CN107922655A - Metal film stack film - Google Patents

Abstract

The present invention provides a kind of patterned metal film stack film, it is also good to the adaptation of metal layer under the conditions of hot and humid, and, metal layer does not change colour, and the oligomer that can suppress to separate out when being heat-treated separates out, even in the deformation of the shape of patterned metal layer, the patterning of metal film stack film becomes fine, pattern width is designed to be narrower, being designed as the response of wiring substrate becomes high precision int, when being used in the type of highly sensitive wiring substrate, also the undesirable condition because caused by patterning is bad can not occur.A kind of metal film stack film is provided, at least there is coating layer in a polyester film face, which is formed by the coating fluid for containing 70 weight % above crosslinking agents relative to nonvolatile component, meets following formula (1).| SMD-STD |≤0.4 ... (1) is (in above-mentioned formula, SMD represents the shrinking percentage (%) of film moving direction (MD), STD represents the shrinking percentage (%) in the direction (TD) orthogonal with film moving direction, and heating condition is 150 DEG C, 90 minutes).

Description

Metal film stack film

Technical field

The present invention relates to the metal film stack film that lamination has patterned metal layer, it is related to the adaptation to metal layer Well, the patterning of metal layer is good, pattern shape is good, is especially suitable for flexible two sides circuit substrate purposes, touches Touch the film of panel component parts (such as conductive film etc.) etc..

Background technology

In the prior art, polyester film plays the advantages that its mechanical property, optical characteristics, dimensional stability, is applied to Various fields.As its an example, flexible base board purposes may be exemplified.

In recent years, it is the small-sized of the e-machine of representative with TV, mobile phone, laptop, digital camera, game machine etc. Change, slimming, lightweight develop rapidly, and for material used in them, demand can be by member storage in small space High density and high performance material.

As the material for coping with such demand, it is widely used thin and can folds into narrow space, resistance to The excellent flexible two-face printing wiring substrate of bendability.

But the flexibility of high, for foldable mobile phone or sliding-type mobile phone etc. the movable part of demand for densification Two-face printing wiring substrate (flexible circuit board) is, it is necessary to more excellent flexibility.In existing flexible printing wiring substrate In construction, in the case of multiple stratification, the technical problem to break after long-term use is deposited, for needing height resistance to bend(ing) Purposes for, it is impossible to it is satisfactory.

Therefore, as being used for realization the countermeasure of high resistance to bend(ing), for example, need flexible two-face printing wiring substrate from The filming of body, carries out the research for for example making dielectric film itself filming.

On the other hand, due to the shrink characteristics as polyester membrane property, there are the shape (example of patterned metal layer Such as clathrate) deform, cannot respond to the technical problem of (reaction) as wiring substrate, for the height of demand wiring substrate For the purposes of response, it is impossible to satisfactory.

Therefore, the countermeasure as the High Level for being used for realization wiring substrate, carries out for example preventing flexible perfecting The research of the pattern deformation of brush wiring substrate.

As the configuration example of flexible two-face printing wiring substrate, such as describe incited somebody to action by bonding agent in patent document 1 Copper foil be pasted onto it is on dielectric film, the metal film stack film that 3 layers of metal film stack are constructed with film is made.

But in 3 layers of metal film stack membrane structure, required Wiring pattern, in etching, occurs in order to obtain The etching not only carried out in the direction vertical with real estate, the side etching for also having in-plane (side wall) to be also etched, Cross sectional shape there are wiring part easily forms the trapezoidal trend in wide bottom portion, as a result, there are the thin spaceization change of Wiring pattern Obtain the problem of difficult.Also, copper foil in this configuration, is pasted with via adhesive linkage on insulating film surface, thus, due to the copper Paper tinsel, the filming naturally occurring limit of conductor layer.

As above-mentioned 2 layers of metal film stack film forming method, such as describe existed by galvanoplastic in patent document The copper of homogeneous film thickness is formed on dielectric film by film layer.In the method, including following manufacture method：Copper is being formed by plating Before film layer, by dry type plating methods such as vacuum vapour deposition, sputtering method, ion plating methods, chromium, oxidation will be included on dielectric film The substrate metal layer of metal beyond the copper such as chromium, nickel is formed as defined thickness, is, for example, Left and right, afterwards, Sequentially form the thin layers of copper using dry type plating method and the non-electrolytic copper facing envelope using electroless plating.

In addition, in patent document 3, as the material of flexible two-face printing wiring substrate, in 2 layers of metal film stack film The adaptation of middle dielectric film and substrate metal layer is insufficient.Therefore, the basalis for being present between dielectric film and metal layer For, it is necessary to which and the adaptation of metal layer to be stacked in basalis on good to the adaptation of dielectric film is also good.

Also, by the material of flexible printing wiring substrate in use, due to because being present in insulation under the conditions of hot and humid The change insufficient, because of caused by the oxidation of metal layer of adaptation caused by the influence of basalis between film and metal layer Color so that the material of flexible printing wiring substrate cannot use under the conditions of hot and humid.Therefore, under the conditions of hot and humid, , it is necessary to adaptation to dielectric film and to being stacked on base for being present in the basalis between dielectric film and metal layer The adaptation of metal layer on bottom is good, and it also requires the discoloration because of caused by the oxidation of metal layer does not occur.

Such as adding during by sputter process lamination metal layer and after the patterning of the metal layer of lamination It is big for the fire damage of the film surface of polyester film in thermal technology's sequence, separated out there are oligomer (mainly cyclic trimer) from the film Tendency, it may occur however that the pollution of manufacture device causes membrane surface process etc. because oligomer is separated out in film surface.

In addition, in recent years, with the high performance of final component, the patterning of metal film stack film becomes fine, schemes Case width is designed to be narrower.

Under normal conditions, mainly for assigning easy slip and preventing from damaging in each operation, in polyester film base material Coordinate particle.If add more particles, design improves the surface roughness of polyester film base material, during the processing of the base material Operability improves, but in the case where the pattern part of metal film stack film is there are the aggregation of particle, gold often occurs Belong to the undesirable undesirable condition of patterning of film lamination film.

On the other hand, when particle is mismatched in polyester base material, the roll-in road (roll pass) in each operation is passed through in film Caused damage occurs in the entire surface of film, and there is also the frequent patterning that metal film stack film occurs is undesirable bad for this The trend of situation, it is extremely difficult to process good metal film stack film.

It is high also, with the high performance of component final in recent years, have devised the response of wiring substrate becomes good The wiring substrate of sensitivity.

Polyester film base material has the shrink characteristics shunk after the heating.Due to film moving direction (MD) and with it just The shrinking percentage in the direction (TD) of friendship is poor (Δ S), and the response of shape distortion, wiring substrate there are patterned metal layer declines Trend, highly sensitive wiring substrate can not be made, it is extremely difficult to be processed into good patterned metal film stack film.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 6-132628 publications

Patent document 2：Japanese Unexamined Patent Publication 8-139448

Patent document 3：Japanese Unexamined Patent Publication 6-120630 publications

Patent document 4：Japanese Unexamined Patent Publication 2014-53410 publications

The content of the invention

Technical problems to be solved by the inivention

The present invention be in view of above-mentioned actual conditions and complete, its technical problems to be solved is to provide a kind of metal film Lamination film, it is also good to the adaptation of metal layer under the conditions of hot and humid, also, metal layer does not change colour, and Can suppress 150 DEG C in the heating process after the patterning of the metal layer after the process of lamination metal film and lamination or The oligomer that 180 DEG C or so of temperature separates out when being heat-treated separates out, the deformation of the shape of patterned metal layer, metal The patterning of film lamination film becomes fine, and pattern width is designed to be narrower, becomes even in the response for being designed as wiring substrate In high precision int, highly sensitive wiring substrate type in use, can not also be occurred because pattern it is bad and The patterning of caused undesirable condition.

For solving the means of technical problem

The present inventor has made intensive studies in view of the foregoing, it turns out that using with specific coating When the polyester film of layer is as component parts, above-mentioned technical problem can be easily solved, so as to complete the present invention.

It is that is, of the invention to be characterized by a kind of metal film stack film, it is characterised in that：At least in a polyester film mask There is the coating layer formed by the coating fluid for containing crosslinking agents more than 70 weight % relative to nonvolatile component, meet following formula (1)。

| SMD-STD |≤0.4 ... (1)

(in above-mentioned formula, SMD represents the shrinking percentage (%) of film moving direction (MD), and STD is represented and film moving direction orthogonal The shrinking percentage (%) in direction (TD), heating condition are 150 DEG C, 90 minutes.)

Also, it containing average grain diameter is 0.1~0.6 μm particle, extremely that in a preferred embodiment of the present invention, polyester film, which is, Include 3 layers of multilayer polester film less, while meet following formula (2) and (3).

0 ＜ Ti≤20 ... (2)

0≤P≤300…(3)

(in above-mentioned formula, Ti represents the titanium elements amount (ppm) in multilayer polester film, and P represents P elements amount (ppm).)

