CN102725336B - Laminated film - Google Patents

Abstract

Provided is a laminated film with excellent tight adhesion and moist-heat resistance. The laminated film is obtained by laminating a coating layer on at least one surface of a substrate film, wherein the coating layer comprises a polycarbonate-based urethane resin as the main component and contains oxazoline groups in an amount of 0.5 to 4.0mmol/g.

Description

Stacked film

Technical field

The present invention relates to the good stacked film of adaptation and humidity resistance.Specifically, the easy adhesive film that relates to the basement membrane of optical functional films such as being suitable as the hard coat film that is mainly used in indicating meter etc., antireflection film, light diffusing sheet, lens, near infrared ray blocking film, transparent and electrically conductive film, antiglare film.

Background technology

Usually, as the base material of the optical functional film used in liquid-crystal display (LCD), use the transparent heat plastic resin film formed by ethylene glycol terephthalate (PET), vinylformic acid (ester), polycarbonate (PC), cellulosetri-acetate (TAC), polyolefine, polymeric amide etc.

State in the use in the situation of heat plastic resin film as the base material of various optical functional films the stacked optical functional layer that meets various uses.For example, in liquid-crystal display (LCD), can list: prevent surface damage protective membrane (hard coat), prevent anti-reflection layer (AR layer) that outer illumination enters, for assembling and the lens jacket of diffusion light, improving the functional layers such as light diffusion layer of brightness.In the middle of these base materials, polyester film particularly, because the transparency, dimensional stability, resistance to chemical reagents are good, and less expensive, therefore be widely used as the base material of various optical functional films.

Usually, when the basement membrane as for stacked functional layer is used, be the cementability of raising with functional layer, and proposed to give by the whole bag of tricks the method for easy-adhesion.For example, usually known method is to take by arranging on the heat plastic resin film surface at base material the overlay that the various resins such as polyester, vinylformic acid (ester), urethane, vinylformic acid (ester) grafted polyester are the main composition composition, thereby gives the base material film easy-adhesion.In this coating process, industrial enforcement be coating process and de-production line coating process in production line, in production line in coating process, heat plastic resin film before completing for crystalline orientation in stretched film, the solution of above-mentioned resin or the water-based coating liquid that contains the dispersion that resin dispersion is obtained by dispersion medium are coated on base material film, after drying, at least along uniaxial extension, then implement thermal treatment, make heat plastic resin film complete orientation; In de-production line coating process, after manufacturing heat plastic resin film, on this film, coating water system or solvent are coating liquid, dry afterwards.

No matter indoor, outdoor can the uses in various environment such as handheld device that the indicating meter such as LCD, PDP and the hard coat film of take are parts.Especially, handheld device is except high transparent, and requirement sometimes can also tolerate the humidity resistance in bathroom, hot and humid area etc.That is, even need also there is high adhesion under hot and humid for the stacked film of such use.For this reason, example, disclose and added linking agent in coating liquid, thereby formed the easy-adhesion heat plastic resin film that crosslinking structure has been endowed humidity resistance during by the stacked overlay of coating process in based on production line in overlay as shown below.

For example, a kind of lens film that is provided with stacked film is disclosed in patent documentation 1, wherein, contain in stacked film and be selected from vinylformic acid (ester) resin, a kind of resin in vibrin and carbamate resins and be selected from the melamine series linking agent, oxazoline is linking agent, the isocyanate-based linking agent, aziridine is that linking agent or epoxy are at least one the linking agent in linking agent, and contain the acid amides ester bond, amino-formate bond, amido linkage, at least one in the urea key, particularly, carbamate resins and melamine series linking agent have been exemplified, vibrin and melamine series linking agent Yi are Ji oxazoline is linking agent, vinylformic acid (ester) resin and vibrin are with oxazoline is linking agent etc.

Exemplified a kind of optics that is provided with overlay easy-adhesion polyester film in patent documentation 2, wherein, the vinylformic acid that overlay contains vibrin and Ju You oxazolinyl and polyoxyalkylene chain (ester) resin.

Having exemplified a kind of polyester that applied in patent documentation 3 is the easy adhesive film of the polymkeric substance of urethane and Han You oxazoline.

Having exemplified polycarbonate-based urethane with anionic property group and melamine series linking agent or epoxy in patent documentation 4 is linking agent.

In addition, the applicant in patent documentation 5, exemplified a kind of stacked by polyester copolymerization resin, urethane resin He oxazoline, be the easy adhesive film of optics of the overlay that forms of linking agent.

The prior art document

Patent documentation

Patent documentation 1: JP 2000-141574 communique

Patent documentation 2: No. 3737738 communique of patent

Patent documentation 3: JP 2000-355086 communique

Patent documentation 4: No. 2544792 communique of patent

Patent documentation 5: No. 3900191 communique of patent

Summary of the invention

Invent problem to be solved

In order to reduce global environment load, the household appliances etc. of expecting to have indicating meter reach above at present long lifetime.For this reason, not only require to have at first adaptation, even and require also to need to keep for a long time adaptation under hot and humid environment.But disclosed easy adhesive film in above-mentioned patent documentation, although, even also demonstrate good adaptation when bonding under hygrothermal environment at first, but can't avoid the reduction of dhering strength during life-time service.For this reason, consider the expansion to various environments for use, be envisioned that owing to reducing in hot and humid lower adaptation, so problem that can't the long term maintenance initial performance will more obviously changed from now on.

The present invention in view of the above problems, provides the stacked film deteriorated, that in other words the adaptation (humidity resistance) under hot and humid environment reduces of the overlay that is considered to hardly under unavoidable hot and humid environment so far.

In addition, the said high temperature of the present invention, adaptation under high humidity (humidity resistance) refer to light-cured type vinylformic acid (ester) layer by layer poststack at 80 ℃, under the environment of 95%RH, place 48 hours, use the cutter guide that clearance gap is 2mm, arrive the latticed scores of base material film at 100 perforation light-cured type vinylformic acid (ester) resin layers of the upper formation in light-cured type vinylformic acid (ester) layer surface, then, cellophane tape is attached to latticed score surface, rub and make it fully closely sealed with eraser, adaptation while firmly same position being peeled to 5 times again, it is the adaptation evaluation method of the criterion stricter than the evaluation method of JIS K5600-5-6 record usually used.Problem of the present invention is to provide a kind of stacked film, and this stacked film not only has initial adaptation (initial stage adaptation), even and also can keep excellent adaptation above-mentioned under hot and humid.

Solve the means of problem

The present application artificially solves above-mentioned problem and is furtherd investigate, found that and a kind ofly take polycarbonate-based carbamate resins as main component the overlay that contains 1.0mmol/g～4.0mmol/g oxazolinyl, not only there is the initial stage adaptation, and present the surprising effect that humidity resistance also improves, thereby completed the present invention.Find that compound Bing Shi oxazolinyl by containing polycarbonate-based carbamate resins and Ju You oxazolinyl in overlay is in they remain in overlay under in fact containing crosslinking structure or the low state of degree of crosslinking, even also can maintain high adhesion under hot and humid, this has overthrown the fact of prior art general knowledge, thereby has completed the present invention.

As putting down in writing in above-mentioned patent documentation, technology general knowledge is up to now thought: in order to improve adaptation, wish mixed cross-linker and the resin with the functional group that can react with linking agent, the crosslinking structure of height of formation while making overlay stacked.But, found that of the present invention further investigation: by being used as the Yu oxazolinyl to present the carboxyl of functional group of hyperergy or its salts contg is few or the polycarbonate-based carbamate resins Yi that do not contain in fact forms uncrosslinked oxazolinyl remaining overlay in specified range Ji oxazoline is linking agent, thereby initial stage adaptation and the adaptation under damp and hot improve, and technological thought has in contrast to the prior art made stacked film based on this.

