JP2017124623A - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film that has a good transportability, fabricability and transparency.SOLUTION: There is provided a laminated film in which an A layer and a B layer having different contact angles from each other are laminated on both sides of a base material respectively, and in which the contact angle of the A layer surface with water is 55 to 85 degrees, the contact angle of the B layer surface is 85 to 120 degrees, and in which the contact angle of the A layer surface after carrying out the blocking test by laminating such that the A layer surface and the B layer surface are brought into contact with each other is 55 to 90 degrees and the SRz (10 point average surface roughness) of the A layer and the B layer surface is 250 nm or less.SELECTED DRAWING: None

Description

The present invention relates to a laminated film having good transportability, processability, and transparency.

Laminated films are magnetic tapes, ferromagnetic thin film tapes, photographic films, packaging films, films for electronic components, electrical insulation films, films for metal laminates, films to be attached to the surface of glass displays, protective films for various members, etc. It is widely used as a support for a dry film resist (DFR) and a material for a release film when manufacturing a multilayer ceramic capacitor (MLCC; Multi Layered Ceramics Condenser). One of them is the display member application. Conventionally, a glass substrate has been used for an image display device represented by a display. In recent years, there has been a demand for image display devices that are thinner, lighter, and larger in screen size, and polymer film substrates have been studied instead of heavy and fragile glass substrates. Various thermoplastic resins including polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, and polycarbonate have been studied as polymer film substrates. Since various image display devices require high barrier properties, studies have been made to increase the adhesion between the polymer film substrate and the barrier layer (see, for example, Patent Document 1). On the other hand, a method of adding particles in order to improve transportability has been proposed (for example, see Patent Document 2).

JP 2014-146582 A JP 2008-212837 A

However, in the method described in Patent Document 1, there is a problem that if the adhesion between the polymer film and the barrier layer is increased, the transportability and the handling property of post-processing are deteriorated. In addition, the method described in Patent Document 2 has problems in that process contamination due to dropping off of particles, poor adhesion with a barrier layer, and functional deterioration due to high haze are caused. An object of the present invention is to provide a laminated film which solves such problems, has no process contamination due to particle dropping, has both transportability and smoothness, and is excellent in permeability and adhesion to a barrier layer.

The above-described problem is that a layer (A layer) having a contact angle with water of 55 to 85 degrees is laminated on one side of the substrate layer, and a contact angle with water is 85 to 120 degrees on the other side of the substrate layer. Layer (B layer) in which the SRz (10-point average surface roughness) on the surface of the A layer and the SRz (10-point average surface roughness) on the surface of the B layer are both 250 nm or less. Yes, it can be achieved by a laminated film having a contact angle of 55 to 90 degrees with water on the surface of the A layer after the blocking test between the surface of the A layer and the surface of the B layer.

The laminated film of the present invention is free from process contamination due to particle dropping, has both transportability and smoothness, and has improved permeability and adhesion with the barrier layer, so that it can be used for display members, printed wiring boards, semiconductor packages, flexible It can be suitably used as a support for a dry film resist used for forming a circuit such as a substrate.

Hereinafter, the present invention will be described in detail with specific examples.
The laminated film of the present invention is a laminated film in which an A layer is laminated on one side of a base material layer and a B layer is laminated on the other side. In the present invention, the base layer of the laminated film is a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polyolefin film such as polyethylene or polypropylene, a polyether sulfone (PES), a polystyrene film, a polyamide film, a poly A vinyl chloride film, a polycarbonate film, a polyacrylonitrile film, a polyimide film, or the like is used. A polyester film is preferred because it is excellent in mechanical properties, heat resistance, dimensional stability, chemical resistance, cost performance and the like.
The polyester in the present invention has a dicarboxylic acid component and a diol component. In addition, in this specification, a structural component shows the minimum unit which can be obtained by hydrolyzing polyester.

  Examples of the dicarboxylic acid component constituting the polyester include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalon. Aliphatic dicarboxylic acids such as acid, ethylmalonic acid and the like, adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene Dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 5-sodiumsulfoisophthalate Acid, fe Toluene boys carboxylic acid, anthracene dicarboxylic acid, phenanthrene carboxylic acid, 9,9'-bis (4-carboxyphenyl) dicarboxylic acids such as fluorene acids and aromatic dicarboxylic acids, or include an ester derivative thereof.

  Examples of the diol component constituting the polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Aliphatic diols such as cyclohexanedimethanol, spiroglycol, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9′-bis (4-hydroxy Phenyl) fluorene, diols such as aromatic diols, and those in which a plurality of the above diols are linked.

  In the present invention, polyethylene terephthalate and / or polyethylene naphthalate is preferably used as the polyester used for the base material layer. More preferably, polyethylene terephthalate is preferable from the viewpoint of applicability such as thickness unevenness.

  The thickness of the base material of the laminated film of the present invention is preferably 5 μm to 50 μm. More preferably, it is 10 μm to 35 μm. When it is less than 5 μm, the gas barrier film may have poor transportability and productivity. On the other hand, if the thickness exceeds 50 μm, it is difficult not only to make the display thinner, but it may be difficult to incorporate it into a display as a film for a display member, and productivity may be reduced.

  The laminated film of the present invention has a contact angle of 55 to 85 degrees with water of layer A laminated on one side of the base material layer, and water of layer B laminated on the other side of the base material layer. Need to be a layer having a contact angle of 85 to 120 degrees.

Generally, in a manufacturing process, a film is wound and wound on a film roll after being conveyed and processed by various rolls. For this reason, when the film is wound on a film roll, the film is wound so that one surface of the film overlaps the other surface. Processing here refers to a process of coating various adhesive layers, anchor coats, overcoats, hard coats, etc. on at least one side of the laminated film, a process of laminating various layers by vapor deposition, the laminated film of the present application, It is a process of laminating a laminated film after processing, another film, a resin base material and the like by lamination. As a result of intensive studies by the present inventors, in the conventional technique such as Patent Document 1, when the adhesion with the barrier layer is increased, the problem that the transportability and the processing handleability are deteriorated is that the film roll is unwound. Furthermore, it has been clarified that the influence of the film surface on the side having improved adhesion to the barrier layer is caused by the influence on the other film surface. And the present inventors set the contact angle with the water of the A layer laminated on one side of the base material layer to 55 to 85 degrees, and the water of the B layer laminated on the other side of the base material layer. It was clarified that the above problem can be solved by using a layer having a contact angle of 85 to 120 degrees.
This will be described in detail below.