Invention effect

Metal film stack film according to the present invention, such as even if film at 150 DEG C, 90 minutes or 180 DEG C, 60 minutes Deng high-temperature atmosphere under exposure for a long time, by after harsh heat treatment step, because oligomer separates out and caused by film mist Degree rises minimum, the adaptation of the adaptation of polyester film and coating layer, metal layer and coating layer under the conditions of hot and humid Also it is good, and metal layer does not change colour, and the patterning of metal film stack film becomes fine, is set even in pattern width In use, bad etc. undesirable condition will not be patterned in fixed narrower type, even in being designed as wiring substrate Response become in the type of high precision int, highly sensitive wiring substrate in use, will not be because of patterned metal The shape distortion of layer and undesirable condition occurs, such as be suitable as flexible two sides circuit substrate or touch panel component parts (such as conductive film etc.), its industrial value are very high.

Embodiment

Polyester film is illustrated first.The polyester film of the present invention can be single layer structure, or sandwich construction, is removed Can be 2 layers, beyond 3-tier architecture, without departing from the main points of the present invention, or 4 layers or more than 4 layers of multilayer, and It is not particularly limited.

Polyester is obtained by making aromatic acid with aliphatic dihydroxy alcohol polycondensation., can be with as aromatic acid Enumerate terephthalic acid (TPA), 2,6-naphthalenedicarboxylic acid etc., as aliphatic dihydroxy alcohol, can enumerate ethylene glycol, diethylene glycol, Isosorbide-5-Nitrae- Cyclohexanedimethanol etc..As representational polyester, polyethylene terephthalate (PET), poly- 2,6- naphthalenes may be exemplified Naphthalate (PEN) etc..

Also, polyester is homopolymerization polyester or copolyester.In the case of for copolyester, to contain 30 moles of % Ternary copolymer below.As the dicarboxylic acid component of copolyester, can enumerate M-phthalic acid, phthalic acid, Terephthalic acid (TPA), 2,6- naphthalenedicarboxylic acids, adipic acid, decanedioic acid and hydroxycarboxylic acid (such as P-hydroxybenzoic acid etc.) one kind or It is two or more；As glycol component, ethylene glycol, diethylene glycol, propane diols, butanediol, Isosorbide-5-Nitrae-hexamethylene diformazan can be enumerated The one or more of alcohol, neopentyl glycol etc..

In multilayer polester film, in order to suppress the precipitation of oligomer, preferably using titanium compound (Ti) and phosphorus compound (P), the content on the compound, preferably meets following formula (2) and (3) at the same time.

0 ＜ Ti≤20 ... (2)

0≤P≤300…(3)

(in above-mentioned formula, Ti represents the titanium elements amount (ppm) in multilayer polester film, and P represents P elements amount (ppm).)

On Ti, the scope of further preferred 2~10ppm.When Ti exceedes the upper limit of above-mentioned formula (2), melted by polyester Melt in the process of extrusion by-product and generate oligomer, can not obtain that oligomer is few and film with high transparency.And, it is difficult to tackle The purposes of optical applications etc., the particularly tone of attention coated film.

On the other hand, on P, further preferred 5~200ppm, the scope of particularly preferred 0~100ppm.Exceed in P upper When stating the upper limit of formula (3), gelation occurs when manufacturing polyester, forms foreign matter, makes the quality decline of film, it is difficult to which reply is for example touched Touch panel use etc., the inspection operation with optical assessment.

By meeting above-mentioned formula (2) and (3) at the same time, oligomeric object amount is included for reducing in multilayer polester film, can be obtained Obtain more significant effect.

In addition, being preferably substantially free of antimony element containing in the layer of titanium compound and phosphorus compound above-mentioned, it is usually Below 10ppm, is preferably below 5ppm, is most preferably substantially free of, i.e. below 1ppm.When the amount of antimony element is excessive, sometimes The reason for being assembled in melting extrusion by the reduction of above-mentioned phosphorus compound, generation and becoming foreign matter, or film blacks, the transparency is not filled Point.

The polyester for the layer for containing titanium compound and phosphorus compound with above range is formed, can pass through melt polymerization Obtained polyester, but small pieces are made after melt polymerization, obtained polyester solid phase polymerization is obtained into raw material, should using During raw material, contained oligomeric object amount reduces in raw material, thus preferably using.

In the layer for containing titanium compound and phosphorus compound with above range contained oligomeric object amount be usually 0.7 weight % with Under, be preferably below 0.5 weight %.In the case that contained oligomeric object amount is few in the polyester layer, drop can be highly played Contained oligomeric object amount and the effect for preventing oligomer from being separated out in film surface in low multilayer polester film.

At least unilateral table in the present invention or with the layer formed in the polyester by common oligomer The few polyester of the oligomer is coextruded the film of the simultaneously structure that lamination forms by face, in the case where having a structure in which, The obtained effect for suppressing oligomer and separating out of the present invention can highly be played.

On the maximal roughness (St) of film surface, preferably each face is the scope of 10~100nm, more preferably 10~ 50nm.In the case where the maximal roughness (St) is less than 10nm, film surface becomes excessively smooth, exists in multilayer polester film system The trend of damage is sent out in membrane process repeatly.On the other hand, in the case of more than 100nm, on nesa coating after patterning, , there is the crystallization step in transparency conducting layer in particularly very imperceptibly patterned position of the wiring width below 4 μm The trend that the middle frequency that distribution broken string occurs increases.Also, when laminated body is made using bonding agent stickup coated film, lamination The mist degree of body significantly increases, and from optical characteristics or distinguishes from the viewpoint of property, is not suitable as optical component use sometimes.

In the present invention, mainly for assigning easy slip and preventing from damaging in each operation, outside two that multilayer is formed It is preferred in layer to coordinate the particle that average grain diameter is 0.1~0.6 μm.

Particle joined together is preferably only a kind, as long as the particle of easy slip can be assigned, is not particularly limited, As concrete example, such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, height can be enumerated The particles such as ridge soil, aluminium oxide, titanium oxide.And it is also possible to use Japanese Patent Publication 59-5216 publications, Japanese Unexamined Patent Application Heat resistance organic granular described in 59-217755 publications etc.., can be with as the example of other heat resistance organic granulars Enumerate Thermocurable urea resin, Thermocurable phenolic resin, heat-curable epoxy resin, benzoguanamine resin etc..Also, also The part precipitation of the metallic compound that makes catalyst etc. in polyester manufacturing process, micro disperse and the precipitation formed can be used Particle.

On the other hand, the shape on used particle, is not particularly limited, can use it is spherical, block, bar-shaped, Flat etc. it is any number of.Also, its hardness, proportion, color etc. are also not particularly limited.

In addition, the granule content in two outer layers is usually 0.05~1.0 weight %, is preferably 0.05~0.5 weight % Scope.In the case where granule content is less than 0.05 weight %, the easy slip of film is insufficient sometimes, as a result, is processed sometimes in film The bad orders such as Shi Fasheng damages.On the other hand, in the case that additive amount is more than 1.0 weight %, the film transparency is insufficient sometimes.

In addition, easy slip is damaged or assigned in order to prevent, in the outermost polyester layer for forming multilayer polester film preferably Use alumina particle.In the case where the average grain diameter of alumina particle exceeds above range, atraumatic effect sometimes Or easily slip is poor.

As the concrete example of alumina particle, for example, can enumerate using anhydrous Aluminum chloride as raw material by flame hydrolysis and Obtained γ types, δ type aluminium oxide etc..

As the method for adding particle in the polyester, it is not particularly limited, conventionally known method can be used.For example, Any stage for the polyester that each layer can be formed in manufacture is added, and is preferably added after esterification or ester exchange reaction.

Also, it can also carry out by the following method：Using the mixing extruder with blow vent, will be dispersed in ethylene glycol or The method of slurry and the polyester raw material mixing of particle in water etc.；Alternatively, using mixing extruder, by dry particle and polyester Method of raw material mixing etc..

Also, in polyester film, in addition to above-mentioned particle, conventionally known ultraviolet can be added as needed on and inhaled Receive agent, antioxidant, antistatic agent, heat stabilizer, lubricant, dyestuff, pigment etc..

It is usually 9~80 μm as long as the thickness of polyester film is not particularly limited in the range of it can be film-made, it is excellent Elect 12~75 μm of scope as.

In the following, the Production Example of the polyester film of the present invention is specifically described, but limited completely from following Production Example It is fixed.

First, it is preferably using polyester raw material described above, the molten sheet extruded from die head is solid using chill roll cooling Change, obtain the method for non-stretched.In this case, in order to improve the flatness of piece, preferably improve piece and cooled down with rotation Bulging adaptation, it is preferred to use electrostatic applies closely sealed method and/or liquid is coated with closely sealed method.

Then, obtained non-stretched is stretched in biaxially oriented.At this time, first with the drawing of roller or stenter mode Machine is stretched to stretch above-mentioned non-stretched in one direction.Draft temperature is usually 70~120 DEG C, is preferably 80~110 DEG C, stretching Multiplying power is usually 2.5~7 times, is preferably 3.0~6 times.Then, drawn in the direction orthogonal with the draw direction of first stage Stretch, at this time, draft temperature is usually 70~170 DEG C, and stretching ratio is usually 3.0~7 times, is preferably 3.5~6 times.Then, connect To be heat-treated under relaxation of 180~270 DEG C of the temperature under anxiety or within 30%, obtain Biaxially oriented film.

In above-mentioned stretching, it can also use in more than the 2 sections methods for carrying out unidirectional stretching.At this time, preferably with most The mode that the stretching ratio in whole two directions respectively reaches above range carries out.