That is, in the present invention in overlay in specified range Can Cun oxazolinyl be essential.According to technology general knowledge, with carboxyl have hyperergy oxazoline be linking agent be with the resin combination with functional groups such as carboxyls after apply, and have no reason and the resin combination that do not contain in fact carboxyl is used, therefore can differentiate clearly with prior art.In addition, the content of overlay Zhong oxazolinyl can absorb infrared measure by total reflection and tries to achieve.

The present invention can reach by following solution.

A first aspect of the present invention is a kind of stacked film, wherein, this stacked film is the stacked stacked film of overlay at least one face of base material film, described overlay be take polycarbonate-based carbamate resins as principal constituent, also contains 0.5mmol/g～4.0mmol/g oxazolinyl in described overlay.

The stacked film of a second aspect of the present invention is based on above-mentioned stacked film, and wherein, described base material film comprises vibrin.

The stacked film of a third aspect of the present invention is based on above-mentioned stacked film, wherein, the stepped construction that described base material film is A layer, B layer, A layer, the A layer contains inorganic particulate, and the B layer is substantially devoid of particle.

A fourth aspect of the present invention is based on above-mentioned stacked film, and wherein, mist degree is below 3.0%.

A fifth aspect of the present invention is the easy adhesive film of a kind of optics, this optics is above-mentioned stacked film with easy adhesive film, by the stacked at least one deck optical functional layer be selected from hard coat, light diffusion layer, lens jacket, electromagnetic wave absorbing layer, near infrared ray blocking layer, transparency conducting layer on above-mentioned overlay surface, uses.

The invention effect

The initial stage adaptation of stacked film of the present invention and hot and humid under adaptation (humidity resistance) extremely excellent.As the preferred embodiment of the present invention, when stacked film of the present invention is used as the base material film of diffuser plate or lens, in the adaptation excellence of hot and humid lower and optical functional layer.Particularly as lens, because functional layer stacked on overlay has part as thin as a wafer, to cause overlay be useful especially hot and humid lower easily being subject in deteriorated application.

In addition, in the preferred embodiment of the present invention, initial stage adaptation and humidity resistance excellence, and can take into account high transparent and operability.

Embodiment

Below the present invention is described in detail.

(base material film)

The thermoplastic resin that forms base material film of the present invention can be used: the polyolefin resines such as polyethylene, polypropylene; The polyamide resins such as nylon 6, nylon 66; Polyethylene terephthalate, polybutylene terephthalate, poly-2,6-(ethylene naphthalate), poly terephthalic acid methylene glycol ester and as the copolymerization diol components such as Diethylene Glycol, neopentyl glycol, polyalkylene glycol that divided polymerization or hexanodioic acid, sebacic acid, phthalic acid, m-phthalic acid, 2, the vibrin that the dicarboxylic acid such as 6-naphthalene dicarboxylic acids become to grade etc.Wherein, from the viewpoint of physical strength, resistance to chemical reagents, preferred polyester resin.

The vibrin that the present invention preferably uses mainly take in polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, PEN at least one be constituent.In these vibrin, consider the balance of physical property and cost, most preferably polyethylene terephthalate.And these polyester films can improve resistance to chemical reagents, thermotolerance, physical strength etc. by biaxial stretch-formed.

For improving operability, base material film of the present invention preferably contains inorganic particulate.Base material film is preferred embodiment at least by three layers of base material film formed.As the layer structure of three-decker, positive and negative outermost layer structure can be that same composition can be also different the composition, comparatively suitable from the viewpoint two kinds three layers (A layer/B layer/A layers) of planarity.

When being made as three-decker, preferably outermost layer (being the A layer in the situation of A layer/B layer/A layer) contains particle, and central core (B layer) is not in fact containing particle.Make the reason that the A layer contains particle be: the contact area that can increase base material film and overlay interface by suitable surfaceness is set, obtain the more effect of high adhesion thereby reach, and improve the wearing characters such as the operability such as sliding, crimp tendency, resistance to blocking of film and wearability, scuff resistance.Can be by the stacked film surface static friction coefficient (μ s) each other above-mentioned characteristic is estimated.Now, preferably static friction coefficient (μ s) is below 0.7.In addition, the B layer is not in order to maintain high transparent containing the reason of particle in fact.

While using the three-decker base material film, although the thickness proportion of each layer is unrestricted arbitrarily, preferably the total of two outermost layer thickness on be limited to the total thickness of 100 μ m, be particularly preferably 80 μ m.While surpassing 100 μ m because the transparency reduces, so sometimes not preferred.

In addition, " not containing in fact particle " refers to be for example the situation of inorganic particulate, by the x-ray fluorometric analysis to the element from particle carry out quantitative analysis the time, its content be 50ppm following, be preferably 10ppm following, most preferably be below detection limit.Even this is because actively in base material film, do not add particle, also exists from the pollutent adhered on production line and device in the manufacturing process of the pollutant component of external foreign matter or material resin or film and peel off and sneak into the situation in film.

The thickness of base material film used in the present invention is not particularly limited, can be according to using specification to determine arbitrarily in the scope of 30 μ m～500 μ m.The upper limit of base material film thickness is preferably 350 μ m, is particularly preferably 250 μ m.On the other hand, the lower limit of film thickness is preferably 50 μ m, and more preferably 75 μ m, be particularly preferably 100 μ m.Film thickness is prescribed a time limit lower than lower, and rigidity and physical strength are easily insufficient.On the contrary, film thickness raises the cost in limited time sometimes over upper.

For these each layers, can make as required in polyester to contain various additives.As additive, such as listing antioxidant, photostabilizer, anti-condensation jelly, organic wetting agent, static inhibitor, UV light absorber, tensio-active agent etc.

The contamination of the contained particle of outermost layer can be that inorganic particulate can be also organic filler, be not particularly limited, can exemplify out the metal oxides such as silicon-dioxide, titanium dioxide, talcum, kaolinite, calcium carbonate, calcium phosphate, barium sulfate etc. and polyester is to the inorganic particulate of inertia.These inert inorganic particles can be used separately any one, or can be used in combination.

The median size of above-mentioned particle is preferably 0.1 μ m～3.5 μ m.The lower limit of above-mentioned median size is preferably 0.5 μ m, more preferably 0.8 μ m, more preferably 1.0 μ m.In addition, the upper limit of above-mentioned median size is 3.0 μ m more preferably, more preferably 2.8 μ m.Median size is prescribed a time limit lower than lower, can not get sometimes enough operability.Surpass the upper transparency that reduces sometimes in limited time.

In addition, preferred Porous particle, particularly porous silica of these particles.Easily be deformed into platypelloid type during the stretching of Porous particle in film making process, be difficult to produce hole around particle during stretching and easily obtain high transparent.

The content of outermost layer inorganic particulate is preferably 0.01 quality % to 0.20 quality % with respect to forming outermost polyester.The lower limit of above-mentioned concentration is 0.02 quality % more preferably, more preferably 0.03 quality %.And the upper limit of above-mentioned concentration is 0.15 quality % more preferably, 0.10 quality % more preferably.Can not get enough operability in limited time lower than lower.Can reduce the transparency in limited time over upper.

Can measure by the following method the median size of above-mentioned particle.

Take the particle photo with electron microscope or opticmicroscope, so that the size of a smallest particles is enlarged into the multiplying power of 2mm～5mm, measure the maximum diameter (being the particle diameter of agglomeration during porous silica) of 300～500 particles, using its mean value as median size.In addition, during average particle size in the overlay of asking stacked film, use transmission electron microscope (TEM), take the cross section of stacked film under 120,000 times of multiplying powers, can try to achieve the maximum diameter of the particle existed on the overlay cross section.

As the method to the above-mentioned particle of vibrin fusion, can adopt known method.For example, can be added in any stage of manufacturing polyester, preferably in Esterification Stage or transesterification reaction, be finished the stage before finishing reaction starts, after being added as the slurry that is scattered in ethylene glycol etc., then be carried out polycondensation.In addition, can be by using squish formula mixing extruder to the method that is scattered in particle slurry in ethylene glycol or water etc. and polyester raw material and mixed or the method for using mixing extruder to be mixed dry particle and polyester raw material.