  In the laminated film of the present invention, it is necessary that the contact angle with water of the A layer laminated on one side of the base material layer is 55 to 85 degrees. If the contact angle of the A layer with water is less than 55 degrees, the slipperiness with the transport roll cannot be sufficiently obtained during processing, and transportability is deteriorated. If it exceeds 85 degrees, the adhesion with the barrier layer is deteriorated during processing. The contact angle with water on the surface of the A layer can be controlled by using a coating formulation described later. The contact angle of the A layer with water is more preferably 58 to 80 degrees. The thickness of the A layer is preferably 30 nm or more and 300 nm or less. If the thickness of the A layer is less than 30 nm, the adhesiveness with the barrier layer and the transportability may be deteriorated. If it exceeds 300 nm, the A layer may fall off during roll running during processing, haze may increase, or a sufficient function may not be obtained. The A layer in the present invention has a property of improving adhesion with the gas barrier layer when the laminated film of the present invention is used as a gas barrier film. The component constituting the A layer is not particularly limited as long as it has adhesiveness to the substrate. For example, polyester, polycarbonate, epoxy resin, alkyd resin, acrylic resin, urea resin, urethane resin and the like are preferably used. be able to. Further, two or more different resins, for example, polyester and urethane resin, polyester and acrylic resin, or urethane resin and acrylic resin may be used in combination. Polyester, acrylic resin, and urethane resin are preferable, and polyester is particularly preferable. In the A layer according to the present invention, when various crosslinking agents are used in combination with the above-described resin, durability can be drastically improved, which is a preferable embodiment. When a crosslinkable functional group is copolymerized with a polyester resin, a urethane resin, or an acrylic resin as the resin used for the A layer, it is particularly preferable to use a crosslinking agent in combination. The crosslinking agent is preferably an oxazoline resin, a melamine resin, an epoxy resin, a carbodiimide resin, or an isocyanate resin. More preferred is an oxazoline resin. The preferred oxazoline resin component refers to a component comprising a resin having an oxazoline group structure in the molecule and a resin obtained by reacting the resin with other components. Specifically, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, bisoxazolines (low molecular oxazoline group-containing compounds) such as 2,2′-bis (2-oxazoline), polyolefins And a polymer type oxazoline group-containing compound such as those in which an oxazoline group is introduced by modifying oxazoline as a skeleton structure, and those in which an oxazoline group is introduced with a skeleton structure as polystyrene. By including the oxazoline resin component in the easy-adhesion layer, the terminal carboxyl group of the polyester film and the oxazoline group react to increase the adhesion. The crosslinking agent can be used by mixing at an arbitrary ratio, but the crosslinking agent is preferably added in an amount of 10 to 40 parts by weight with respect to 100 parts by weight of the base resin of the A layer, and more preferably. 20 to 35 parts by weight are added. When the addition amount of the crosslinking agent is less than 10 parts by weight, the durability improving effect may be reduced, and when it exceeds 40 parts by weight, the adhesion may be low and the durability may be deteriorated. In the A layer according to the present invention, particles may be added. The particle diameter of the added particles is preferably 30 to 500 nm. More preferably, it is 50 nm-400 nm. The addition amount is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the base resin of the A layer.

  In the laminated film of the present invention, it is necessary that the B layer having a contact angle with water of 85 to 120 degrees is laminated on the other side of the base material layer. When the contact angle of the B layer with water is less than 85 degrees, when unrolling from the roll film, the peelability from the surface of the A layer is not sufficient, and the transportability deteriorates. If it exceeds 120 degrees, when the laminated film is stored in a roll, the composition of the B layer moves to the A layer and causes the contact angle with water on the surface of the A layer to increase. For example, when processed into a gas barrier film, Adhesion decreases. The contact angle of the B layer with water is more preferably 90 to 110 degrees. In addition, a contact angle with the water of the B layer surface can be controlled by setting it as the coating agent prescription mentioned later. The thickness of the B layer is preferably 10 nm or more and 300 nm or less. If the thickness of the B layer is less than 10 nm, the transportability may be deteriorated or the B layer may be detached during roll running during processing. If it exceeds 300 nm, haze may increase or the B layer may be detached during roll running during processing, and a sufficient function may not be obtained.

  The laminated film of the present invention needs to have a contact angle of 55 to 90 degrees on the surface of the A layer after performing a blocking test by laminating so that the surface of the A layer and the surface of the B layer are in contact with each other under the following conditions. The blocking test in the present application can be used as an index for confirming the presence or absence of the transfer of the B layer component to the A layer or the blocking of the A layer component to the B layer when the laminated film is stored in a roll state. . The blocking test was performed using a C-type heatable 60t press machine (manufactured by Gonno Hydraulic Machinery Co., Ltd.), with a load of 150 kgf, a temperature of 50 degrees, and a time of 5 hours. And pressed. If the contact angle with water on the surface of the layer A after the blocking test is less than 55 degrees, it may cause deterioration in workability and transportability. Also, when the contact angle with water on the surface of the A layer after the blocking test exceeds 90 degrees, the B layer affected the A layer (the composition of the B layer was transferred to the A layer). When the film is unwound from the film roll wound up to process the film, workability deteriorates. The contact angle with water on the surface of the A layer after the blocking test can be controlled by adjusting the coating agent applied to the A layer and the B layer to a coating agent described later.