Also, manufactured on polyester film, simultaneously biaxial drawing method can also be used.Simultaneously biaxial drawing method is will be above-mentioned Non-stretched typical temperature control makes it in operating direction and width in this condition at 70~120 DEG C, preferably 80~110 DEG C The method that direction stretches orientation at the same time.As stretching ratio, be usually 4~50 times with area dynameter, be preferably 7~35 times, More preferably 10~25 times.Then, then heat is carried out with 170~270 DEG C of temperature under the relaxation under anxiety or within 30% Processing, obtains stretching alignment films.On using biaxial stretch-formed device while above-mentioned stretching mode, screw rod side can be used The conventionally known stretching modes such as formula, scalable manner, line style type of drive.

Then the coating layer for forming coated film is illustrated.The formation of coating layer can be by being coated with film Liquid, the online coating carried out in film manufacturing process are set, can also be so-called using the film of manufacture is coated with outside system Coated off-line.

In coating layer, in order to reduce because of caused by fire damage oligomer externally to the increasing of the amount of precipitation of coating layer Add, it is necessary to have the coating layer formed by the coating fluid for containing crosslinking agents more than 70 weight % relative to nonvolatile component.Its In, other compositions can also be contained in coating fluid.

Crosslinking agent can use various known crosslinking agents, such as can lift oxazoline compound, melamine chemical combination with row Thing, epoxide, isocyanates based compound, carbodiimides based compound, silane coupling compound etc..Wherein, especially It is that from the viewpoint of durable adaptation is improved, Shi closes Shi oxazolines when being equipped with the purposes of functional layer on coating layer Compound.In addition, from preventing from causing because of heating ester cyclic trimer to film surface precipitation or the durability of raising coating layer From the viewpoint of coating, it is adapted to use melamine compound.

Oxazoline compound is the compound of intramolecular Ju You oxazolinyls, the polymerization of particularly preferred Han You oxazolinyls Thing, can make by the homopolymerization of the monomer of polyaddition Han oxazolinyls or with polymerizeing for other monomers.As addition polymerization The monomer of property Han oxazolinyls, can enumerate 2- vinyl -2- oxazolines, 2- vinyl -4- methyl -2- oxazoles Quinoline, 2- vinyl -5- methyl -2- oxazolines, 2- isopropenyl -2- oxazolines, 2- isopropenyl -4- first Base -2- oxazolines, 2- isopropenyl -5- ethyl-2-oxazolines etc., can use the one kind or two or more of them Mixture.Wherein, 2- isopropenyls -2- oxazolines because be industrially readily available and it is preferred that.As long as other monomers can With the monomer of the monomer copolymerization of polyaddition Han oxazolinyls, do not limit, such as (methyl) alkyl acrylate can be enumerated Base ester (is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2- ethylhexyls, hexamethylene as alkyl Base) etc. (methyl) esters of acrylic acid；Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene The unsaturated carboxylic acid class of sulfonic acid and its salt (sodium salt, sylvite, ammonium salt, tertiary ammonium salt etc.) etc.；The insatiable hunger of acrylonitrile, methacrylonitrile etc. And nitrile；(methyl) acrylamide, N- alkyl (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide is (as alkane Base, is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2- ethylhexyls, cyclohexyl etc.) etc. no Saturated amide class；The vinyl esters of vinyl acetate, vinyl propionate etc.；The second of methyl vinyl ether, ethyl vinyl ether etc. Alkenyl ethers；The alpha-olefines of ethene, propylene etc.；The halogen-containing α of vinyl chloride, vinylidene chloride, vinyl fluoride etc., β-unsaturation Monomer class；The α of styrene, α-methylstyrene etc., β-unsaturation aromatic monomer etc., can use their a kind or 2 kinds Monomer above.

The oxazoline base unit weight of oxazoline compound is usually 0.5~10mmol/g, is preferably 3~9mmol/g, more preferably The scope of 5~8mmol/g.By being used with above range, the durability of film improves.

Melamine compound is the compound for having in compound melamine structure, such as can use alkanolized three Paracyanogen amine derivative, the compound for reacting alcohol and alkanolized melamine derivative and being partially or even wholly etherified and Their mixture.As alcohol used in etherificate, it is adapted to using methanol, ethanol, isopropanol, n-butanol, isobutanol etc..Separately Outside, as melamine compound, polymer more than monomer or 2 aggressiveness, or can also use their mixture. Also, the material that a part of cocondensation of urea etc. and melamine can also be used and formed, in order to improve melamine amination The reactivity of compound, can also use catalyst.

Epoxide is the compound that intramolecular has epoxy group, such as can enumerate epichlorohydrin and ethylene glycol, poly- second The hydroxyl of glycol, glycerine, polyglycereol, bisphenol-A etc. or the condensation product of amino, there is polyepoxides, di-epoxy compounds, monocyclic Oxygen compound, glycidol amine compounds etc..As epoxide, for example, can enumerate d-sorbite polyglycidyl ether, Polyglycereol polyglycidyl ether, pentaerythrite polyglycidyl ether, two glycerine polyglycidyl ethers, three (2- of triglycidyl group Ethoxy) isocyanates, glycerine polyglycidyl ether, trimethylolpropane polyglycidyl ether；As di-epoxy compounds, example Can such as enumerate neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, resorcinolformaldehyde resin, Ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, polypropylene glycol diglycidyl Ether, polytetramethylene glycol diglycidyl ether；As mono-epoxy compounds, for example, can enumerate allyl glycidyl ether, 2- hexyl glycidyl ethers, phenyl glycidyl ether；As glycidol amine compounds, N, N, N ' can be enumerated, N '- Double (N, N- diglycidyl amino) hexamethylenes of four glycidyl group-m-xylylenediamine, 1,3- etc..

Isocyanates based compound refers to isocyanates or using blocked isocyanate as representative there is isocyanates to derive The compound of structure.As isocyanates, such as can enumerate：Toluene di-isocyanate(TDI), xylylene diisocyanate, methylene The aromatic isocyanate of base diphenyl diisocyanate, phenylene vulcabond, naphthalene diisocyanate etc.；α,α,α′, α '-tetramethyl xylylene diisocyanate etc. has the aliphatic isocyanates of aromatic rings；Methylene diisocyanate, Asia Propyl group diisocyanate, lysine diisocyanate, trimethyl hexamethylene diisocyanate, hexamethylene diisocyanate etc. Aliphatic isocyanates；Cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, Asia Alicyclic isocyanate of methyl double (4- cyclohexyl isocyanates), isopropylidene dicyclohexyl diisocyanate etc. etc..And And the biuret compounds of these isocyanates, isocyanuric acid carboxylate, urea diketonate, carbodiimides can also be enumerated and changed The polymer or derivative of property body etc..They may be used alone, and can also be used in a variety.Among above-mentioned isocyanates, it is The xanthochromia because of caused by ultraviolet is avoided, compared to aromatic isocyanate, more preferably aliphatic isocyanates or alicyclic Isocyanates.

Using the state of blocked isocyanate in use, as its end-capping reagent, such as can enumerate：Bisulfite salt, The phenol system compounds such as phenol, cresols, ethyl -phenol；The alcohol system of propylene glycol monomethyl ether, ethylene glycol, phenmethylol, methanol, ethanol etc. Compound；Methyl isobutyrylacetate, dimethyl malenate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetyl The active methylene group based compound of acetone etc.；The mercaptan based compound of butanethiol, lauryl mercaptan etc.；Epsilon-caprolactams, The lactams based compound of δ-valerolactam etc.；The amine compounds such as diphenyl aniline, aniline, ethylene imine；Antifebrin, acetyl The amide compound of amine；The oxime compound of formaldehyde, acetaldoxime, acetoxime, methyl ethyl ketone oxime, cyclohexanone oxime etc., these envelopes End agent can be used alone, and can also be two kinds or more.

In addition, isocyanates based compound can be used in the form of monomer, can also be with the mixing with various polymer The form of thing or conjugate uses.In the sense that the dispersiveness of isocyanates based compound and bridging property is improved, preferably using With polyester resin or the mixture or conjugate of polyurethane resin.

Carbodiimides based compound refers to the compound with carbodiimides structure, be in the molecule have one with On carbodiimides structure compound, for better adaptation etc., more preferably gather in the molecule with more than 2 Carbodiimides based compound.

Carbodiimides based compound can be synthesized by conventionally known technology, usually utilize diisocyanate cpd Condensation reaction.As diisocyanate cpd, be not particularly limited, fragrant family, fatty family can be used, it is specific and Speech, it is different can to enumerate toluene di-isocyanate(TDI), xylylene diisocyanate, methyl diphenylene diisocyanate, phenylene two Cyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, two isocyanide of hexamethylene Acid esters, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexyl methyl hydride Diisocyanate etc..

On the content of the carbodiimide-based contained by carbodiimides based compound, (it is used for carbodiimides equivalent Assign the weight [g] of the carbodiimide compound of carbodiimide-based 1mol) meter, it is usually 100~1000, is preferably 250 ~700, it is more preferably 300~500 scope.By being used with above range, the durability of film improves.

Also, in the range of the effect of the present invention does not disappear, in order to improve the water-soluble of polycarbodiimide based compound Property or water dispersible, can add surfactant or addition polyalkylene oxide, the quaternary ammonium salt of dialkyl amido alcohol, hydroxy alkyl sulphur The hydrophilic monomers such as hydrochlorate use.