And, for base material film, in the scope of not damaging the object of the invention, also can implement to above-mentioned base material film the surface activation process such as Corona discharge Treatment, glow discharge processing, flame treating, uviolizing processing, electron beam irradiation processing, ozonize.

Then, overlay of the present invention is described.

(overlay)

In the overlay of stacked film of the present invention, take polycarbonate-based carbamate resins as main component and in specified range the Shi oxazolinyl remaining extremely important.At this, " principal constituent " refers to that in all solids composition contained in overlay, content is the meaning more than 30 quality %.In stacked film of the present invention, the compound of above-mentioned polycarbonate-based carbamate resins and Ju You oxazolinyl is preferably not low containing crosslinking structure or degree of crosslinking in fact.

As mentioned above, think up to now, the viewpoint from the humidity resistance that improves overlay, preferably actively import crosslinking structure.But, thereby the present inventor finds that being set to structure as above by overlay can significantly improve humidity resistance.Although improve the mechanism of the adaptation under hot and humid indefinite by this structure, the present inventor thinks that reason is as follows.

In overlay of the present invention, owing to not containing as Yu oxazolinyl, presenting carboxyl or its salt of the functional group of hyperergy, or its content is few, so has a lot of Wei reaction oxazolinyls in overlay.On the other hand, the resin used in stacked functional layer, such as there being the functional groups such as carboxyl in light-cured type vinylformic acid (ester) resin and unreacted reactant.And, as also there being functional group in the thermoplastic resin of base material film.Supposition under hot and humid environment, the functional group existed in these functional layer and/or base material film Yu oxazolinyl interacted, thereby can obtain firmly adaptation.

In overlay of the present invention the concentration of oxazolinyl under be limited to 0.5mmol/g, be preferably 0.07mmol/g, more preferably 1.0mmol/g, above be limited to 4.0mmol/g, is preferably 3.8mmol/g, more preferably 3.5mmol/g.Can not get sometimes the adaptation under fully hot and humid lower than above-mentioned lower limit.Surpass above-mentioned upper prescribing a time limit, the ratio of polycarbonate-based carbamate resins diminishes relatively, and adaptation, particularly initial stage adaptation can reduce sometimes.

The present invention by the way, can significantly improve the adaptation (humidity resistance) under hot and humid with optical functional layers such as lens jacket, hard coat, light diffusion layer, electromagnetic wave absorbing layer, near infrared ray blocking layer, transparency conducting layers.Below, structure of the present invention is elaborated.

Overlay of the present invention is preferably used the water system coating liquid to be arranged by coating process in production line described later.Therefore, carbamate resins preferably water dissolubility of the present invention.While using the water-soluble carbamate resin, with the intermiscibility of the resin of Ju You oxazolinyl, increase, thereby can improve the transparency.In addition, above-mentioned " water-soluble " refers to and is dissolved in water or contains the meaning lower than the aqueous solution of the water-miscible organic solvent of 50 quality %.

In order to give carbamate resins with water-soluble, sulfonic acid (salt) base or carboxylic acid (salt) base can be imported to (copolymerization) in the molecule carbamate skeleton.At this, sulfonic acid (salt) base is strongly-acid, and because its hygroscopic property causes sometimes being difficult to maintain humidity resistance, therefore general the employing imports weakly acidic carboxylic acid (salt) base.

But as mentioned above, if use the so-called anionic carbamate resins that has imported carboxyl as carbamate resins, it produces and reacts Yu oxazolinyl Zhong coating liquid, the situation that while existing overlay to form, Wei reaction oxazolinyl reduces.For this reason, do not contain in fact carboxyl in the preferred coated layer.Thus, water-soluble and import polyoxyalkylenes and take that to replace carboxyl be the preferred embodiment of the present invention in order to give carbamate resins.Use to import the carbamate resins during as carbamate resins that polyoxyalkylenes is arranged, owing to basically not importing just water-solubleization of possibility of carboxyl in overlay, therefore can make the oxazolinyl that do not react stably remaining, and the more excellent humidity resistance of performance.

The polycarbonate-based carbamate resins that coating liquid of the present invention is used is described in further detail.

In the present invention, be characterised in that have polycarbonate polyol as polycarbonate-based carbamate resins, be the constituent of carbamate resins.

Carbamate resins is divided into polyester urethane resin, polyethers urethane resin and polycarbonate-based carbamate resins substantially, wherein due to polyester urethane resin, adding water under hot and humid is easy to decompose, polyethers urethane resin water absorbability is high, thereby the film toughness of overlay easily reduces and adaptation is insufficient.On the contrary, polycarbonate-based carbamate resins has excellent humidity resistance.Based on this reason, the present invention uses polycarbonate-based carbamate resins.

That is, the present invention is by overlay being contained take the carbamate resins that polycarbonate is constituent, thereby can improve humidity resistance.As constituent, polycarbonate-based carbamate resins of the present invention at least contains polyhydroxy reactant, polyisocyanates composition, and then contains as required chain extension agent.Polycarbonate-based carbamate resins of the present invention is to take these constituents as main, the macromolecular compound obtained by the amino-formate bond copolymerization.In addition, the constituent of these polycarbonate-based carbamate resins can be identified by nuclear magnetic resonance spectroscopy (NMR) etc.

Polycarbonate polyol as the constituent of carbamate resins of the present invention, can list PCDL, polycarbonate trivalent alcohol etc., can preferably use PCDL.PCDL as the constituent of carbamate resins of the present invention, can list by making for example ethylene glycol, propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, 1, the 8-nonanediol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, 1, the 4-cyclohexanediol, 1, the 4-cyclohexanedimethanol, one or more in the glycolss such as dihydroxyphenyl propane and for example methylcarbonate, diphenyl carbonate, ethylene carbonate, the carbonates such as carbonyl chloride reactions and the fatty family PCDL that obtains etc.As the number-average molecular weight of PCDL, be preferably 300～5000, more preferably 500～3000.

In the present invention, when the whole polyisocyanates compositions by carbamate resins are set as 100 % by mole, constitutive molar ratio as the polycarbonate polyol of the constituent of carbamate resins is preferably 3 % by mole to 100 % by mole, more preferably 5 % by mole to 50 % by mole, more preferably 6 % by mole to 20 % by mole.When above-mentioned constitutive molar ratio is low, sometimes can not obtain the weather resistance effect based on polycarbonate polyol.In addition, when above-mentioned constitutive molar ratio is higher, reduce sometimes the initial stage adaptation.

As polyisocyanates, can list: the isomer class, 4 of tolylene diisocyanate, the aromatic diisocyanate classes such as 4-diphenylmethanediisocyanate; The aromatic series aliphatic diisocyanate classes such as xylylene vulcabond; Isophorone diisocyanate and 4,4-dicyclohexyl methane diisocyanate, 1, the ester ring type diisocyanates such as 3-bis-(isocyanato-methyl) hexanaphthene; The aliphatic diisocyanate classes such as hexamethylene diisocyanate and 2,2,4-trimethyl hexamethylene diisocyanate; Or make in advance single or multiple above-claimed cpd and TriMethylolPropane(TMP) addition and the polyisocyanates that obtains.

As chain extension agent, can list: the glycolss such as ethylene glycol, Diethylene Glycol, BDO and 1,6-hexylene glycol; The polyalcohols such as glycerine, TriMethylolPropane(TMP) and tetramethylolmethane; The Diamines such as quadrol, hexamethylene-diamine and piperazine; The alkamine such as monoethanolamine and diethanolamine; The Thiodiglycol classes such as thio-diethylene glycol; Or water.

Wei Shi oxazolinyl is effectively remaining, the structure that contains polyoxyalkylene chain on the side chain of the preferred carbamate resins of polycarbonate-based polyurethane(s) used in the present invention.