  The B layer in the present invention has characteristics that are smooth, highly transparent, and improve transportability. The resin component (hereinafter referred to as base resin) constituting the base of the B layer is not particularly limited as long as it has adhesiveness to the base material. For example, polyester, polycarbonate, epoxy resin, alkyd resin, acrylic resin, urea Resin, urethane resin, etc. can be used suitably. Polyester, acrylic resin, and urethane resin are preferable, and acrylic resin is particularly preferable. Further, two or more different resins, for example, polyester and urethane resin, polyester and acrylic resin, or urethane resin and acrylic resin may be used in combination.

  In addition, it is preferable to add an additive such as a long-chain alkyl compound, a wax, a fluorine compound, or a silicone compound to the B layer because both transportability and smoothness can be achieved. Among these, a long-chain alkyl compound is more preferable from the viewpoint of good adhesion and low contamination.

  The long-chain alkyl compound is a compound having a linear or branched alkyl group having 6 or more, particularly preferably 8 or more carbon atoms. Specific examples include, but are not limited to, long-chain alkyl group-containing polyvinyl resins, long-chain alkyl group-containing acrylic resins, long-chain alkyl group-containing polyester resins, long-chain alkyl group-containing amine compounds, long-chain alkyl groups. And an ether compound, a long-chain alkyl group-containing quaternary ammonium salt, and the like.

  The wax is a wax selected from natural waxes, synthetic waxes, and blended waxes thereof. Natural waxes are plant waxes, animal waxes, mineral waxes, and petroleum waxes. Examples of plant waxes include candelilla wax, carnauba wax, rice wax, wood wax, and jojoba oil. Animal waxes include beeswax, lanolin, and whale wax. Examples of the mineral wax include montan wax, ozokerite, and ceresin. Examples of petroleum wax include paraffin wax, microcrystalline wax, and petrolatum. Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters, and ketones. As synthetic hydrocarbons, Fischer-Tropsch wax (also known as Sazoir wax) and polyethylene wax are famous, but in addition to this, low molecular weight polymers (specifically, polymers having a viscosity number average molecular weight of 500 to 20000) Some of the following polymers are also included. That is, there are polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, polyethylene glycol and polypropylene glycol block or graft conjugate. Examples of the modified wax include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives. The derivative herein is a compound obtained by any of purification, oxidation, esterification, saponification treatment, or a combination thereof. Hydrogenated waxes include hardened castor oil and hardened castor oil derivatives.

The silicone compound is a compound having a silicone structure in the molecule, and examples thereof include silicone emulsion, acrylic graft silicone, silicone graft acrylic, amino-modified silicone, perfluoroalkyl-modified silicone, and alkyl-modified silicone. In view of heat resistance and contamination, it is preferable to contain a curable silicone resin.
As the type of the curable silicone resin, any of the curing reaction types such as an addition type, a condensation type, an ultraviolet curable type, and an electron beam curable type can be used.

  The additive is preferably added in an amount of 5 to 70 parts by weight with respect to 100 parts by weight of the base resin of the B layer from the viewpoint of improving transportability, and more preferably 20 to 60 parts by weight. When the addition amount of the crosslinking agent is less than 5 parts by weight, the effect of improving the transportability may be reduced, and when it exceeds 70 parts by weight, the transparency is low or the surface roughness is increased and the transportability is increased. It may get worse. These release agents may be used alone or in combination.

  Moreover, it is preferable to add a crosslinking agent as a component which comprises B layer. The durability can be drastically improved by using various crosslinking agents in combination with the aforementioned resin. The crosslinking agent is preferably an oxazoline resin, a melamine resin, an epoxy resin, a carbodiimide resin, or an isocyanate resin. From the viewpoint of controlling the compatibility with the long-chain alkyl compound and the contact angle to an appropriate range, melamine resin, carbodiimide resin, and isocyanate resin are more preferable, and more preferable for controlling the contact angle to an appropriate range. Is a melamine resin. The crosslinking agent can be used by mixing at an arbitrary ratio, but the crosslinking agent is preferably added in an amount of 50 to 150 parts by weight with respect to 100 parts by weight of the base resin of the B layer, more preferably 80 to 120 parts by weight is added. When the added amount of the crosslinking agent is less than 50 parts by weight, blocking with the A layer may occur and sufficient barrier performance may not be obtained. On the other hand, when it exceeds 150 parts by weight, the adhesion with the substrate is low and the barrier performance may be deteriorated.

  In the laminated film of the present invention, SRz (10-point average surface roughness) on the surface of the A layer and the B layer needs to be 250 nm or less. If SRz (10-point average surface roughness) on the surface of either the A layer or the B layer exceeds 250 nm, the surface protrusions will be caught, causing the coating material to be scraped or dropped off. In addition, when processed as a gas barrier film, sufficient adhesion may not be obtained and defects may increase. More preferably, it is 200 nm or less. The method for controlling SRz (10-point average surface roughness) of the A layer and B layer surfaces of the laminated film is not particularly limited. For example, the content of particles contained in the base material or coating material of the laminated film, It can be adjusted by the particle size. When the content of particles contained in the base material or coating material of the laminated film increases, the SRz tends to increase as the particle size increases. In order to reduce SRz, it is preferable that the substrate does not contain particles. Also, from the viewpoint of transparency, it is preferable that the substrate does not contain particles. In addition, if the coating is applied to the A layer and the B layer, if the particles are contained, haze may be deteriorated, or process deterioration due to particle dropping or functional deterioration may occur due to shaving or dropping of the coating. is there. In particular, it is preferable that the coating agent applied to the A layer and the B layer is adjusted to the coating agent described later.

  In the laminated film of the present invention, the difference in contact angle between the surface of the layer A and the surface of the layer B after the blocking test is preferably 20 to 60 degrees. More preferably, it is 22-50 degrees, More preferably, it is 25-45 degrees. If it is less than 20 degrees, the adhesion between the surface of the A layer and the surface of the B layer is increased, blocking occurs, the transportability is deteriorated, and sufficient performance may not be obtained after processing. If it exceeds 60 degrees, the composition of the B layer may have moved to the A layer, and the adhesion of the A layer may be reduced during processing, and the transportability may deteriorate.