These crosslinking agents may be used alone, two or more kinds can also be used, however, it was found that by the way that two or more is combined, energy Enough improve is difficult to taking into account with functional layer adaptation and prevent the characteristic of the ester cyclic trimer precipitation after heating.Wherein, energy It is enough to improve with the oxazoline compound of the adaptation of functional layer, with preventing the characteristic that the fat cyclic trimer after heating separates out good Melamine compound combination it is especially suitable, thus preferably.

It is effective by 3 kinds of crosslinker combinations it has also been found that in order to further improve the adaptation with functional layer.As 3 kinds More than crosslinking agent combination, be most suitable for selection melamine compound as one of crosslinking agent, as with melamine chemical combination The combination of thing, the other You Xuan oxazoline compounds of Te and epoxide, carbodiimides based compound and epoxide.

Wherein, these crosslinking agents make it react and improve the design of the performance of coating layer in drying process or film-forming process Middle use.Can speculate unreacted reactant in obtained coating layer there are these crosslinking agents, the compound after reaction or Their mixture.

In the case of containing such crosslinking component, such as it can be crosslinked at the same time and with being used to promote crosslinked component Catalyst etc..

In addition, when forming coating layer, in order to improve coating appearance or improve when on coating layer formed with functional layer Adaptation etc., polymer and can also be used.

As the concrete example of polymer, polyester resin, acrylic resin, polyurethane resin, polyethylene kind tree can be enumerated Fat (polyvinyl alcohol etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxylated cellulose, starch etc..Wherein, From the viewpoint of the adaptation with various surface functional layers is improved, preferably using polyester resin, acrylic resin, polyurethane tree Fat.Wherein, when content increases, prevent the characteristic that the fat cyclic trimer after heating separates out to be deteriorated sometimes, therefore be usually Below 30 weight %, be preferably below 20 weight %, more preferably below 10 weight %.When ratio exceeds the situation of above range Under, the fat cyclic trimer after heating cannot be effectively inhibited sometimes to be separated out.

In addition, when forming coating layer, in order to improve adhesive, sliding, particle and can also be used.From the transparency of film From the viewpoint of, its average grain diameter is usually less than 1.0 μm, is preferably less than 0.5 μm, more preferably less than 0.2 μm of scope. In addition, in order to more effectively improve sliding, lower limit is usually more than 0.01 μm, is preferably more than 0.03 μm, more preferably big In the scope of the thickness of coating layer.As the concrete example of particle, can enumerate silica, aluminium oxide, kaolin, calcium carbonate, Organic granular etc..Wherein, from the viewpoint of the transparency, preferred silica.

In addition, in the range of the main points of the present invention are not damaged, can also be as needed and with disappearing when forming coating layer Infusion, coating modifying agent, thickener, organic lubricant, antistatic agent, ultra-violet absorber, antioxidant, foaming agent, Dyestuff, pigment etc..

Based on the ratio of whole nonvolatile components in the coating fluid for forming coating layer, the ratio of crosslinking agent is 70 More than weight %, is preferably more than 80 weight %, more preferably more than 90 weight %.When ratio is below above range, have Shi Buneng effectively inhibits the precipitation of the ester cyclic trimer after heating.

From prevent heating after ester cyclic trimer precipitation from the viewpoint of, selection melamine as crosslinking agent it In the case of one, based on the ratio of whole nonvolatile components in the coating fluid for forming coating layer, the ratio of melamine Example is usually 5~95 weight %, is preferably the scope of 15~80 weight %, more preferably 30~65 weight %.When ratio is upper When stating below scope, the precipitation of the ester cyclic trimer after heating cannot be effectively inhibited sometimes.When ratio above range with When upper, degraded appearance was coated with sometimes.

It is usually 0.003~1 with the thickness gauge of the coating layer on the film that finally obtains in addition, the thickness on coating layer μm, it is preferably 0.005~0.5 μm, more preferably 0.01~0.2 μm of scope.When thickness is less than 0.003 μm, exist by film The situation that the ester cyclic trimer amount of precipitation cannot be substantially reduced.And when more than 1 μm, it sometimes appear that the appearance of coating layer becomes Difference or the problem of be easily adhered etc..

As the method for the applied coating solution on polyester film, such as airblade coating, scraper plate coating, rod painting, bar can be used Painting, scraper for coating, extrusion coated, dip-coating, reversion roller coat, transmission roller coat, intaglio plate coating, contact roller coat, cast coat, spraying, The conventionally known coating method such as curtain coating, calendering coating, extrusion coated.

In order to improve the coating of smears and film, adaptation, chemical treatment or corona can be implemented to film before coating Discharge treatment, corona treatment etc..

The metal film stack film of the present invention, such as when for touch panel etc., even if being exposed to High Temperature Gas for a long time After under atmosphere, the transparency of height is also required to sometimes.From such a viewpoint, in order to adapt to as touch panel component, Film haze change rate (heating mist degree, Δ H) before and after heat treatment (150 DEG C, 90 minutes) is usually less than 0.5%, is preferably Less than 0.3%, more preferably less than 0.1%.In the case where Δ H is more than 0.5%, as film mist degree rises, distinguishes and decline regarding property, Sometimes be not suitable for the needs such as touch panel purposes and highly distinguish the purposes regarding property.In addition, Δ H is lower, oligomer is represented Precipitation it is fewer.

In the metal film stack film of the present invention, using dimethylformamide from through Overheating Treatment (150 DEG C, 90 minutes) Oligomer (cyclic trimer) amount (OL) of front and rear painting layer surface (single side) extraction is usually 1.5mg/m²Hereinafter, it is preferably 1.0mg/m²Below.In OL more than 1.5mg/m²When, in post-processing, such as in the heat treatment steps such as sputtering process, such as companion Heat with prolonged under 150 DEG C, 90 minutes etc., high-temperature atmosphere, sometimes oligomer amount of precipitation increase, the transparency of film Decline.

Conventionally, as at a temperature of 150 DEG C or 180 DEG C or so in the process of lamination metal film into The precipitation of the oligomer separated out during row heat treatment, exists and is being designed as the patterning miniaturization, pattern width of metal tunic more In narrow type, there is the problem of a problem that patterning is bad.The present inventor thinks to form the multilayer of coated film The maximal roughness (St) of the most surface of polyester film base material is one of the reason for patterning is bad.

The maximal roughness (St) on the surface of the coating layer before and after the heat treatment of coated film is usually 10~100nm, preferably For the scope of 10~50nm.

In the coated film of the present invention, it is necessary to consider that coating layer contacts for a long time with metal layer and draws in the composition of film The corrosion risen.From such a viewpoint, on form coating layer material, the present invention purposes on, preferably substantially by The material for being halogen-free isoiony material is formed.Specifically, it is small on coated film to be placed to 24 in pure water at normal temperatures When after the total amount of halogen ion that detects, be preferably below 1ppm.

As for meeting such condition specific means, such as avoid using as far as possible and with surfactant The means of emulsion types or antistatic agent isoiony material, make water-soluble cross-linker preferably as coating layer constituent material For main constituent (more than 50%), more preferably more than 70%.

The metal film stack of the present invention must is fulfilled for formula (1) with film.Film moving direction (MD) and the direction struck a bargain with it (TD) absolute value of the shrinking percentage poor (Δ S) heated with the condition of 150 DEG C, 90 minutes must is fulfilled for following formula (1).

| SMD-STD |≤0.4 ... (1)

(in above-mentioned formula, SMD represents the shrinking percentage (%) of film moving direction, and STD represents the direction orthogonal with film moving direction Shrinking percentage (%).)

That is, the condition with 150 DEG C, 90 minutes of film moving direction (MD) and orthogonal to that direction (TD) are heated The absolute value of shrinking percentage poor (Δ S) is necessary for less than 0.4.

On SMD, it is usually 0.1~1.5%, is preferably 0.1~0.7%, more preferably 0.1~0.3% scope.

On STD, it is usually -0.3~1.0%, is preferably -0.1~0.4%, more preferably 0.1~0.3% model Enclose.

When SMD, STD are close to 0.1~0.3% scope, the pattern width of metal layer can be designed narrower.

It is preferably less than 0.3 on Δ S.More preferably less than 0.1.When Δ S is more than 0.4, patterned metal layer Shape distortion, there are the response downward trend of wiring substrate, it is difficult to use of the reply as highly sensitive wiring substrate.

In the prior art, using the coated film of polyester film base material by the process of metal film stack with 150 DEG C or 180 DEG C or so temperature when being heat-treated, coated film is shunk, since the contraction of MD and TD are poor, the shape of patterned metal layer Deformation, there are the response downward trend of wiring substrate.Therefore, it is necessary to highly sensitive wiring substrate.The present inventor Think to form the reason for metal film stack with the heat shrink rate poor (Δ S) of film, coated film MD and TD is the undesirable condition One of.