As the polyoxyalkylenes imported in carbamate resins, can list polyoxyethylene groups, polyoxypropylene base, poly-tetramethylene glycol chain etc., these can use separately, also can be used in combination.Wherein can preferably use polyoxyethylene groups.

In order in carbamate resins, to import polyoxyethylene groups, for example can realize by the following method: by the isocyanate group with vulcabond, with respect to the hydroxyl of the polyoxyethylene glycol of single end-capped, reach excessive ratio, making polyisocyanates, with the polyoxyethylene glycol (alkyl that is 1～20 by carbonatoms carries out the alkoxyl group ethylene glycol of single end-capped) of single end-capped, urethane occur reacts, afterwards, remove as required unreacted polyisocyanates, make thus the monoisocyanates containing polyoxyethylene chain, then, the monoisocyanates containing polyoxyethylene chain of gained is reacted with the esterification of vulcabond generation allophanic acid.

In order to give water-soluble, in carbamate resins, import in the situation of polyoxyethylene groups, when when in carbamate resins, total polyisocyanates becomes to be divided into 100 % by mole, in carbamate resins, the constitutive molar ratio of polyoxyethylene groups is preferably more than 3 % by mole, more preferably more than 10 % by mole, more preferably more than 20 % by mole.When being 3 % by mole, there is the situation of water dispersible variation in above-mentioned constitutive molar ratio.

The polycarbonate-based carbamate resins made by aforesaid method, do not contain in fact as Yu oxazolinyl, presenting carboxyl or its salt of the functional group of hyperergy, or content is less.

In overlay, the content of preferred above-mentioned polycarbonate-based carbamate resins is below the above 90 quality % of 30 quality %.Especially, in the situation that require high adhesion as lens jacket, more preferably below the above 80 quality % of 40 quality %.When the content of carbamate resins is many, the content of the compound of Ju You oxazolinyl tails off relatively, so the adaptation under hot and humid reduces; Otherwise, when the content of carbamate resins is few, not only the adaptation at initial stage reduces, and exist overlay in working procedure of coating to peel off and form the situation of defect.

In order to improve adaptation, in the present invention, also can contain the resin except polycarbonate-based carbamate resins.Such as listing vinylformic acid (ester) resin, vibrin etc.Preferably carboxyl or the few resin of its salts contg, more preferably containing the resin of carboxyl or its salt.When carboxyl or its salt are more, because it produces and react Yu oxazolinyl, and cause producing in hot and humid lower and contained in base material film or the optical functional layer functional groups such as carboxyl, react the minimizing of oxazolinyl, so not by preferably.

In the present invention, contain the compound of Ju You oxazolinyl in overlay.When coating liquid is the water system coating liquid, because the intermiscibility of the compound of Ju You oxazolinyl and other water soluble resins is good, the transparency of overlay is improved, therefore be preferably water miscible.

For the compound of Shi Ju You oxazolinyl becomes water misciblely, in preferably making to form, contain wetting ability monoploid.As wetting ability monoploid, can list: the monoester compound of (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid methoxy poly (ethylene glycol) ester, (methyl) vinylformic acid and polyoxyethylene glycol etc. has monoploid, (methyl) vinylformic acid-2-amino ethyl ester and salt thereof, (methyl) acrylamide, N-methylol (methyl) acrylamide, N-(2-hydroxyethyl) (methyl) acrylamide, (methyl) vinyl cyanide, Sodium styrene sulfonate of polyglycol chain etc.Wherein, monoester compound that preferably contains solvability is high in water (methyl) vinylformic acid methoxy poly (ethylene glycol) ester, (methyl) vinylformic acid and polyoxyethylene glycol etc. has the monoploid of polyglycol chain.

In addition, the compound oxazoline equivalent of Ju You oxazolinyl used in the present invention is not particularly limited, particularly for example be preferably below 1000g-solid/eq., more preferably below 500g-solid/eq., more preferably below 300g-solid/eq..On state the oxazoline equivalent surpass upper in limited time, existence can not performance and base material film or optical functional layer in enough interactions between contained carboxyl etc., can not obtain satisfactorily the situation of weather resistance, water tolerance.In addition, above state the polymer weight that oxazoline equivalent (g-solid/eq.) is set as every 1 Mo Er oxazolinyl.Thereby this content that means the less Ju compound of Gai oxazoline equivalent value Zhong oxazolinyl is more, the content that is worth larger Ju compound Zhong oxazolinyl is fewer.

In addition, the compound of Ju You oxazolinyl used in the present invention can be also the compound of selling on market.As the water-soluble or water dispersible compound of the Ju You oxazolinyl of selling on market, such as the Epocross WS-300 (ェ Port Network ロ ス WS-300) that can list Japanese catalyst company system, Epocross WS-500, Epocross WS-700, Epocross K-2010 etc.

The compound that preferably contains the following above-mentioned Ju You oxazolinyl of the above 70 quality % of 10 quality % in overlay.Especially, in the situation that need high adhesion as lens jacket, more preferably below the above 70 quality % of 30 quality %.When the compounds content of Ju You oxazolinyl is more, particularly with the initial stage adaptation of optical functional layer, reduce, otherwise, hot and humid lower adaptation reduction when content is less.

In overlay, have without oxazolinyl with and content can try to achieve by known method.For example can list the method detected by infrared measure as described later, or cut and get overlay, this is cut and gets thing and be dissolved in methylethylketone, trichloromethane or dimethyl formamide, adopt magnetic nuclear resonance analyzer (NMR) from its integration the method than the molar percentage to determine each component etc.

In the present invention, from the viewpoint preferred coated layer of operability, contain particle.Particle can list: the inorganic particulates such as (1) silicon-dioxide, kaolinite, talcum, light calcium carbonate, water-ground limestone, zeolite, aluminum oxide, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, stain white, pure aluminium silicate, diatomite, Calucium Silicate powder, aluminium hydroxide, halloysite, magnesiumcarbonate, magnesium hydroxide, (2) vinylformic acid (ester) or methacrylic acid (ester) class, polyvinyl chloride-base, the vinyl acetate between to for plastic class, nylon, styrene/acrylic (ester) class, the phenylethylene/butadiene class, polystyrene/vinylformic acid (ester) class, polystyrene/isoprene acids, polystyrene/isoprene acids, methyl methacrylate/butyl methacrylate class, melamine class, polycarbonate-based, the urea class, epoxies, amino formate, phenol, the Phthalic acid, diallyl ester class, the organic fillers such as polyester.

The median size of above-mentioned particle is preferably 1mm～500nm.Median size is not particularly limited, but from the viewpoint of the transparency that maintains film, preferably 1mm～100nm.

Above-mentioned particle also can contain the particle that two or more median sizes are different.

As the content of particle, preferably below the above 20 quality % of 0.5 quality %.When content is less, can't obtain sufficient resistance to blocking.In addition, scuff resistance worsens.When content is more, the not only transparent variation of overlay, and coating strength reduces.

It is preferred embodiment that the surfaceness of overlay (Ra) is set as to 2mm～25nm.5mm～20nm more preferably.During lower than 2nm, resistance to blocking reduces, transparency reduction while surpassing 25nm.

For the planarization that improves when coating and make the coating liquid deaeration, can make in overlay to contain tensio-active agent.Tensio-active agent can be any one in cationic, anionic, non-ionic type etc., but preferably silicon class, acetylenediol class or fluorinated tensio-active agent.In the extent and scope do not damaged with the adaptation of optical functional layer, preference is as the above-mentioned tensio-active agent of the scope that makes in coating liquid to contain 0.005 quality % to 0.5 quality %.

The preferred mist degree of stacked film of the present invention is below 3.0%, more preferably below 2.5%, more preferably below 2.0%.This stacked film preferably adopts water miscible compound by the compound of Ju You oxazolinyl contained in the overlay that makes above-mentioned record, thereby the intermiscibility of itself and other resin is obtained, improves.