  In the laminated film of the present invention, the friction coefficient μd on the surface of the A layer and the surface of the B layer is preferably 0.35 or less. More preferably, it is 0.3 or less. More preferably, it is 0.25 or less. The friction coefficient μd is preferably as low as possible. However, if it is too low, it is liable to cause winding slippage in the production process and the productivity may be deteriorated. If the friction coefficient μd on either the surface of the A layer or the surface of the B layer is larger than 0.35, the slipperiness is not sufficient, so that wrinkles or wrapping may occur at the time of conveyance, and productivity may deteriorate. The coefficient of friction μd can be controlled by adjusting the coating applied to the A layer and the B layer to the coating described later.

  The laminated film of the present invention preferably has a haze of 3% or less. More preferably, it is 0 to 2%. If it exceeds 3%, the image quality may be deteriorated when a gas barrier film for display is used. The haze can be controlled by adjusting the raw material to be the base material of the film and the coating agent applied to the A layer and the B layer to the coating agent described later.

  Next, the manufacturing method of the laminated | multilayer film of this invention is demonstrated. This is an example, and the present invention should not be construed as being limited to the product obtained by such an example.

  First, polyester will be described as an example of the base material of the laminated film of the present invention. The polyester resin used as a raw material can be obtained by subjecting a dicarboxylic acid or its ester derivative and a diol to a transesterification or esterification reaction by a well-known method. Examples of conventionally known reaction catalysts include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and phosphorus compounds. Preferably, an alkali metal compound, a manganese compound, an antimony compound or a germanium compound, or a titanium compound is preferably added as a polymerization catalyst at any stage before the normal production method is completed, and the moisture and heat resistance of the laminated film substrate is improved. It is more preferable to add a sodium compound and a manganese compound from the viewpoint of enhancing the above. As such a method, for example, when a manganese compound is taken as an example, it is preferable to add the manganese compound powder as it is.

    Moreover, the terminal carboxyl group amount of the polyester resin is heated at a polymerization temperature or after polymerization of the polyester resin at a temperature of 190 ° C. to less than the melting point of the polyester resin under reduced pressure or a flow of an inert gas such as nitrogen gas. It can be controlled by the so-called solid phase polymerization time. Specifically, the amount of terminal carboxyl groups increases as the polymerization temperature increases, and the amount of terminal carboxyl groups decreases as the time of solid phase polymerization increases.

    As a method for producing a laminated film substrate, a method (melt casting method) in which a polyester resin raw material is heated and melted in an extruder and extruded from a die onto a cast drum cooled to be processed into a sheet shape can be used. At this time, in order to remove the unmelted material in the polymer, the polymer may be filtered with a fiber sintered stainless metal filter. Furthermore, various additives such as compatibilizers, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, conductive agents, ultraviolet absorbers, as long as the effects of the present invention are not impaired. An agent, a flame retardant, a flame retardant aid and the like may be added. As another method, the raw material is dissolved in a solvent, and the solution is extruded from a die onto a support such as a cast drum or an endless belt to form a film, and then the solvent is dried and removed from the film layer to form a sheet. A method (solution casting method) or the like can also be used. In addition, the manufacturing method in the case where the base material of the laminated film has a laminated structure is such that when the material of each layer to be laminated is mainly composed of a thermoplastic resin, two different thermoplastic resins are put into two extruders and melted. Preferably, a method (coextrusion method) of co-extrusion onto a cast drum cooled from the die and processed into a sheet shape can be preferably used.

  Raw material is charged into an extruder (multiple extruders in the case of a laminated structure), melted, extruded from a die (coextrusion in the case of a laminated structure), and cooled to a surface temperature of 10 to 60 ° C. Above, it cools and solidifies by static electricity to produce an unstretched sheet. Next, this unstretched sheet is led to a group of rolls heated to a temperature of 70 to 140 ° C., and stretched 3 to 4 times in the longitudinal direction (longitudinal direction, that is, the traveling direction of the sheet). Cool with rolls. Subsequently, the both ends of the sheet are guided to a tenter while being gripped by clips, and are stretched 3 to 4 times in a direction (width direction) perpendicular to the longitudinal direction in an atmosphere heated to a temperature of 80 to 150 ° C. The stretching ratio is 3 to 5 times in each of the longitudinal direction and the width direction, and the area ratio (longitudinal stretching ratio x lateral stretching ratio) is preferably 9 to 15 times. When the area magnification is less than 9 times, the durability of the resulting biaxially stretched sheet is insufficient, and conversely when the area magnification exceeds 15 times, there is a tendency that tearing tends to occur during stretching. As the biaxial stretching method, in addition to the sequential biaxial stretching method in which the stretching in the longitudinal direction and the width direction is separated as described above, simultaneous biaxial stretching in which stretching in the longitudinal direction and the width direction is simultaneously performed. Either method can be used.

  As a method for preparing a coating composition for forming the A layer and the B layer in the laminated film of the present invention, first, as a dispersion solvent, for example, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone , Tetrahydrofuran, dimethylformamide, dimethylacetamide, methanol, ethanol, water and the like, and any of emulsion type and dissolution type may be used. In recent years, emphasis has been placed on environmental protection, resource saving, exhaust problems of organic solvents at the time of production, etc., and a dissolved type or an emulsion type with water as the main solvent is a preferred form. The method for emulsifying the resin component contained in the easy-adhesion layer in water for preparing the coating composition is not particularly limited, and is widely known to those skilled in the art as a solid / liquid stirring device or an emulsifier. It can be produced by a device that is used.

  Moreover, after preparing the coating composition for forming A layer and B layer, it is preferable to store in the room temperature environment of 5 degreeC or more and 35 degrees C or less as an environment to store. The storage period from adjustment to application is preferably within one week. When the storage environment of the coating composition does not satisfy the above conditions, the stability of the dispersed resin component is impaired, and an easy-adhesion layer having desired characteristics may not be obtained.