In the coated film for forming metal film stack film, due to that can suppress in 150 DEG C or 180 DEG C or so of temperature Endurancing under heat treatment or hot and humid atmosphere when being used in the manufacturing procedure under conditions of stringent because oligomeric Thing from coated film separate out caused by mist degree significantly rises, the maximal roughness (St) that will be heat-treated front and rear film surface suppresses It is in lower degree, the shrinking percentage poor (Δ S) of the MD and TD that make coated film | SMD-STD | less than=0.4, even in for gold Film lamination is designed to miniaturization to category with the patterning of film, pattern width is designed to be narrower, there is highly sensitive wiring substrate Type when, can also solve to pattern bad etc. unfavorable condition.Wherein, the MD of coated film mentioned here represents processing work Film moving direction in sequence.In addition, TD is represented relative to the orthogonal direction of the film moving direction in manufacturing procedure.

In the present invention, in order to further improve the effect of above-mentioned thermal dimensional stability, preferably made annealing treatment.Close In annealing, known gimmick all the time can be used.Specifically, such as the temperature of annealing is usually 160~200 DEG C, be preferably 165~195 DEG C, more preferably 170~190 DEG C of scope.The annealing time is usually 1~30 second, is preferably 3~20 seconds, more preferably 5~15 seconds.In addition, film translational speed is usually that 10~300m/min, layer tension (in baking oven) are usual For 1kg~10kg/ films are wide, preferably 1kg~7kg/ films are wide, more preferably 1kg~5kg/ films are wide, preferably while being removed to film Send while being made annealing treatment.

In the following, the metal for forming metal film stack film is illustrated.As metal, can also use gold, platinum, silver, copper, The solid solution of two or more metal such as the metal simple-substance or nickel-chromium alloy of aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, indium etc. (alloy).Wherein, it is contemplated that versatility that metal film is formed, cost, the easiness etc. removed using etching, preferred chromium, nickel, Titanium, nickel-chromium alloy, aluminium, zinc, copper-nickel alloy, copper-titanium alloy, gold, silver and copper, more preferably chromium, nickel, titanium, nickel-chromium alloy, aluminium, Zinc, gold, silver and copper.Most preferably copper (also including cupric oxide).Also, metallic diaphragm can be individual layer, or different Metal laminated more than 2 layers and formed multi-ply construction.

The thickness of the metal film formed in the coating aspect of coated film is not particularly limited, and is usually 5~500nm, preferably For the scope of 10~300nm.When the layer thickness of metal layer is less than 5nm, metal layer is easily cracked sometimes.And in metal layer When layer thickness is more than 500nm, forming metal layer needs for a long time, and there are the trend of Expenses Cost.

Method on forming metal layer on coating layer, can use known gimmick all the time.Specifically, it is excellent Gate more than 1 in vapour deposition method, sputtering method and ion plating method kind of method to be formed, and particularly preferably pass through sputtering method shape Into.Two or more can be applied in combination for the above method, and arbitrary method can also be used alone.

On vapour deposition method (vacuum vapour deposition), it is put into very (in the present invention equivalent to two sided coatings film) preferably by supporter In empty container, by making METAL HEATING PROCESS evaporation form metal layer on coating layer.

On sputtering method, preferably supporter is put into vacuum tank (in the present invention equivalent to two sided coatings film), is led Enter the inactive gas such as argon, apply DC voltage, ionized inactive gas is hit target metal, using by knocking-on gold Category forms metal layer on coating layer.

On ion plating method, preferably supporter is put into vacuum tank (in the present invention equivalent to two sided coatings film), Under glow discharge atmosphere, METAL HEATING PROCESS is evaporated, metal layer is formed on coating layer using ionized evaporated metal.

In patterning, conventionally known technology can be utilized to implement.Such as in Japanese Unexamined Patent Publication 2014-150118 public affairs Have in report described.

Embodiment

Hereinafter, the present invention is described in more detail using embodiment, but the present invention without departing from its main points simultaneously Do not limited by following embodiment.Wherein, " parts by weight " are represented when " part " described in embodiment and comparative example.In addition, this hair The bright middle assay method used and evaluation method is as follows.

(1) assay method of the inherent viscosity of polyester：

The polyester 1g after removing other polymers component not compatible with polyester and pigment is accurately weighed, adds benzene The mixed solvent 100ml of phenol/tetrachloroethanes=50/50 (weight ratio) makes its dissolving, is measured with 30 DEG C.

(2) average grain diameter (d50) and size distribution：

The centrifugal type particle size distribution device SA-CP3 types produced using Shimadzu Scisakusho Ltd, are utilized The size of sedimentation measure particle based on stokes' law of resistance, obtains average grain diameter.With the assay method of average grain diameter Size distribution is obtained in same operation.That is, added up from the bulky grain side in equivalent spherical distribution, grain is calculated according to following formula Degree distribution is than (R).

(r) particle diameter (3) polyester raw material when particle diameter/particle cumulative weight when=particle cumulative weight is 25% is 75% In the contained assay method for including oligomeric object amount：

Polyester raw material about 200mg is weighed, the ratio for dissolving it in chloroform/HFIP (hexafluoro -2- isopropanols) is 3: 2 In mixed solvent 2ml.After dissolving, after additional chloroform 20ml, methanol 10ml is little by little marginally added.By filtering sediment Remove, the mixed solvent for being further 2: 1 using the ratio of chloroform/methanol cleans sediment, and filtrate, cleaning solution are returned Receive, concentrated using evaporator, make its dry solidification afterwards.Dry solidification thing is set to be dissolved in DMF (dimethylformamide) 25ml Afterwards, which is supplied to liquid chromatogram (Shimadzu Seisakusho Ltd.'s production：LC-7A in), the oligomeric object amount in DMF is obtained, is used The value divided by the polyester raw material amount for being dissolved in chloroform/HFIP in the mixed solvents, as including oligomeric object amount (weight %).In DMF Oligomeric object amount according to standard specimen peak area with measure sample peak area peak area ratio obtain (absolute standard curve method).

(4) assay method for including oligomeric object amount contained in coated film：

Weigh coated film about 200mg, the ratio for dissolving it in chloroform/HFIP (hexafluoro -2- isopropanols) be 3: 2 it is mixed In bonding solvent 2ml.After dissolving, after additional chloroform 20ml, methanol 10ml is little by little marginally added.Sediment is removed by filtering Go, the mixed solvent for being further 2: 1 using the ratio of chloroform/methanol cleans sediment, and filtrate, cleaning solution are returned Receive, concentrated using evaporator, make its dry solidification afterwards.Dry solidification thing is set to be dissolved in DMF (dimethylformamide) 25ml Afterwards, which is supplied to liquid chromatogram (Shimadzu Seisakusho Ltd.'s production：LC-7A in), the oligomeric object amount in DMF is obtained, with the value Divided by the coated film amount of chloroform/HFIP in the mixed solvents is dissolved in, as including oligomeric object amount (weight %).It is oligomeric in DMF Object amount is obtained (absolute standard curve method) according to standard specimen peak area and the peak area ratio of measure sample peak area.

On the preparation of standard specimen, point oligomer (ester cyclic trimer) taken in advance is weighed exactly, is dissolved in standard Prepared in the DMF really weighed.The concentration of the standard specimen preferably scope of 0.001~0.01mg/ml.

Wherein, the condition of liquid chromatogram is as follows.

Mobile phase A：Acetonitrile

Mobile phase B：2% acetic acid aqueous solution

Column：Mitsubishi chemical Co., Ltd produces, " MCI GEL ODS 1HU "

Column temperature：40℃

Flow velocity：1ml/ minutes

Detection wavelength：254nm

(5) thickness of lamination polyester layer：

After the film of small pieces is fixed shaping using epoxy resin, cut using slicer, utilize transmission electron microscope Photo observes the section of film.In this section, 2 interfaces that by light and shade are formed substantially parallel with film surface can be observed.Root The distance of 2 interfaces and film surface is measured according to 10 photos, using average value as laminated thickness.

(6) metallic element in polyester film and P elements amount quantify：

Using fluorescent x-ray analyzer (Shimadzu Scisakusho Ltd produces, model " XRF-1500 "), following Under conditions of shown in table 1, the amount of element obtained in film is measured by monolithic using film FP methods.Wherein, the detectable limit of this method is led to Often it is 1ppm or so.

[table 1]

(7) coating thickness：

Film is fixed using embeding resin, using slicer cutting section, 2% osmic acid carry out 60 DEG C, 2 it is small when dye, make Standby sample.Utilize the obtained sample of transmission electron microscope (Jeol Ltd. produces JEM2010) observation, measure The thickness of coating layer.Amounting to for film, is measured at 15, will remove from the big side of numerical value at 3 points, remove 3 from small side 9 points of average value after point is as coating thickness.

(8) the measure side for the oligomeric object amount (OL) extracted from the painting layer surface for the coated film for forming metal film stack film Method：

Coated film is heated 90 minutes with 150 DEG C in atmosphere in advance.Afterwards, top is made in the film through Overheating Treatment Open 10cm in length and breadth, height 3cm, the shape of the box-shaped of inner face is used as using aspect of measure (coating layer).Then, according to above-mentioned DMF (dimethylformamide) 4ml is added in case made of method, after placing 3 minutes, DMF is recycled.The DMF of recycling is supplied To liquid chromatogram, (Shimadzu Seisakusho Ltd. produces：LC-7A in), the oligomeric object amount in DMF is obtained, with the value divided by the film of contact DMF Area, as the oligomeric object amount (mg/m of film surface²).Oligomeric object amount in DMF is according to standard specimen peak area and measure sample peak The peak area ratio of area is obtained in (absolute standard curve method) (A faces).Opposed surface side (B faces) is also according to side similar to the above Method is measured, and obtains the oligomeric object amount (OL) extracted by painting layer surface.