In order to give overlay other function, in the scope of not damaging with the degree of the adaptation of optical functional layer, also can make it contain various additives.As above-mentioned additive, can list such as fluorescence dye, white dyes, plasticizer, UV light absorber, pigment dispersing agent, suds suppressor, defoamer, sanitas, static inhibitor etc.

In the present invention, as the method that overlay is set on base material film, can list the coating liquid that coating contains solvent, particle, resin on polyester film and carry out dry method.As solvent, can list the mixed solvent class of organic solvent, water or the water such as toluene and water-miscible organic solvent, but from the viewpoint of environmental pressure, preferably water or in water the mixing water solubleness organic solvent and solvent.

As be used to form the method for the coating liquid of overlay for coating on base material film, can use known any means.Can list such as: reverse roll coating process, gravure coating method, the coating process that coincide, mold pressing coating process, brush roll coating process, spraying method, air knife coating process, the excellent coating process of silk, pipe scraper coating process (pipe doctor method), dip coating method, curtain coating method etc.Can use separately aforesaid method, also it can be combined to be applied.

In the present invention, do not stretch or unilateral stretching after film apply above-mentioned coating liquid dry, at least carry out afterwards uniaxial extension, then heat-treat, thereby form overlay.

In the present invention, the dried coating amount of the overlay finally obtained is preferably 0.02g/m ²～0.5g/m ².The coating amount of overlay is lower than 0.02g/m ²the time, there is the situation to the effect reduction of cementability.On the contrary, coating amount surpasses 0.5g/m ²the time, resistance to blocking reduces.

Stacked film of the present invention can be laminated to less a kind of optical functional layer that is selected from hard coat, light diffusion layer, lens jacket, electromagnetic wave absorbing layer, near infrared ray blocking layer, transparency conducting layer on the overlay surface of above-mentioned base material film.In addition, although no matter as said lens layer shape, such as can preferably using prism-shaped lens, Fresnel shape lens, micro lens etc.

The above-mentioned material for optical functional layer is not particularly limited, and can use by any and resin compound that polymerization and/or reaction obtain in dry, heat, chemical reaction or irradiating electron beam, radioactive rays, ultraviolet ray.As above-mentioned curable resin, can list melamine class, vinylformic acid (ester) class, silicon class, polyvinyl alcohol curable resin, obtaining aspect high surface hardness or optical design, preferred light curing vinylformic acid (ester) is curable resin.As aforesaid propylene acid (ester), it is curable resin, can use multifunctional (methyl) acrylic ester monomer and acrylic ester oligopolymer, as the example of acrylic ester oligopolymer, can list polyester acrylate system, epoxy acrylate system, urethane acrylate system, polyether acrylate system, PBAA ester system, Si acrylate system etc.By being hybrid reaction thinner, Photoepolymerizationinitiater initiater, sensitizing agent etc. in curable resin in aforesaid propylene acid (ester), can access the composition for coating that is used to form above-mentioned optical functional layer.

In addition, the overlay of the resulting stacked film of the present invention has good cementability to hard coat, light diffusion layer, prism-shaped lens jacket, electromagnetic wave absorbing layer, near infrared ray blocking layer, transparency conducting layer.And, even also can obtain good bonding strength beyond above-mentioned optical applications.Particularly, can list: photograph sensitive layer, two azo sensitive layers, calendering layer (mat layer), magnetosphere, jetted ink are accommodated layer, hard coat, ultraviolet curable resin, heat reactive resin, printing-ink or UV printing ink, dry laminate or are extruded caking agent, metal or the inorganicss such as lamination or thin film layer that their oxide compound obtains by vacuum evaporation, electron beam evaporation plating, sputter, ion plating, CVD, plasma polymerization etc., organic barrier layer etc.

Embodiment

Below, the present invention is described in detail to use embodiment and comparative example, but the present invention is certainly and be not limited by the following examples.In addition, the evaluation method of using in the present invention is as follows.

(1) overlay Zhong oxazolinyl concentration is quantitative

Absorb infrared measure by total reflection, the overlay surface of the stacked film that obtains in embodiment and comparative example is measured, the special absorbancy that contrast obtains from base material film is tried to achieve the concentration of oxazolinyl overlay.

; absorbing infrared measure by total reflection under condition as follows is measured; obtain infrared absorption spectrum, thereby try to achieve the ratio of the absorbancy of Lai Zi oxazolinyl and the absorbancy of base material film (being ethylene glycol in the situation of PET film), (infrared absorbency compares A ₁₆₅₅/ A ₁₃₄₀).In addition, will be at 1655 ± 10cm ^-1zone in there is maximum absorption absorption peak height value (A ₁₆₅₅) as the absorbancy of Lai Zi oxazolinyl, will be at 1340 ± 10cm ^-1zone in there is maximum absorption absorption peak height value (A ₁₃₄₀) as the absorbancy from PET.The straight line that baseline is got a foothold for the both sides that connect maximum absorption band separately.

In addition, try to achieve the thickness of overlay by transmission electron microscope.The sample of stacked film is embedded into to visible-light curing type resin, and (Japan new EM company manufactures, and D-800), at room temperature with radiation of visible light, makes it curing.Use is equipped with the ultramicrotome of diamond cutting knife and makes the ultrathin section(ing) of thickness for 70nm～100nm degree from resulting embedded block, and dyes 30 minutes in the ruthenium tetroxide steam.And, after implementing plating carbon, (Jeol Ltd. manufactures, and TEM-2010) observes cross section and takes pictures, and instrumentation draws the thickness of overlay thus to use transmission electron microscope.In addition, taking pictures is 10,000～100, in the scope of 000 times, is suitably set.

Infrared absorbency by gained compares A ₁₆₅₅/ A ₁₃₄₀and the thickness of overlay, use by being coated with in advance and be covered with the known coating liquid of the oxazolinyl concentration standard lines that also air-dry standard test specimen makes, and try to achieve the concentration of oxazolinyl in overlay.

In addition, when the production standard line, so that the coating liquid (solvent: water/Virahol=1/1 that the concentration of the mode Tu Fu oxazolinyl that the thickness of dried overlay is 50nm, 100nm, 200nm is 0.5mmol/g, 1.4mmol/g, 2.7mmol/g, 4.5mmol/g, and the combined amount of adjustment and vinylformic acid (ester) resin, making solid component concentration is 30 quality %) and air-dry, the sample of gained is absorbed to infrared measure according to condition shown in following by total reflection and measure infrared absorbency and compare A ₁₆₅₅/ A ₁₃₄₀, obtain You oxazolinyl concentration, overlay thickness, infrared absorbency from the result of gained and compare A ₁₆₅₅/ A ₁₃₄₀the following simple equation that these three variablees form, using this as standard lines.

(oxazolinyl concentration)=A * (infrared absorbency compares A ₁₆₅₅/ A ₁₃₄₀)/(overlay thickness)+B

(at this, A, B are by the constant by making data that standard lines obtains and trying to achieve)

(measuring condition)

Device: Varian company manufactures FTS-60A/896

Primary event ATR device: SPECTRA TECH company manufactures Silver Gate

Optical crystal: Ge

Input angle: 45

Resolving power: 4cm ^-1

Integral number of times: 128 times

In addition, overlay thinner thickness, while can not get enough sensitivity, (65 degree) device (for example ST Japan company manufactures VeeMax) that also can be larger by input angle replaces primary event device to be measured.

(2) initial stage adaptation

Under light-cured type vinylformic acid (ester) resin composition and condition of cure as follows, at light-cured type vinylformic acid (ester) layer of the resulting stacked film overlay stacked 3 μ m in surface.Use the cutter guide that clearance gap is 2mm, give 100 to this light-cured type vinylformic acid (ester) layer surface and connect the latticed score that light-cured type vinylformic acid (ester) layer reaches base material film.Then, cellophane tape (manufacture of meter Qi Bang company, No. 405, wide 24mm) is attached to latticed score surface, with eraser, rubs and make it fully closely sealed.Afterwards, carry out once by cellophane tape from light-cured type vinylformic acid (ester) the layer Surface Vertical of stacked film the operation of peeling off, afterwards, visual counting is from the quantity of the grid of the light-cured type vinylformic acid (ester) of stacked film layer sur-face peeling, obtains the adaptation of light-cured type vinylformic acid (ester) layer and base material film by following formula.In addition, the grid that in grid, part is peeled off is also counted as the grid be stripped from, and according to following criteria grade.