  Next, the method for forming the A layer and the B layer is not particularly limited, but a coating method is preferably used. As a coating method, a known method can be applied, and for example, a roll coating method, a dip coating method, a bar coating method, a die coating method, a gravure roll coating method, or a combination of these methods can be used. it can. Among them, the bar coating method is preferable from the viewpoint of a wide selection range of coating materials, while the die coating method and the gravure roll coating method can be preferably selected from the viewpoint of thick film coating property when it is desired to increase the thickness of the A layer and the B layer. .

  Furthermore, the formation of the A layer and the B layer is more preferably performed by in-line coating provided in the production process of the laminated film base material from the viewpoint of process simplification and cost reduction. Specifically, in the case of the sequential biaxial stretching method, after forming an unstretched sheet or a uniaxially stretched sheet, in the case of the simultaneous biaxial stretching method, after forming the unstretched sheet, the above coating step After applying the coating composition that forms the easy-adhesion layer, the laminated film is heat-set simultaneously with the drying step of the coating composition. At this time, the drying temperature of the coating composition is preferably 150 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C. or higher and 230 ° C. or lower, more preferably 180 ° C. or higher and 220 ° C. or lower, from the viewpoint of durability of the display laminated film. .

If necessary, from the viewpoint of improving the wettability of the coating composition to the laminated film substrate and improving the interlayer adhesion after forming the A layer and the B layer, a corona treatment is performed on the surface of the laminated film substrate immediately before the coating process. Alternatively, plasma treatment may be performed.
The laminated film of the present invention thus obtained is preferably used as a DFR support. In general, the DFR has a sandwich structure in which a photosensitive layer (photoresist layer) is sandwiched between a support made of a polyester film and a protective film (cover film) made of an LDPE film or the like. In order to produce a conductor circuit using this DFR, the following operations are generally performed.

  That is, the protective film is peeled off from the DFR and laminated with the substrate / conductive substrate layer so that the exposed surface of the resist layer and the surface of the conductive substrate layer such as copper foil on the substrate are in close contact with each other. . Next, the reticle onto which the conductor circuit pattern is baked is placed on a support made of a polyester film, and the resist layer mainly composed of a photosensitive resin is exposed to light by irradiating light. Thereafter, after the reticle and polyester film are peeled off, unreacted components in the resist layer are dissolved and removed with a solvent. Next, etching is performed with an acid or the like to dissolve and remove the exposed portion in the conductive base material layer. As a result, the photoreactive portion in the resist layer and the conductive base material layer portion corresponding to the photoreactive portion remain as they are. Thereafter, if the remaining resist layer is removed, a conductor circuit on the substrate is formed.

  Since a conductor circuit is formed by such a method, a release layer is required for the polyester film as a support, and it is preferable to form a resist layer on the B layer of the laminated film of the present invention. It is one of. When the contact angle of the B layer with water is in the range of 85 to 120 degrees, when the laminated film of the present invention is peeled off from the resist layer, the releasability with the resist layer is improved and the resist property is improved. When the contact angle of the B layer is less than 85 degrees, the releasability with the resist layer is deteriorated, and the resist property may be lowered. On the other hand, when the contact angle of the B layer exceeds 120 degrees, the adhesion with the resist layer is lowered, and it becomes difficult to form the resist layer on the B layer, so that the resist property is deteriorated.

  In addition, if SRz of the B layer is 250 nm or less, it is preferable to form a resist layer on the B layer because scratches on the resist layer can be reduced. Furthermore, if the difference in contact angle between the water on the surface of the A layer and the surface of the B layer after the blocking test is 20 to 60 degrees, the releasability between the resist layer and the B layer is good.

  Moreover, it is preferable that the contact angle of the surface of the A layer after the lamination test is performed so that the surface of the A layer and the surface of the B layer are in contact with each other under the above conditions is 55 degrees or more and 90 degrees or less. When the contact angle is less than 55 degrees, the transportability of the film is deteriorated and the resist property may be inferior. Also, when the contact angle with water on the surface of the A layer after the blocking test exceeds 90 degrees, the B layer affected the A layer (the composition of the B layer was transferred to the A layer). When the film is unwound from the film roll wound up to process the film, the resist property may deteriorate.

[Measurement and evaluation method of characteristics]
(1) Contact angle with water (degrees)
Measurement was performed according to JIS R 3257 (1999) using a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.). The laminated film is left in an atmosphere of room temperature 23 ° C. and relative humidity 60% for 24 hours. Thereafter, 5 contact angles of pure water were measured with respect to the measurement surface under the same atmosphere, and an average value of 3 points excluding the maximum value and the minimum value of the 5 measured values was defined as the contact angle.

(2) Blocking property (peelability after blocking test)
Cut the laminated film into 5cm squares. The laminated film was laminated so that the surface of the A layer and the surface of the B layer were in contact with each other, and a 150 kgf load was processed at 50 ° C. for 5 hours using a C-type 60t press machine (manufactured by Gonno Hydraulic Machine Works). The blocking property was evaluated according to the following criteria for the resistance when the sample after being processed by stacking two laminated films was peeled off with tweezers.
A: There is almost no resistance at the time of peeling, and there is no delamination in the peeled laminated film.
B: Although there is resistance at the time of peeling, there is no delamination in the peeled laminated film.
C: Delamination of the A layer and the B layer occurs in at least one of the peeled laminated films.
D: Delamination between the A layer and the B layer occurs in at least one of the peeled laminated films, and at least one of the peeled laminated films curls.

(3) Contact angle with water after blocking test (degrees)
Cut the laminated film into 5cm squares. The laminated film was laminated so that the surface of the A layer and the surface of the B layer were in contact with each other, and a 150 kgf load was processed at 50 ° C. for 5 hours using a C-type 60t press machine (manufactured by Gonno Hydraulic Machine Works). The contact angle (degree) with water was measured for the laminated film after the treatment by the method of “(1) Contact angle with water”.