On the preparation of standard specimen, point oligomer (cyclic trimer) taken in advance is weighed exactly, it is accurate to be dissolved in Prepared in the DMF of weighing.The concentration of the standard specimen preferably scope of 0.001~0.01mg/ml.

Wherein, the condition of liquid chromatogram is as follows.

Mobile phase A：Acetonitrile

Mobile phase B：2% acetic acid aqueous solution

Column：Mitsubishi chemical Co., Ltd produces, " MCI GEL ODS 1HU "

Column temperature：40℃

Flow velocity：1ml/ minutes

Detection wavelength：254nm

(9) measure of coated film mist degree (H0)：

For sample film, according to JIS-K-7136, color research institute production " HM-150 " measure film mist in village is utilized Degree.

(10) measure of the coated film mist degree (H1) after heating：

It is same with (5) item to operate after being handled with defined heat treatment condition (150 DEG C, 90 minutes) sample film, survey Determine film mist degree.

(11) measure of coated film haze change amount (heating mist degree, Δ H)：

According to the measured value of (7) item He (8) item, coated film haze change amount (heating mist degree, Δ H) is calculated.

Δ H=(H1)-(H0)

Δ H is lower, represents that the oligomer that is separated out by high-temperature process is fewer, more well.

(12) maximal roughness (St) for being coated with film surface is measured (before heat treatment)：

For the aspect of measure of sample film, using employing, Direct Phase detects interferometric method, so-called utilization Michael interferes 2 beam interference methods the non-planar contact surfaces measuring system Micromap 512 of production " Micromap companies) " measure surface it is thick Rugosity (St).Wherein, measure wavelength is set to 530nm, and object lens use 20 times, carry out 20 ° of perimetries, measure 12 points altogether, The average value for amounting to 10 points for removing its maximum and minimum value in measured value is taken, as its surface roughness (St).Root According to said determination method, in coated film, the surface roughness (St1) (A faces) of the film surface before measure heat treatment.Opposed surface Side (B faces) is also according to method similar to the above measure surface roughness (St2).

(13) maximal roughness (St) for being coated with film surface is measured (after heat treatment)：

According to the method same with above-mentioned (12), in coated film, the film after 150 DEG C of measure progress, heat treatment in 90 minutes The surface roughness (St3) (A faces) on surface.

Opposed surface side (B faces) is also according to method similar to the above measure surface roughness (St4).

(14) maximal roughness (St) measure on the metal layer region surface after patterning：

In coated film, the copper oxide of thickness 20nm is formed on the surface of the film by reactive sputtering method.In the oxidation Coating is patterned (most thin portion in layers of copper：20 μm) photoresist and after making its dry solidification, by obtained oxidation Layers of copper is immersed in 4% ferric chloride in aqueous solution and is etched.Obtained by being made by the heating of 150 DEG C × 90 minutes It is patterned after copper oxide crystallization.According to the method same with above-mentioned (12), after measuring obtained patterning The surface roughness (St5) (A faces) of the metal layer region of copper oxide.

(15) maximal roughness (St) measure on the metal layer region surface after patterning：

(14) opposing face (B faces) there is also metal layer in the case of, carried out according to above-mentioned (14) same method Patterning, according to the method same with above-mentioned (12), measures the metal layer region of the copper oxide after obtained patterning Surface roughness (St6).

(16) maximal roughness (St) measure on the surface in the region for the metal layer being not provided with after patterning：

For the surface roughness (St) in the non-metallic layer region of (14), according to the method same with above-mentioned (12), measure Surface roughness (St7) (A faces).

(17) maximal roughness (St) measure on the surface in the region for the metal layer being not provided with after patterning：

For the surface roughness (St) in the non-metallic layer region of (14), according to the method same with above-mentioned (12), measure Surface roughness (St8) (B faces).

(18) measure of the shrinking percentage (SMD, STD) of coated film：

For sample film, carried out 90 minutes in the baking oven for being maintained at set point of temperature (150 DEG C) in the state of no-station pole canopy Heat treatment, is measured the length of sample before and after the heat treatment, is calculated using following formula.Wherein, all carried out for the MD and TD of coated film Measure.

Shrinking percentage={ (sample length before heat treatment)-(sample length after heat treatment) }/(sample before heat treatment Length) × 100

(19) adaptation (before warming and humidifying) evaluation to metal layer (practical characteristic substitutes evaluation)：

In coated film, the cupric oxide of thickness 20nm is formed on the painting layer surface of coated film by reactive sputtering method Layer.After the photoresist being patterned is coated with the copper oxide and makes its dry solidification, by obtained copper oxide It is immersed in 4% ferric chloride in aqueous solution and is etched so that copper oxide is remained with the width of 3mm.By 150 DEG C × The heating of 90 minutes makes the copper oxide crystallization after obtained patterning.Then, made using Shimano Inc " Ezgraph " is produced, according to the regulation of JISC 5016, the tension test in 90 degree of directions is carried out, measures for the close of metal layer With joint efforts, judged in (A faces) according to following determinating references.In the case where opposed surface side (B faces) is there is also metal layer, press It is measured according to method similar to the above, is judged according to following determinating references.

《Determinating reference》

A：Closing force is more than 0.5N/mm, and adaptation is good (grade having no problem in practicality)

B：Closing force is 0.3~0.4N/mm, and adaptation is common (problematic grade sometimes in practicality)

C：Closing force is below 0.2N/mm, and adaptation is bad (grade of problems in practicality)

(20) adaptation (after warming and humidifying) evaluation to metal layer (practical characteristic substitutes evaluation)：

In coated film, the cupric oxide of thickness 20nm is formed on the painting layer surface of coated film by reactive sputtering method Layer.After the photoresist being patterned is coated with the copper oxide and makes its dry solidification, by obtained copper oxide It is immersed in 4% ferric chloride in aqueous solution and is etched so that 12mm width residual oxidization layers of copper.Pass through 150 DEG C × 90 The heating of minute makes the copper oxide crystallization after obtained patterning.Afterwards, it is put into and is maintained at 85 DEG C of temperature, humidity In the thermostat of the condition of 85%RH 48 it is small when.Afterwards, according to the method same with above-mentioned (11), measure to the closely sealed of metal layer Power, is judged in (A faces) according to following determinating references.In the case where opposed surface side (B faces) is there is also metal layer, according to Method similar to the above is measured, and is judged according to following determinating references.

《Determinating reference》

A：Closing force is more than 0.5N/mm, and adaptation is good (grade having no problem in practicality)

B：Closing force is 0.3~0.4N/mm, and adaptation is common (problematic grade sometimes in practicality)

C：Closing force is below 0.2N/mm, and adaptation is bad (grade of problems in practicality)

(21) the discolouration evaluation of metal layer (practical characteristic substitutes evaluation)：

In coated film, the cupric oxide of thickness 20nm is formed on the painting layer surface of coated film by reactive sputtering method Layer.Afterwards, be put into be maintained in the thermostat of 85 DEG C of temperature, the condition of humidity 85%RH 48 it is small when, afterwards, visual observations metal The copper oxide surface of film lamination film surface, is judged in (A faces) according to following determinating references.In opposed surface side (B Face) there is also metal layer in the case of, be measured according to method similar to the above, sentenced according to following determinating references It is fixed.

《Determinating reference》

A：Do not change colour, well (grade having no problem in practicality)

B：Confirm discoloration (problematic grade sometimes in practicality) slightly

C：Confirm discoloration (grade of problems in practicality)

(22) pattern form (deformation) evaluation after layers of copper patterning：

In coated film, the cupric oxide of thickness 20nm is formed on the painting layer surface of coated film by reactive sputtering method Layer.Clathrate it is coated with the copper oxide and is patterned (most thin portion：12 μm) photoresist and make its dry solidification Afterwards, obtained copper oxide is immersed in 4% ferric chloride in aqueous solution and be etched.After obtained patterning Copper oxide, the pattern (length of the X before heating on the clathrate before and after the heating of 150 DEG C × 90 minutes is carried out Degree=3.00mm, heating before Y length=3.00mm) change in size (X, Y), observed, pressed using measuring microscope Judged according to following determinating references.Wherein, MD and TD of the deformation of the shape of the metal layer after patterning due to coated film Contraction it is poor.Therefore, in this evaluation, evaluated for the sake of easy in A faces.

(determinating reference)

A：The length difference of X and Y after heating (there's almost no change in size, in fact for below 0.01mm before and after heating Use the grade having no problem)

B：The length difference of X and Y after heating (due to heating front and rear very little method change, are deposited more than 0.01mm in practicality In the grade of problem)

Evaluated in this evaluation with the pattern of clathrate, but it's not limited to that.

(23) the distribution broken string evaluation after layers of copper patterning (the practical characteristic of heat resistance substitutes evaluation)：

In coated film, the copper oxide of thickness 20nm is formed on the surface of the film by reactive sputtering method.In the oxidation Linearly coating is patterned (most thin portion in layers of copper：4 μm, 8 μm, 12 μm, 20 μm) photoresist and carry out dry solidification Afterwards, obtained copper oxide is immersed in 4% ferric chloride in aqueous solution and be etched.Pass through 150 DEG C × 90 minutes Heating make the crystallization of the copper oxide after obtained patterning.