Adaptation (%)=(grid number that 1-is stripped from/100) * 100

◎: 100% or the material breaks of light-cured type vinylformic acid (ester) layer

○：99％～90％

△：89％～70％

×：69％～0％

(light-cured type vinylformic acid (ester) resin composition)

On the SUS plate that is 1mm at the thickness kept clean (SUS304) to place the following light-cured type vinylformic acid of about 5g (ester) be coating liquid, overlay surface and light-cured type vinylformic acid (ester) with the film sample are that the contacted mode of coating liquid is carried out overlapping, carry out pressing from the top of film sample by the wide manual type load rubber roll that is 4cm for the 10cm diameter, making light-cured type vinylformic acid (ester) is that coating liquid extends.Then, use high-pressure mercury light irradiation 800mJ/cm from the film side ²ultraviolet ray, make light-cured type vinylformic acid (ester) resin solidification.The film sample that will have thickness and be light-cured type vinylformic acid (ester) layer of 20 μ m from the SUS plate is peeled off, thereby obtains the optical functional film.

(light-cured type vinylformic acid (ester) is coating liquid)

Light-cured type vinylformic acid (ester) resin 54.00 quality %

(waste river chemical industry is manufactured beamset 505A-6)

Light-cured type vinylformic acid (ester) resin 36.00 quality %

(waste river chemical industry is manufactured beamset 550)

Photoepolymerizationinitiater initiater 10.00 quality %

(BASF chemical company manufactures IRGACURE 184)

(3) humidity resistance

In hot and humid groove, under 80 ℃, the environment of 95%RH, will place 48 hours with the optical functional film that is laminated with light-cured type vinylformic acid (ester) resin obtained with above-mentioned (2) same method.Then, take out the optical functional film, often wet lower placement of room temperature 12 hours.Afterwards, except carry out 5 times by cellophane tape from the light-cured type vinylformic acid (ester) of optical functional film layer Surface Vertical the operation of peeling off, remaining uses the method same with above-mentioned (2) to obtain the adaptation of light-cured type vinylformic acid (ester) layer and base material film, and according to following criteria grade.

◎: 100% or the material breaks of light-cured type vinylformic acid (ester) layer

○：99％～90％

△：89％～70％

×：69％～0％

(4) operability

Cut out the area of 8cm * 5cm from the film of embodiment and comparative example gained, make sample film.By its take the mode of overlay surface in the outside be fixed in there is bottom surface that size is 6cm * 5cm, the bottom surface of the metal-made rectangular parallelepiped of heavy 4.4kg.Now, the 5cm width of sample film is consistent with the 5cm width of metal rectangular parallelepiped, and the side of metal rectangular parallelepiped is fixed in one side bending of the length direction of sample film with adhesive tape.

Then, cut out the sample film of the area of 20cm * 10cm from identical stacked film, make the overlay surface upward, with adhesive tape, the end of length direction is fixed on smooth metal sheet.The mode contacted with the measurement face of the metal-made rectangular parallelepiped with being pasted with sample film is thereon placed, and under draw speed is 200mm/ minute, 23 ℃, the condition of 65%RH, has measured static friction coefficient (μ s).The RTM-100 that has used Japan BALDWIN company to manufacture during measurement, calculated static friction coefficient (μ s) according to the JISK-7125 benchmark.

Static friction coefficient (μ s) while being the situation below 0.7 operability be set as well (zero), surpass 0.7 o'clock operability and be set as bad (*).

(5) mist degree

Take JIS K 7105 as benchmark, use integrating sphere type light penetration measuring apparatus (Japanese electric look industry is manufactured) to be estimated.

(6) oxazoline equivalents

To carry out containing the resin that oxazoline is arranged freeze-driedly, with 1H-NMR, it be analyzed, from the absorption peak strength from oxazolinyl, from the absorption peak strength meter of other monomers, calculate out the oxazoline equivalent.

(synthesizing of polycarbonate-based carbamate resins (A-1))

In the reactor that possesses thermometer, nitrogen ingress pipe and stirrer, add hexamethylene diisocyanate 627.1 mass parts when importing nitrogen, methoxy poly (ethylene glycol) 372.9 mass parts that the number-average molecular weight that is heated to 50 ℃ is 1000, under 80 ℃, reaction is 6 hours.After reaching predetermined isocyanate group content, remove unreacted hexamethylene diisocyanate by Smith's formula film distillator, obtain the monoisocyanates a that contains the Pluronic F-127 chain.

Then, in the reactor that possesses thermometer, nitrogen ingress pipe and stirrer, under room temperature, import nitrogen, add diethanolamine 83.9 mass parts simultaneously.In cooling, add monoisocyanates a 916.1 mass parts that contain the Pluronic F-127 chain, under 60 ℃, reaction is 3 hours.Confirm the generation of urea key by infrared spectra, obtain the polyvalent alcohol A that contains the Pluronic F-127 side chain.

Possessing reflux condensing tube, nitrogen ingress pipe, in the four-hole boiling flask of thermometer and stirrer, add as 1 of polyisocyanates, 3-bis-(isocyanato-methyl) hexanaphthene 53.7 mass parts, poly-hexylene glycol carbonic ether 88.6 mass parts that number-average molecular weight is 2000, neopentyl glycol 15.0 mass parts, above-mentioned polyvalent alcohol A 52.9 mass parts that contain the Pluronic F-127 side chain, acetonitrile 60 mass parts as organic solvent, N-Methyl pyrrolidone 30 mass parts, under nitrogen atmosphere, reacting liquid temperature is adjusted to 75 ℃～78 ℃, add stannous octoate (manufacture of Nakalai Tesque company) 0.06 mass parts as catalysts, react 7 hours until reactivity reaches more than 99%.Then, it is cooled to 30 ℃, obtains isocyanate-terminated prepolymer.But then in the reaction vessel of the homogenizer with high-speed stirring, add water 450g, be adjusted to 25 ℃, with 2000min ^-1be uniformly mixed, add isocyanate-terminated prepolymer simultaneously and carry out water-dispersion.Thereafter, under reduced pressure remove portion acetonitrile and water, the aqueous solution (A-1) of the polycarbonate-based carbamate resins that to be modulated into thus solids component be 35%.

(synthesizing of polycarbonate-based carbamate resins (A-2))

Possessing reflux condensing tube, nitrogen ingress pipe, in the four-hole boiling flask of thermometer and stirrer, add as 1 of polyisocyanates, 3-bis-(isocyanato-methyl) hexanaphthene 73.0 mass parts, poly-hexylene glycol carbonic ether 112.7 mass parts that number-average molecular weight is 2000, neopentyl glycol 11.7 mass parts, dimethylol propionic acid 12.6 mass parts, acetonitrile 60 mass parts as organic solvent, N-Methyl pyrrolidone 30 mass parts, under nitrogen atmosphere, temperature of reaction is adjusted to 75 ℃～78 ℃, add stannous octoate (manufacture of Nakalai Tesque company) 0.06 mass parts as catalysts, react 7 hours until reactivity reaches more than 99%.Then, it is cooled to 30 ℃, obtains isocyanate-terminated prepolymer.But then in the reaction vessel of the homogenizer with high-speed stirring, add water 450g, be adjusted to 25 ℃, with 2000min ^-1be uniformly mixed, add isocyanate-terminated prepolymer simultaneously and carry out water-dispersion.Thereafter, under reduced pressure, remove portion acetonitrile and water, the aqueous solution (A-2) of the polycarbonate-based carbamate resins that to be modulated into thus solids component be 35%.