(4) SRz (10-point average surface roughness) (nm)
The surface morphology of the polyester film was measured under the following conditions in accordance with JIS-B0601 (1994) using a high-definition fine shape measuring instrument (three-dimensional surface roughness meter) of the stylus method.
・ Measuring device: 3D fine shape measuring instrument (model ET-4000A), manufactured by Kosaka Laboratory Ltd./Analyzing equipment: 3D surface roughness analysis system (model TDA-31)
-Stylus: Tip radius 0.2 μm R, made of diamond-Needle pressure: 50 μN
・ Measurement direction: film longitudinal direction and film width direction average after each measurement ・ X measurement length: 380 μm
-X feed speed: 0.1 mm / s (measurement speed)
・ Y measurement length: 280μm
・ Y feed pitch: 5μm (measurement interval)
・ Z magnification: 100,000 (vertical magnification)
・ Low frequency cut-off: 0.08mm (swell cut-off value)
・ High frequency cutoff: None (Roughness cutoff value)
-Filter method: Gaussian line type-Leveling: Available (tilt correction).

(5) Transportability (friction coefficient μd)
Using a slip tester manufactured by Toyo Seiki Co., Ltd., according to JIS K 7125 (1999), the values when the A layer and the B layer of two laminated films were rubbed and rubbed were measured three times. The longitudinal friction coefficient μd was determined from the average value. The friction coefficient μd was evaluated according to the following criteria as an index of transportability.
A: 0.25 or less B: 0.35 or less and exceeding 0.25 C: exceeding 0.35

(6) Transparency (Haze (%))
Using a turbidimeter “NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd., it was measured three times according to JIS K 7136 (2000), and the average value was taken as the haze value. The haze was evaluated according to the following criteria as an index of transparency.
A: 0 to 2% or less B: Over 2% to 3% or less C: Over 3%.

(7) Film thickness (μm)
The film thickness was measured at any five locations using a dial gauge in accordance with JIS K7130 (1992) A-2 method with 10 films stacked. The average value was divided by 10 to obtain the film thickness.

(8) Adhesive Acrylic polyol and triidyl isocyanate are added so that the NCO group is equivalent to the OH group of the acrylic polyol, and diluted with ethyl acetate so that the total solid content is 5 w%. Add β- (3,4 epoxycyclohexyl) trimethoxysilane to 5% by weight of the total solid content, mix, and add zirconia sol (methanol solvent dispersion, average particle size 30 nm) as a refractive index adjuster to the total solid content. 15 wt% was added to obtain an anchor coat solution. This was applied to the laminated film using a gravure coating method so that the film thickness after drying was 0.1 μm to obtain an anchor coat layer. A vapor deposition material made of a silicon oxide material (manufactured by High-Purity Chemical Laboratory Co., Ltd.) is heated on the anchor coat layer surface by an electron beam heating method so that the film formation pressure is 1.1 × 10 ⁻² Pa and the film thickness is 20 nm. An evaporated thin film layer was formed on the substrate. Next, 89.6 g of hydrochloric acid (0.1N) was added to 10.4 g of tetraethoxysilane on the vapor-deposited thin film layer, and a hydrolyzed solution having a solid content of 3 wt% (converted to SiO ₂ ) was stirred for 30 minutes for hydrolysis. And a 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol {water: isopropyl alcohol = 90: 10 (weight ratio)} in a gravure coating method so that the film thickness after drying becomes 0.3 μm A gas barrier layer was produced on the laminated film to obtain a gas barrier laminated film.
Using the water vapor permeability measuring device (model name: DELTAPERRM (registered trademark)) manufactured by Technolox Co., Ltd., the produced gas barrier laminated film was subjected to water vapor permeability under the conditions of a temperature of 40 ° C., a humidity of 90% RH, and a measurement area of 50 cm ^2. It was measured. Ten points were measured 10 times for each point, the average value at that point was determined, and the value was taken as the water vapor permeability (g / (m ² · 24 hr · atm)). When the adhesion between the gas barrier layer and the laminated film is good, the barrier property is high and the water vapor permeability is small. Further, if the adhesion between the gas barrier layer and the laminated film is poor, the barrier property is insufficient and the water vapor permeability is increased. The water vapor permeability was evaluated according to the following criteria as an adhesion index.
A (good adhesion): water vapor permeability is 1.0 × 10 ⁻³ (g / (m ² · 24 hr · atm)) or less B (adhesion is possible): water vapor permeability is 1.0 × 10 ⁻³ ( g / (m ² · 24 hr · atm)) to 10.0 × 10 ⁻³ (g / (m ² · 24 hr · atm)) or less C (adhesion not possible): water vapor permeability is 10.0 × 10 ⁻³ (g / (m ² · 24 hr · atm)) is exceeded.

(9) Evaluation of resist properties: a. To c. The method is used for evaluation.
a. A negative resist “PMERN-HC600” manufactured by Tokyo Ohka Co., Ltd. is applied onto a 6-inch Si wafer that has been mirror-polished on one side, and is rotated with a large spinner to form a resist layer having a thickness of 7 μm. Next, pre-heat treatment is performed for about 20 minutes under a temperature condition of 70 ° C. using a ventilation oven with nitrogen circulation.
b. The layer B of the laminated film of the present invention is laminated so as to be in contact with the resist layer, a polyester film is laminated on the resist layer using a rubber roller, and a reticle patterned with chromium metal is placed thereon. Then, exposure is performed from above the reticle using an I-line (ultraviolet light having a peak at a wavelength of 365 nm) stepper.
c. After peeling the laminated film from the resist layer, the resist layer is put in a container containing a developer “PMER N-A5” manufactured by Tokyo Ohka Kogyo Co., Ltd. and developed for about 1 minute. Thereafter, the developer is taken out and washed with water for about 1 minute. Thirty states of L / S (μm) (Line and Space) = 10/10 μm of the resist pattern created after development were observed at a magnification of about 800 to 3000 using a scanning electron microscope SEM. A certain number is evaluated as follows.

