use Na⁺As counter ion.

3. optical film according to claim 1, wherein, the coating composition includes 5 to 30 weight % refractive index 1.4 The wetting agent of polyester resin, 0.1 to 0.4 weight %, 0.1 to 0.5 weight % particle mean size 100 to the two of 200nm to 1.6 The moisture that silica and 0.5 to 30 weight % solid content are 5 to 40 weight % dissipates zirconia sol that surface is modified to have There is 2 to 10 weight % total solid content, wherein the content of the whole components included in the coating composition is 100 weight %.

4. optical film according to any one of claim 1 to 3, the optical film is in the one or both sides of the primer coating On further comprise the acrylic resin coating of refractive index 1.51 to 1.53.

5. optical film according to claim 4, wherein, the dry coating thickness of the acrylic resin coating is 1 to 10 μm.

6. optical film according to claim 5, wherein, in the situation that the acrylic resin coating is formed on side Under, the optical film has less than 1.0% mist degree and more than 91% total light transmittance, and exists in the acrylic resin coating In the case of being formed on both sides, the optical film has less than 0.5% mist degree and more than 92% total light transmittance.