(synthesizing of polyester urethane resin (A-3))

Possessing stirrer, serpentine condenser, nitrogen ingress pipe, in the four-hole boiling flask of silica dehydrator pipe and thermometer, add 1, 3-bis-(isocyanato-methyl) hexanaphthene 72.96 mass parts, dimethylol propionic acid 12.60 mass parts, neopentyl glycol 11.74 mass parts, the polyester glycol that molecular weight is 2000 (goods number Plaxel 220EB (プ ラ Network セ Le 220EB, Daicel chemical company manufactures) 112.70 mass parts and as acetonitrile 85.00 mass parts of solvent, N-Methyl pyrrolidone 5.00 mass parts, under nitrogen atmosphere, under 75 ℃, stir 3 hours, confirm that reaction solution has reached predetermined amine equivalent.Then, this reaction solution is cooled to after 40 ℃, adds triethylamine 9.03 mass parts and obtain polyester-urethane prepolymer solution.Then, but add water 450g in the reaction vessel of the homogenizer with high-speed stirring, be adjusted to 25 ℃, limit is with 2000min ^-1being uniformly mixed limit adds isocyanate-terminated prepolymer and carries out water-dispersion.Thereafter, under reduced pressure, remove portion acetonitrile and water, the aqueous solution (A-3) of the polyurethane resin that to be modulated into thus solids component be 35%.

(polyethers of take is the polymerization of the polyvalent alcohol carbamate resins (A-4) that is constituent)

In the four-hole boiling flask that possesses stirrer, serpentine condenser, nitrogen ingress pipe, silica dehydrator pipe and thermometer, add 1, polytetramethylene ether diol 112.70 mass parts that 3-bis-(isocyanato-methyl) hexanaphthene 72.96 mass parts, dimethylol propionic acid 12.60 mass parts, neopentyl glycol 11.74 mass parts, molecular weight are 2000 and as acetonitrile 85.00 mass parts, N-Methyl pyrrolidone 5.00 mass parts of solvent, under nitrogen atmosphere, stir 3 hours under 75 ℃, confirm that reaction solution has reached predetermined amine equivalent.Then, this reaction solution is cooled to after 40 ℃, adds triethylamine 9.03 mass parts and obtain polyester-urethane prepolymer solution.Then, but add water 450g in the reaction vessel of the homogenizer with high-speed stirring, be adjusted to 25 ℃, limit is with 2000min ^-1being uniformly mixed limit adds isocyanate-terminated prepolymer and carries out water-dispersion.Thereafter, under reduced pressure, remove portion acetonitrile and water, the polyethers that to be modulated into thus solids component be 35% is the aqueous solution (A-4) of polyurethane resin.

Synthesizing of the resin (B-1) of (Ju You oxazolinyl)

In the flask that possesses stirrer, reflux condensing tube, nitrogen ingress pipe and thermometer, add 460.6 parts of Virahols, limit flows into lentamente the nitrogen limit and is heated to 80 ℃.By funnel, through 2 hours, splash into respectively wherein in advance modulation by 126 parts of (methyl) methyl acrylates, 2-pseudoallyl-210 parts of 2-oxazolines and 84 parts of formed monoploid mixtures of methoxy polyethylene glycol acrylate and by 21 parts of ABN-E (polymerization starter that Japanese hydrazine Industrial Co., Ltd manufactures: 2,2 '-azo two (2-methylbutyronitrile)) and 189 parts of formed initiator solutions of Isopropanediol.Continue in reaction to flow into nitrogen, and make temperature in flask remain on 80 ± 1 ℃.Splash into after end the temperature 5 hours that still keeps identical, cooling afterwards, obtain the resin (B-1) of Ju You oxazolinyl, (B-1) oxazoline equivalent is 220g-solid/eq to the resin of resulting Ju You oxazolinyl.

The polymer dissolution of gained is obtained to the aqueous solution (B-1) that solid component concentration is 25 quality % in ion exchanged water.

Synthesizing of the resin (B-2) of (Ju You oxazolinyl)

In the glass that possesses thermometer, stirrer, nitrogen ingress pipe, reflux condensing tube reactor processed, add 100 parts of the poly glycol monomethyl ethers that molecular-weight average is 500, be warming up to 140 ℃ under nitrogen gas stream.

Then, make the temperature in glass reactor processed remain on 140 ℃～142 ℃, through 2 hours, splash into continuously separately respectively 10 parts of 50 parts of butyl acrylates, 2-pseudoallyl-50 parts of 2-oxazolines and ditertiary butyl peroxides simultaneously.After splashing into end, limit keeps 2 hours limits to be stirred at 140 ℃～142 ℃, add 0.5 part of ditertiary butyl peroxide, limit keeps 1.5 hours limits to be stirred at 140 ℃～142 ℃ more afterwards, obtain thus the resin (B-2) of Ju You oxazolinyl, (B-2) oxazoline equivalent is 440g-solid/eq to the resin of resulting Ju You oxazolinyl.

The polymer dissolution of gained is obtained to the aqueous solution (B-2) that solid component concentration is 25 quality % in ion exchanged water.

Synthesizing of the resin (B-3) of (Ju You oxazolinyl)

In the flask that possesses stirrer, reflux condensing tube, nitrogen ingress pipe and thermometer, add 460.6 parts of Virahols, limit flows into lentamente the nitrogen limit and is heated to 80 ℃.By funnel, through 2 hours, splash into respectively wherein in advance modulation by 213 parts of methyl methacrylates, 2-pseudoallyl-58 parts of 2-oxazolines and 123 parts of formed monoploid mixtures of methoxy polyethylene glycol acrylate and by 21 parts of ABN-E (polymerization starter that Japanese hydrazine Industrial Co., Ltd manufactures: 2,2 '-azo two (2-methylbutyronitrile)) and 189 parts of formed initiator solutions of Virahol.Continue in reaction to flow into nitrogen, and make temperature in flask remain on 80 ± 1 ℃.Splash into after end the temperature 5 hours that still keeps identical, cooling afterwards, obtain the resin (B-3) of Ju You oxazolinyl, (B-3) oxazoline equivalent is 550g-solid/eq to the resin of resulting Ju You oxazolinyl.By the polymer dissolution of gained in ion exchanged water, the aqueous solution (B-3) that to obtain solid component concentration be 25 quality %.

(synthesizing of copolymer polyester resin (C-1))

Add dimethyl terephthalate (DMT) (95 mass parts), dimethyl isophthalate (95 mass parts), ethylene glycol (35 mass parts), neopentyl glycol (145 mass parts), tin acetate (0.1 mass parts) and ANTIMONY TRIOXIDE SB 203 99.8 PCT (0.1 mass parts) in reaction vessel, at 180 ℃, carry out 3 hours transesterification reactions.Then, add 5-sodium sulfo isophthalate (6.0 mass parts), after 240 ℃ are carried out 1 hour esterification, in 250 ℃ under reduced pressure (10mmHg～0.2mmHg) carry out polycondensation in 2 hours, the polyester copolymerization resin (A) that obtain number-average molecular weight and be 19,500, the glass tansition temperature is 62 ℃.

By the polyester copolymerization of gained, be that resin 300 mass parts and ethylene glycol monobutyl ether 140 mass parts carry out stirring in 3 hours at 160 ℃ the fused solution that obtains thickness, slowly add water in this viscous fluid, obtain the aqueous dispersions (C-1) that even pale solid component concentration is 35% after 1 hour.

Embodiment 1

(1) allotment of coating liquid (A)

Mix following paint, be deployed into coating liquid (A).