S: The number of missing pieces is 0 to 3 A; The number of missing pieces is 4 to 8 B; The number of missing pieces is 9 to 13 C; The number of missing pieces is 13 or more

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not necessarily limited to these.

  [Production of PET] 100 parts by mass of dimethyl terephthalate, 57.5 parts by mass of ethylene glycol, 0.03 parts by mass of magnesium acetate dihydrate and 0.03 parts by mass of antimony trioxide were melted at 150 ° C. in a nitrogen atmosphere. . While stirring this melt, the temperature was raised to 230 ° C. over 3 hours to distill methanol, and the transesterification reaction was completed. After completion of the transesterification reaction, an ethylene glycol solution (pH 5.0) in which 0.005 parts by mass of phosphoric acid was dissolved in 0.5 parts by mass of ethylene glycol was added. The intrinsic viscosity of the polyester composition at this time was less than 0.2. Thereafter, the polymerization reaction was performed at a final temperature of 285 ° C. and a degree of vacuum of 0.1 Torr to obtain polyethylene terephthalate having an intrinsic viscosity of 0.52 and a terminal carboxyl group amount of 15 equivalents / ton. The obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours. Thereafter, solid-state polymerization was performed at 220 ° C. and a vacuum degree of 0.3 Torr for 8 hours to obtain polyethylene terephthalate (PET chip-1) having an intrinsic viscosity of 0.80 and a terminal carboxyl group amount of 10 equivalents / ton. The obtained PET chip had a glass transition temperature of 82 ° C. and a melting point of 255 ° C.

Reference example 1
(Preparation of coating agent A)
76 parts by weight of a polyester resin and 24 parts by weight of an oxazoline-based cross-linking agent (“Epocross (registered trademark) WS300 manufactured by Nippon Shokubai Co., Ltd.) are mixed and stirred in water so that the solid concentration is 8 wt%. It was.

Reference example 2
(Preparation of coating agent B)
38 parts by weight of an acrylic resin, 38 parts by weight of a methylol-type melamine cross-linking agent (“Nicarac (registered trademark)” MW12LF manufactured by Sanwa Chemical Co., Ltd.), a long-chain alkyl polymer (“Resem” manufactured by Chukyo Yushi Co., Ltd.) )) Was mixed and stirred with water so that the solid content concentration was 8 wt%, and a coating material B was obtained.

Reference example 3
(Preparation of coating agent C)
30 parts by weight of an acrylic resin, 30 parts by weight of a methylol-type melamine cross-linking agent (“Nikalac (registered trademark)” MW12LF manufactured by Sanwa Chemical Co., Ltd.), a long-chain alkyl polymer (“Rezem manufactured by Chukyo Yushi Co., Ltd.) )) Was mixed and stirred with water so that the solid concentration was 8 wt%, and coating material C was obtained.

Reference example 4
(Preparation of coating agent D)
44 parts by weight of acrylic resin, 44 parts by weight of methylol-type melamine cross-linking agent (“NIKALAC (registered trademark)” MW12LF manufactured by Sanwa Chemical Co., Ltd.), long-chain alkyl polymer compound (“RESEM manufactured by Chukyo Yushi Co., Ltd.) )) Was mixed and stirred with water so that the solid concentration was 8 wt%.

Reference Example 5
(Preparation of coating E)
38 parts by weight of acrylic resin, 38 parts by weight of methylol type melamine cross-linking agent (“Nikarak (registered trademark)” MW12LF manufactured by Sanwa Chemical Co., Ltd.), fluororesin (“Megafuck (registered trademark)” manufactured by DIC Corporation) F-477) was mixed and stirred with water so that the solid content concentration was 8 wt%, and a coating material E was obtained.

Reference Example 6
(Preparation of coating agent F)
38 parts by weight of acrylic resin, 38 parts by weight of methylol type melamine cross-linking agent (“Nikarak (registered trademark)” MW12LF manufactured by Sanwa Chemical Co., Ltd.), silicone resin (“KM9738-A” manufactured by Shin-Etsu Chemical Co., Ltd.) A coating agent F was prepared by mixing and stirring with water so that the solid content concentration was 24 wt parts.

Reference Example 7
(Preparation of coating agent G)
76 parts by weight of a polyester resin, 23 parts by weight of an oxazoline-based crosslinking agent (“Epocross (registered trademark) WS300 manufactured by Nippon Shokubai Co., Ltd.), 0.8 parts by weight of silica particles having a particle diameter of 150 nm, and silica having a particle diameter of 300 nm A coating agent G was prepared by mixing and stirring 0.2 parts by weight of the particles with water so that the solid concentration was 8 wt%.

Reference Example 8
(Preparation of coating H)
66 parts by weight of acrylic resin, 10 parts by weight of methylol-type melamine cross-linking agent (“Nikalac (registered trademark)” MW12LF manufactured by Sanwa Chemical Co., Ltd.), long-chain alkyl polymer compound (“Rezem manufactured by Chukyo Yushi Co., Ltd.) )) Was mixed and stirred with water so that the solid content concentration was 8 wt%, and a coating material H was obtained.

Reference Example 9
(Preparation of coating agent I)
80 parts by weight of a polyester resin and 20 parts by weight of a methylol-type melamine cross-linking agent (“NIKALAC (registered trademark)” MW12LF manufactured by Sanwa Chemical Co., Ltd.) are mixed and stirred in water so that the solid content concentration is 8 wt%. Agent I was designated.

Example 1
The PET chip was dried under reduced pressure at 180 ° C. for 3 hours. Using a cast electric heater and a water cooling jacket for temperature control, the cylinder was heated to 282 ° C. and supplied to an extruder E and introduced into a T die die.