Using light microscope, (KEYENCE CORPORATION are produced, digital microscope, model：VHX-200), with again Rate 40 is again checked at 100 the position as most thin portion of the copper oxide after obtained patterning, checks for oxygen Change the broken string of layers of copper, the distribution broken string property (A faces) after being patterned according to following benchmark evaluation.Also press opposed surface side (B faces) Checked according to method similar to the above, judged according to following determinating references.

《Determinating reference》

A：A faces, B faces do not confirm the broken string of copper wiring

B：A faces, B faces do not confirm the broken string of copper wiring, but confirm the crack phenomenon of distribution

C：A faces, B faces confirm the broken string of the copper wiring more than at 1

(24) halogen ion amount in coated film quantifies：

Sample film (coated film) is cut into 10cm square, in pure water with room temperature immersion 24 it is small when.Afterwards, ion color is passed through Spectrometry, with the halogen ion amount of following determination conditions measure detection.

(ion chromatography condition)

Analytical equipment：The production of DIONEX companies, DX-320

Splitter：Ion Pac AS15(4mm×250mm)

Guard column：Ion Pac AG15(4mm×50mm)

Removing system：ASRS-ULTRA (exterior demodulation modes, 100mA)

Detector：Electrical conductivity detector

Eluent：7mM KOH (0~20 minute)

45mM KOH (20~30 minutes)

(using eluent generator EG40)

Elute flow quantity：1.0ml/ minute

Sample injection rate：250μl

(determinating reference)

A：Halogen ion amount is below 1ppm (grade having no problem in practicality)

B：Halogen ion amount is more than 1ppm (there may be problem in practicality)

(25) overall merit：

The patterned metal film stack film on the painting layer surface of coated film obtained in embodiment and comparative example In, the pattern shape after discolouration evaluation, layers of copper patterning based on the adaptation (before and after warming and humidifying) to metal layer, metal layer Distribution broken string evaluation after shape (deformation), copper oxide patterning, overall merit is carried out according to following determinating references.

《Determinating reference》

A：The discolouration of adaptation (before and after warming and humidifying), metal layer to metal layer is evaluated, the figure after layers of copper patterning Distribution broken string evaluation after case shape (deformation), copper oxide patterning is zero (grade having no problem in practicality)

B：The discolouration of adaptation (before and after warming and humidifying), metal layer to metal layer is evaluated, the figure after layers of copper patterning In distribution broken string evaluation after case shape (deformation), copper oxide patterning, at least one is (problematic sometimes in practicality for △ Grade)

C：The discolouration of adaptation (before and after warming and humidifying), metal layer to metal layer is evaluated, the figure after layers of copper patterning Case shape (deformation), copper oxide patterning after distribution broken string evaluation in, at least one for × it is (of problems etc. in practicality Level)

Operation is prepared the polyester used in embodiment and comparative example as described below.

The manufacture ＞ of ＜ polyester

[manufacture method of polyester (I)]

Using 100 parts by weight of dimethyl terephthalate (DMT) and 60 parts by weight of ethylene glycol as starting material, add as catalysis The butyl titanate of agent, is put into reactor, and reacting initial temperature is set to 150 DEG C, makes while methanol is distilled off anti- Answer temperature slowly to rise, 3 it is small when after reach 230 DEG C.4 it is small when after, ester exchange reaction substantially terminates.The reaction mixture is moved Enter polycondensation groove, polycondensation reaction when progress 4 is small.That is, temperature is slowly heated up from 230 DEG C and reaches 280 DEG C.On the other hand, pressure from Normal pressure starts slowly to depressurize, and is finally reached 0.3mmHg.After reaction starts, by the change of the stirring power of reactive tank, suitable Stop reaction at the time of inherent viscosity 0.55, polymer is discharged under nitrogen pressurization, obtains inherent viscosity 0.59, oligomer The polyester (I) of 0.89 weight % of (ester cyclic trimer) content.

[manufacture method of polyester (II)]

After polyester (I) is given crystallization in advance with 160 DEG C, solid phase is carried out under the blanket of nitrogen of 220 DEG C of temperature, is obtained The polyester (II) of inherent viscosity 0.72,0.46 weight % of oligomer (ester cyclic trimer) content.

[manufacture method of polyester (III)]

Using 100 parts by weight of dimethyl terephthalate (DMT) and 60 parts by weight of ethylene glycol as starting material, add as catalysis Four water magnesium acetates of agent, are put into reactor, and reacting initial temperature is set to 150 DEG C.Make while methanol is distilled off anti- Answer temperature slowly to rise, 3 it is small when after reach 230 DEG C.4 it is small when after, ester exchange reaction substantially terminates.The reaction mixture is moved Enter polycondensation groove, after adding orthophosphoric acid, add germanium dioxide, polycondensation reaction when progress 4 is small.That is, temperature is slowly risen from 230 DEG C Temperature, reaches 280 DEG C.On the other hand, pressure is slowly depressurized since normal pressure, is finally reached 0.3mmHg.After reaction starts, pass through The change of the stirring power of reactive tank, stops reaction at the time of equivalent to inherent viscosity 0.63, by polymer under nitrogen pressurization Discharge, obtains the polyester (III) that inherent viscosity is 0.63.

[manufacture method of polyester (IV)]

In the manufacture method of polyester (I), the alumina particle being dispersed in ethylene glycol of 0.3 μm of average grain diameter is added, Particle is set to reach 1.5 weight % relative to the content of polyester, in addition, same operation is manufactured, and obtains polyester (IV).Institute The inherent viscosity of obtained polyester (IV) is that 0.59, oligomer (ester cyclic trimer) content is 0.87 weight %.

[manufacture method of polyester (V)]

On alumina particle, except average grain diameter is different, it is changed into beyond 0.04 μm, is carried out with polyester (IV) equally operation Manufacture, obtains polyester (V).The inherent viscosity of obtained polyester (V) is 0.59, oligomer (ester cyclic trimer) content is 0.87 weight %.

[manufacture method of polyester (VI)]

On alumina particle, except average grain diameter is different, it is changed into beyond 0.8 μm, is carried out with polyester (IV) equally operation Manufacture, obtains polyester (VI).The inherent viscosity of obtained polyester (VI) is 0.59, oligomer (ester cyclic trimer) content is 0.87 weight %.

[manufacture method of polyester (VII)]

Using 100 parts by weight of dimethyl terephthalate (DMT) and 60 parts by weight of ethylene glycol as starting material, catalyst will be used as Four water magnesium acetates, 0.09 parts by weight be put into reactor, will reaction start temperature be set to 150 DEG C, methanol is distilled off same When reaction temperature is slowly increased, 3 it is small when after reach 230 DEG C.4 it is small when after, ester exchange reaction substantially terminates.Mixed in the reaction After adding 0.04 part of acid phosphate ester in compound, 0.04 part of antimony trioxide, polycondensation reaction when progress 4 is small are added.That is, by temperature From 230 DEG C of slowly heatings, reach 280 DEG C.On the other hand, pressure is slowly depressurized since normal pressure, is finally reached 0.3mmHg.Instead After should starting, by the change of the stirring power of reactive tank, stop reaction at the time of equivalent to inherent viscosity 0.63, in nitrogen plus Polymer is discharged in pressure.Obtained polyester (VII) inherent viscosity be 0.63.

Embodiment 1：

The mixing that above-mentioned polyester (II), (III), (IV) are mixed with 89.5%, 10%, 0.5% ratio respectively Raw material, using the raw material of polyester (I) 100% as b layers of raw material, is fed separately in 2 extruders, divides as a layers of raw material After not with 285 DEG C of meltings, using a layers as outermost layer (top layer), b layers as intermediate layer.Roused in the curtain coating for being cooled to 40 DEG C, with The mode that 2 kinds 3 layers (aba), laminated polyester film thickness form than a: b: a=2: 19: 2 is coextruded, and is allowed to cool curing, is obtained To No yield point piece.Then, using roller circumference speed difference, after 85 DEG C of 3.3 times of stretchings in the vertical of film temperature.Will be by table 2 below institute The coating layer that the smears composition shown is formed, 0.04 μm of amount is reached in single side with dried coated weight and is coated on film two sides (relative to film moving direction, upper surface is A faces, lower surface is B faces), afterwards, imports stenter, in the horizontal with 120 DEG C of drawings 4.9 times are stretched, after being heat-treated with 235 DEG C, is relaxed in the horizontal, by film roll on roller, obtains the wide 1000mm of film, coiling length The two sided coatings film of 6000m, coating layer equipped with 23 μm of thickness.Wherein, under forming the compound of coating layer for example.Also, close In the micro-adjustment of STD, it is micro-adjusted so that the film after relaxation in transverse direction is wide.(compound example)

(A1)：Hexa methoxy melamine methylol

(A2)：The EPOCROS (Nippon Shokubai Co., Ltd's production) of Zuo Wei oxazoline compounds

Oxazoline base unit weight 7.7mmol/g

(A3)：Make EPOCROS (Nippon Shokubai Co., Ltd's production) oxazoline base unit weight for oxazoline compound 4.5mmol/g

(A4)：Polyglycereol polyglycidyl ether

(A5)：The blocked polyisocyanate synthesized by the following method

With 60 DEG C to hexamethylene diisocyanate 1000 parts be stirred, add sad tetramethyl-ammonium as catalyst 0.1 part.4 it is small when after, add 0.2 part of phosphoric acid, make reaction terminating, obtain isocyanurate type polyisocyanate composition.Add Obtained 100 parts of isocyanurate type polyisocyanate composition, the methoxy poly (ethylene glycol) 42.3 of number-average molecular weight 400 Part, 29.5 parts of propylene glycol methyl ether acetate, with 80 DEG C keep 7 it is small when.Afterwards, reacting liquid temperature is maintained at 60 DEG C, added 35.8 parts of methyl isobutyrylacetate, 32.2 parts of diethyl malonate, 0.88 part of 28% methanol solution of sodium methoxide, when holding 4 is small. Add 58.9 parts of n-butanol, with 80 DEG C of reacting liquid temperature keep 2 it is small when, afterwards, add the own ester 0.86 of acid phosphate -2- methyl Part, obtain blocked isocyanate.