(1) manufacture of stacked film

Respectively will be as the middle layer of base material film containing particle and limiting viscosity, being not 0.62 and (being dissolved in phenol: 1 with raw material, 1,2, in the mixed solvent of 2-tetrachloroethane=6: 4, under 30 ℃, measured) PET (A) under 135 ℃ through 6 hours drying under reduced pressure (1Torr) afterwards, be supplied to forcing machine 2 (middle layer B layer with); Particulate state PET (A) and limiting viscosity are 0.62 and (are dissolved in phenol: 1,1,2, in the mixed solvent of 2-tetrachloroethane=6: 4, under 30 ℃, measured), the PET (B) that contains the silicon dioxide granule 0.025 quality % that median size is 2.5 μ m is supplied to forcing machine 1 (outer A layer with), and 285 ℃ of dissolvings.These two kinds of vibrin are filtered by the filtering material (nominal filter fineness: the particle of 10 μ m removes 95%) of stainless steel sintered compact respectively, stacked in three laminated stream districts, after being extruded by the die head slabbing, use applies the static film casting method and is wound on the upper also cooling curing of casting drum that surface temperature is 30 ℃, obtains unstretching film.Now, take mode that the Thickness Ratio of A layer, B layer, A layer is 1.5: 7: 1.5 adjusts the discharge-amount of each forcing machine.Then by heated roller group and infrared heater, this unstretching film is heated to 100 ℃, afterwards, by having roll surface speed, poor roller group stretches 3.5 times in the longitudinal direction, obtains uniaxial orientation PET film.

Then, by rolling method, above-mentioned coating liquid is coated on a face of PET film, afterwards dry 5 seconds under 100 ℃.In addition, adjusted so that the dried coating amount of final (after biaxial stretch-formed) is 0.1g/m ².Then this uniaxial extension polyester film is guided to the transverse drawing mill of pincers tool mode, after 100 ℃ of lower preheatings, under 130 ℃, at width, stretch 4.0 times, after then under 230 ℃, carrying out heat fixation, carrying out the relaxation of 3% width under 150 ℃ processes, then, obtain by the film coiler is curling the stacked film that thickness is 250 μ m.

Embodiment 2

Except the coating liquid by embodiment 1 (A) changes to coating liquid (B), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (B))

Mix following paint, be deployed into coating liquid (B).

Embodiment 3

Except the coating liquid by embodiment 1 (A) changes to coating liquid (C), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (C))

Mix following paint, be deployed into coating liquid (C).

Embodiment 4

Except the coating liquid by embodiment 1 (A) changes to coating liquid (D), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (D))

Mix following paint, be deployed into coating liquid (D).

Embodiment 5

Except the coating liquid by embodiment 1 (A) changes to coating liquid (E), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (E))

Mix following paint, be deployed into coating liquid (E).

Embodiment 6

Except the coating liquid by embodiment 1 (A) changes to coating liquid (F), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (F))

Mix following paint, be deployed into coating liquid (F).

Embodiment 7

Except being 0.62, the particulate state PET by A layer use and limiting viscosity (be dissolved in phenol: 1,1,2,2, in the mixed solvent of-tetrachloroethane=6: 4, under 30 ℃, measured), the PET (C) that contains the silicon dioxide granule 0.035 quality % that median size is 2.5 μ m is supplied to forcing machine 1 (outer A layer with) and in addition, with the method identical with embodiment 2, obtains stacked film.

Embodiment 8

Except being 0.62, the particulate state PET by A layer use and limiting viscosity (be dissolved in phenol: 1,1,2,2, in the mixed solvent of-tetrachloroethane=6: 4, under 30 ℃, measured), the PET (C) that contains the silicon dioxide granule 0.010 quality % that median size is 2.5 μ m is supplied to forcing machine 1 (outer A layer with) and in addition, with the method identical with embodiment 2, obtains stacked film.

Embodiment 9

Except being 0.62, the particulate state PET by A layer use and limiting viscosity (be dissolved in phenol: 1,1,2,2, in the mixed solvent of-tetrachloroethane=6: 4, under 30 ℃, measured), the PET (C) that contains the silicon dioxide granule 0.025 quality % that median size is 1.4 μ m is supplied to forcing machine 1 (outer A layer with) and in addition, with the method identical with embodiment 2, obtains stacked film.

Embodiment 10

Except the A layer is not set, the B layer with the raw material PET (B) that use contains the silicon dioxide granule 0.025 quality % that median size is 2.5 μ m as stock polymer in addition, obtains stacked film with the method identical with embodiment 2.

Embodiment 11

Except the thickness setting of base material film is 100 μ m, with the method identical with embodiment 2, obtain stacked film.

Embodiment 12

According to embodiment 2, except the A layer is not set, the B layer is used and not to contain beyond polyethylene terephthalate (PET) resin particle that particle, limiting viscosity are 0.62dl/g as stock polymer with raw material, with the method identical with embodiment 2, obtains stacked film.

Comparative example 1

Except the coating liquid by embodiment 1 (A) changes to coating liquid (G), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (G))

Mix following paint, be deployed into coating liquid (G).

Comparative example 2

Except the coating liquid by embodiment 1 (A) changes to coating liquid (H), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (H))

Mix following paint, be deployed into coating liquid (H).

Comparative example 3

Except the coating liquid by embodiment 1 (A) changes to coating liquid (I), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (I))

Mix following paint, be deployed into coating liquid (I).

Comparative example 4

Except the coating liquid by embodiment 1 (A) changes to coating liquid (J), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (J))

Mix following paint, be deployed into coating liquid (J).

Comparative example 5

Except the coating liquid by embodiment 1 (A) changes to coating liquid (K), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (K))

Mix following paint, be deployed into coating liquid (K).

Comparative example 6

Except the coating liquid by embodiment 1 (A) changes to coating liquid (L), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (L))

Mix following paint, be deployed into coating liquid (L).

Comparative example 7

Except the coating liquid by embodiment 1 (A) changes to coating liquid (M), with the method identical with embodiment 1, obtain stacked film.

(allotment of coating liquid (M))

Mix following paint, be deployed into coating liquid (M).

Comparative example 8

Except using, the water soluble resin of Ju You oxazolinyl (B-1) is changed to epoxy compounds (the manufacture Denacol EX-521 of Nagase ChemteX company, solid component concentration 100 quality %) coating liquid (N) in addition, obtains stacked film with the method identical with embodiment 2.

Comparative example 9

Except using, the water soluble resin of Ju You oxazolinyl (B) is changed to melamine compound (the manufacture BECKAMINE M-3 of DIC company, solid component concentration 60 quality %) coating liquid (O) in addition, obtains stacked film with the method identical with embodiment 2.

[table 1]

Industrial utilizability

Stacked film of the present invention has excellent initial stage adaptation and humidity resistance.Especially, therefore due to the initial stage adaptation with optical functional layer and humidity resistance excellence, be applicable to as the hard coat film that is mainly used in indicating meter etc. and the basement membrane that used the optical functional films such as antireflection film, light diffusing sheet, prism-shaped lens, near infrared ray blocking film, transparent and electrically conductive film, antiglare film of this film.

Claims (5)

1. a stacked film is characterized in that:

Described stacked film is the stacked stacked film of overlay at least one face of base material film,

Described overlay be take polycarbonate-based carbamate resins as principal constituent,

Also contain 0.5mmol/g～4.0mmol/g oxazolinyl in described overlay,

Described polycarbonate-based carbamate resins in described overlay in contained all solids composition content be more than 30 quality %.

2. stacked film according to claim 1 is characterized in that:

Described base material film comprises vibrin.

3. stacked film according to claim 1 and 2 is characterized in that:

The stepped construction that described base material film is A layer, B layer, A layer, the A layer contains inorganic particulate, and the B layer does not contain particle.

4. stacked film according to claim 1 and 2 is characterized in that:

Mist degree is below 3.0%.

5. the easy adhesive film of optics is characterized in that:

Described optics is the described stacked film of any one in claim 1 to 4 with easy adhesive film, by using after the stacked at least one deck optical functional layer be selected from hard coat, light diffusion layer, lens jacket, electromagnetic wave absorbing layer, near infrared ray blocking layer, transparency conducting layer on described overlay surface.