  Next, from the inside of the T die die, the melt of PET chips is extruded into a sheet to form a molten single layer sheet, which is cooled and solidified while applying an electrostatic charge to a cast drum having a surface temperature of 25 ° C. to produce an unstretched film did. Subsequently, after the obtained unstretched film was preheated with a heated roll group, the tension was cut using a silicone-made stretching roll and a nip roll, and 3.5 times MD stretching was performed at a temperature of 90 ° C. in the longitudinal direction. Then, it was cooled with a roll group having a temperature of 25 ° C. to obtain a uniaxially stretched film. Next, the uniaxially stretched sheet was subjected to corona treatment. Next, the coating A of (Reference Example 1) is applied to the A layer, and the coating B of (Reference Example 2) is applied to the B layer on both sides with a Meyer bar, and then the both ends of the film are cooled to 60 ° C. or less. While gripping, the film was guided to a preheating zone at a temperature of 80 ° C. in the tenter, and continuously stretched by 4.0 times in the width direction (TD direction) perpendicular to the longitudinal direction in a heating zone at a temperature of 90 ° C. Subsequently, a heat treatment was performed at a temperature of 232 ° C. for 5 seconds in a heat treatment zone in the tenter, and a relaxation treatment was further performed in the 4% width direction at a temperature of 232 ° C. Next, the film was gradually cooled in a cooling zone and wound up to obtain a laminated film. The properties of the obtained film are shown in Table 1. It was a laminated film excellent in all of transportability, blocking property, adhesion, transparency, and resist properties.

(Example 2)
A laminated film was obtained in the same manner as in Example 1 except that the coating agent C of (Reference Example 3) was used as the coating agent for the B layer. The evaluation results of the obtained film are shown in Table 1.

(Example 3)
A laminated film was obtained in the same manner as in Example 1 except that the coating material D of (Reference Example 4) was used as the coating material for the B layer. The evaluation results of the obtained film are shown in Table 1.

Example 4
A laminated film was obtained in the same manner as in Example 1 except that the coating agent G of (Reference Example 7) was used as the coating agent for the A layer. The evaluation results of the obtained film are shown in Table 1.

(Example 5)
A laminated film was obtained in the same manner as in Example 1 except that the coating material H of (Reference Example 8) was used as the coating material for the B layer. The evaluation results of the obtained film are shown in Table 1.
Example 4
A laminated film was obtained in the same manner as in Example 1 except that the coating material I of (Reference Example 9) was used as the coating material for the A layer. The evaluation results of the obtained film are shown in Table 1.

(Comparative Example 1)
A laminated film was obtained in the same manner as in Example 1 except that the coating material G of (Reference Example 7) was used as the coating material for the A layer and the B layer. The evaluation results of the obtained film are shown in Table 1. The contact angle difference between the water of the A layer and the B layer was small, and a laminated film inferior in transportability, blocking property, adhesion, and resist properties was obtained.

(Comparative Example 2)
A laminated film was obtained in the same manner as in Example 1 except that the coating E of (Reference Example 5) was used as the coating for the B layer. The evaluation results of the obtained film are shown in Table 1. The composition of the B layer moved to the A layer, resulting in a laminated film having poor adhesion between the gas barrier layer and the A layer. Moreover, it was a film inferior to resist property.

(Comparative Example 3)
A laminated film was obtained in the same manner as in Example 1 except that the coating agent F of (Reference Example 6) was used as the coating agent for the B layer. The evaluation results of the obtained film are shown in Table 1. It became a laminated film having high haze and inferior transparency. Moreover, it was a film inferior to resist property.

(Comparative Example 4)
A laminated film was obtained in the same manner as in Example 1 except that a 20 μm polypropylene film was used as the substrate. The evaluation results of the obtained film are shown in Table 1. SRz (10-point average surface roughness) was large, resulting in a laminated film inferior in adhesion, transparency, and resist properties.

(Comparative Example 5)
A laminated film was obtained in the same manner as in Example 1 except that the coating material B of (Reference Example 2) was used as the coating material for the A layer and the B layer. The evaluation results of the obtained film are shown in Table 1. The contact angle of A layer and B layer was high, and it became a laminated film inferior to adhesiveness. Moreover, it was a film inferior to resist property.

(Comparative Example 6)
A laminated film was obtained in the same manner as in Example 1 except that the coating material H of (Reference Example 9) was used as the coating material for the B layer. The evaluation results of the obtained film are shown in Table 1. The B layer dropped off in the transporting process, or the A layer was blocked, resulting in a laminated film having poor transportability and adhesion. Moreover, it was a film inferior to resist property.

The laminated film of the present invention is suitable for use as a display member because it is free from process contamination due to particle dropping, has both transportability and smoothness, and is excellent in permeability and adhesion to the barrier layer.

Claims (9)

A layer having a contact angle with water of 55 to 85 degrees (A layer) is laminated on one side of the base material layer, and a layer having a contact angle with water of 85 to 120 degrees on the other side of the base material layer (B layer) ) Are laminated films,
SRz (10-point average surface roughness) on the surface of the A layer and SRz (10-point average surface roughness) on the surface of the B layer are both 250 nm or less, and the A layer surface and the B layer surface performed under the following conditions: A laminated film having a contact angle with water on the surface of the A layer after the blocking test of 55 to 90 degrees.
[Blocking test conditions]
Cut the laminated film into 5cm squares. The laminated film is laminated so that the surface of the A layer and the surface of the B layer are in contact with each other, and a 150 kgf load is processed at 50 ° C. for 5 hours using a C-type heatable 60 t press machine (manufactured by Gonno Hydraulic Machine Works). The laminated film according to claim 1, wherein a difference in contact angle between the water on the surface of the A layer and the surface of the B layer after the blocking test is 20 to 60 degrees. The laminated film according to claim 1 or 2, wherein both the surface of the A layer and the surface of the B layer have a friction coefficient μd of 0.35 or less. The laminated film according to any one of claims 1 to 3, wherein the haze of the laminated film is 3% or less. The laminated film according to any one of claims 1 to 4, wherein the base material layer is a layer made of polyester. The laminated film according to any one of claims 1 to 5, which is used as a base material for a gas barrier film of a member of a display. The gas barrier film for display members using the laminated | multilayer film in any one of Claims 1-6. A display using the gas barrier film according to claim 7. The laminated film according to any one of claims 1 to 5, which is used as a support for a dry film resist.