(A6)：CARBODILITE (Nisshinbo Chemical Inc. lifes as polycarbodiimide based compound Production) carbodiimides equivalent 340

(B1)：Obtained glass transition temperature is polymerize as 40 DEG C of aqueous acrylic resin dispersion using following form

Ethyl acrylate/n-butyl acrylate/methyl methacrylate/N hydroxymethyl acrylamide/acryllic acid= Emulgating polymers (the emulsifying agent of 65/21/10/2/2 (weight %)：Anionic surfactant)

(B2)：Will be with 315 parts by weight of terephthalic acid (TPA), 299 parts by weight of M-phthalic acid, 74 parts by weight of ethylene glycol and diethyl 265 parts by weight of glycol for component polyester polyol as (B2a) when, using ammonia by (B2a) 953 parts by weight, isophorone two The poly- ammonia of polyester of 267 parts by weight of isocyanates, 56 parts by weight of ethylene glycol and 67 parts by weight of dihydromethyl propionic acid as constituent Ester neutralizes, and obtains the water dispersion viscosity 30mPas of when (concentration 23%, 25 DEG C)

(B3)：Polyvinyl alcohol (saponification degree 88 moles of %, degree of polymerization 500)

(C1)：2- amino-2-methyl propanol hydrochlorides as melamine crosslinking catalyst

(D1)：Polymer containing quaternary ammonium salt base.

2- hydroxy-3-methyl acryloxypropyl leptodactyline polymer

Ion balance：Pyrovinic acid radical average molecular weight：30000

(F1)：The silica dioxide granule that 0.07 μm of average grain diameter.

(F2)：The Alumina modified silica particle of 0.02 μm of average grain diameter.

Then, in the painting layer surface of obtained coated film, by sputtering method, on two sides, lamination copper oxide makes it thick Degree reaches 20nm, the photoresist being patterned is coated with the copper oxide, after curing is dried, by obtained oxygen Change layers of copper to be immersed in 4% ferric chloride in aqueous solution, be etched, obtain patterned two sides metal film stack and use Film.Characteristic is shown in table 10 below~16 by obtained film.

Embodiment 2~19：

In embodiment 1, except forming the coating layer formed from the smears shown in table 2 below, (following tables with raw material 3~9) stretching ratio, horizontal stretching ratio, oikocryst temperature, thickness, are indulged and forms ratio, film thickness, the film width after transverse relaxation Beyond difference, manufacture similarly to Example 1, obtain film.The characteristic of obtained film is shown in table 10 below~16.

Embodiment 20：

In embodiment 6, in addition to changing the coating weight of coating layer, manufacture similarly to Example 6, obtain film.By institute The characteristic of obtained film is shown in table 10 below~16.

Embodiment 21：

In embodiment 1, outside system, by the film of manufacture in hot air type baking oven, layer tension is set as (in baking oven) The condition of 3kg/1000mm width, the film conveyance speed of 60m/min, 180 DEG C, heating (offline annealing) again in 10 seconds, except this with Outside, manufacture similarly to Example 1, obtain film.The characteristic of obtained film is shown in table 10 below~16.

Embodiment 22：

In embodiment 10, outside system, by the film of manufacture in hot air type baking oven, layer tension is set as (in baking oven) The condition of 3kg/1000mm width, the film conveyance speed of 60m/min, 190 DEG C, heating (offline annealing) again in 10 seconds, except this with Outside, manufacture similarly to Example 1, obtain film.The characteristic of obtained film is shown in table 10 below~16.

Embodiment 23：

In embodiment 11, outside system, by the film of manufacture in hot air type baking oven, layer tension is set as (in baking oven) The condition of 3kg/1000mm width, the film conveyance speed of 60m/min, 170 DEG C, heating (offline annealing) again in 10 seconds, except this with Outside, manufacture similarly to Example 11, obtain film.The characteristic of obtained film is shown in table 10 below~16.

Embodiment 24：

In embodiment 6, outside system, by the film of manufacture in hot air type baking oven, layer tension is set as (in baking oven) The condition of 3kg/1000mm width, the film conveyance speed of 60m/min, 160 DEG C, heating (offline annealing) again in 10 seconds, except this with Outside, manufacture similarly to Example 6, obtain film.The characteristic of obtained film is shown in table 10 below~16.

Embodiment 25：

In embodiment 22, by sputtering method, the only painting layer surface lamination copper oxide in the A faces of coated film makes it thick Degree reaches 20nm, the photoresist being patterned is coated with the copper oxide, after curing is dried, by obtained oxygen Change layers of copper to be immersed in 4% ferric chloride in aqueous solution, be etched, obtain patterned one-sided metallic film lamination and use Film, in addition, manufactures, obtains film similarly to Example 22.The characteristic of obtained film is shown in table 10 below~16.

Comparative example 1~6：

In embodiment 6, in addition to changing into and forming the coating layer formed by the smears shown in table 2 below, with reality Apply example 6 equally to manufacture, obtain film.The characteristic of obtained film is shown in table 10 below~16.

In comparative example 5, comparative example 6, comparative example 7, in the discolouration evaluation of (21) metal layer, as being put into constant temperature In groove 48 it is small when the 24th hour of intermediate point when, also metal film stack is carried out with the discoloration on the copper oxide surface of film surface Confirm, as a result, at 24 hours confirmed discoloration.The characteristic of obtained film is shown in table 10 below~16.

Comparative example 8：

In embodiment 1, in addition to being not provided with coating layer, manufacture similarly to Example 1, obtain film.Will be obtained The characteristic of film is shown in table 10 below~16.

Comparative example 9~11：

In embodiment 6, in addition to a layers of raw material difference, manufacture similarly to Example 6, obtain film.

Comparative example 12：

In embodiment 6, the polyester (IV) on top layer is changed to polyester (VI), manufactures similarly to Example 1, obtains two sides Coated film, as a result, the surface of two sided coatings film is roughened, in the distribution broken string evaluation after (23) layers of copper patterning, it is difficult to should The patterning of most 4 μm of thin portion is processed.The characteristic of obtained film is shown in table 10 below~16.

Comparative example 13：

In embodiment, as a layers of raw material, by polyester (III), (IV), (VII) respectively with 10%, 0.5%, 89.5% ratio mixing, in addition, manufactures, obtains film similarly to Example 6.The characteristic of obtained film is shown in following Table 10~16.

Comparative example 14：

In embodiment 1, in addition to the film width difference after relaxation in horizontal stretching ratio, transverse direction, similarly to Example 1 Manufacture, obtains film.The characteristic of obtained film is shown in table 10 below~16.

Comparative example 15：

It is same with embodiment 18 in addition to the film width difference after relaxation in horizontal stretching ratio, transverse direction in embodiment 18 Sample manufactures, and obtains film.The characteristic of obtained film is shown in table 10 below~16.

The smears composition of the coating layer used in above-described embodiment and comparative example is shown in table 2 below.

In the polyester used in above-described embodiment and comparative example, top layer, the raw material in intermediate layer coordinate such as Table 3 below~9 It is shown.

The characteristic of the film obtained in above-described embodiment and comparative example is shown in table 10 below~16.

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

[table 13]

[table 14]

[table 15]

[table 16]

Claims (4)

1. A kind of 1. metal film stack film, it is characterised in that：

   At least there is coating layer in a polyester film face, the coating layer relative to nonvolatile component by containing 70 weight % to submit The coating fluid of connection agent is formed,

   The metal film stack film meets following formula (1),

   | SMD-STD |≤0.4 ... (1)

   In above-mentioned formula, SMD represents the shrinking percentage of film moving direction (MD), and unit %, STD represent orthogonal with film moving direction The shrinking percentage in direction (TD), unit %, heating condition are 150 DEG C, 90 minutes.
2. 2. metal film stack film as claimed in claim 1, it is characterised in that：

   Polyester film be containing average grain diameter be 0.1~0.6 μm it is particle, including at least 3 layers of multilayer polester films, meet at the same time Following formula (2) and (3),

   0 ＜ Ti≤20 ... (2)

   0≤P≤300…(3)

   In above-mentioned formula, Ti represents the titanium elements amount in multilayer polester film, and unit ppm, P represent P elements amount, unit ppm.
3. 3. metal film stack film as claimed in claim 1 or 2, it is characterised in that：

   Metal layer is patterned layer.
4. 4. such as metal film stack film according to any one of claims 1 to 3, it is characterised in that：

   Metal layer includes copper.