JPWO2010071009A1 - Flexible resin substrate and display device using the same - Google Patents

Abstract

An object of the present invention is to provide a flexible resin substrate having a low coefficient of linear expansion and an excellent gas barrier property while maintaining the characteristics of the flexible resin substrate such as lightness, transparency and heat resistance. A display device using the same is also provided. The flexible resin substrate of the present invention is a flexible resin substrate having a moisture-proof layer on at least one surface, and a metal element having a valence of 6 or a plurality of metal elements having an average valence of 6 in the resin, or manganese It contains the heat shrink material containing this.

Description

  The present invention relates to a flexible resin substrate and a display device using the same.

  In general, glass plates are widely used as display element substrates (particularly active matrix type) for liquid crystal display elements and organic EL display elements, color filter substrates, solar cell substrates and the like. However, in recent years, resin (plastic) materials have been studied as an alternative to glass plates because they are easily broken, cannot be bent, have a large specific gravity, and are not suitable for weight reduction.

  However, these conventional glass substitute resin (plastic) materials have a larger coefficient of linear expansion than glass plates. In particular, when used for active matrix display element substrates, problems such as warpage and disconnection of aluminum wiring occur in the manufacturing process. These are difficult to use. Accordingly, there is a demand for a resin (plastic) material having a small linear expansion coefficient while satisfying the transparency, heat resistance, etc. required for a display element substrate, particularly an active matrix display element substrate.

  Thus, in order to improve the linear expansion coefficient, means for improving the linear expansion of the resin substrate by mixing a low linear expansion material such as an inorganic filler or glass fiber in the matrix as a domain is performed (for example, Patent Document 1). ~ 5).

  However, in order to improve the linear expansion coefficient, it was necessary to add a large amount of domain. When a large amount is added, there is a problem that the resin (plastic) substrate is not light, and the flexibility (flexibility) is lowered, so that it is easily broken and brittle like glass.

  On the other hand, in the case of a glass substitute resin material, a moisture-proof layer is usually provided in order to prevent fluctuations in humidity, particularly deterioration of the resin substrate due to high humidity.

  However, in the above method, the surface becomes rough by adding a large amount of low linear expansion material such as glass fiber. If an inorganic gas barrier layer is formed directly on this rough surface, a dense film is not formed and the gas barrier property is deteriorated. Further, since a dense film cannot be formed, the gas barrier property is remarkably lowered due to easy cracking. There was a problem.

JP 2004-307845 A Japanese Patent Laid-Open No. 2005-8721 International Publication No. 03/64535 International Publication No. 05/047206 JP 2005-213084 A

  The present invention has been made in view of the above problems and situations, and the solution to the problem is that the linear expansion coefficient is small while maintaining the characteristics such as lightness, transparency and heat resistance of the flexible resin substrate. And it is providing the flexible resin substrate excellent in gas-barrier property. Another object is to provide a display device using the same.

  The above-mentioned problem according to the present invention is solved by the following means.

  1. A flexible resin substrate having a moisture-proof layer on at least one surface, and containing a heat-shrinkable material containing a metal element having a valence of 6, a plurality of metal elements having an average valence of 6, or manganese in the resin A flexible resin substrate.

  2. 2. The flexible resin substrate according to item 1, wherein the resin is thermoplastic.

  3. 3. The flexible resin substrate according to item 1 or 2, wherein the heat-shrinkable material is a complex oxide of tungstic acid.

  4). 3. The flexible resin substrate according to item 1 or 2, wherein the heat-shrinkable material is manganese nitride having a reverse perovskite crystal structure.

  5). A display device using the flexible resin substrate according to any one of the first to fourth items.

  By the above means of the present invention, there is provided a flexible resin substrate having a low coefficient of linear expansion and excellent gas barrier properties while maintaining the characteristics of the flexible resin substrate such as lightness, transparency and heat resistance. Can do. In addition, a display device using the same can be provided.

  That is, in the present invention, by using a material having a negative linear expansion coefficient as means for improving the linear expansion coefficient, the amount of low linear expansion material added can be reduced, and a resin (resin (plastic)) substrate can be reduced. It became possible to keep the characteristics of. Since it is possible to produce a flat surface roughness, a dense film is formed even when a moisture-proof layer (gas barrier layer) is formed, and it is possible to prevent a decrease in gas barrier properties. is there.

  Furthermore, it has become possible to prevent the display quality from being deteriorated during use against distortion locally applied in the manufacturing process.

Schematic flow sheet showing one embodiment of an apparatus for producing a film-like flexible resin substrate

  The flexible resin substrate of the present invention is a flexible resin substrate having a moisture-proof layer on at least one surface, and a metal element having a valence of 6 or a plurality of metal elements having an average valence of 6 in the resin, or manganese It contains the heat shrink material containing this. This feature is a technical feature common to the inventions according to claims 1 to 5.

  As an embodiment of the present invention, the resin is preferably thermoplastic from the viewpoint of the effects of the present invention. The heat shrinkable material is preferably a complex oxide of tungstic acid or a manganese nitride having a reverse perovskite crystal structure.

  The flexible resin substrate of the present invention can be suitably used for various display devices.

  Hereinafter, the present invention, its components, and the best mode and mode for carrying out the invention will be described in detail.

(Base material of flexible resin substrate)
As the base material of the flexible resin substrate in the present invention, a resin can be used. For example, as the resin, phenol resin, epoxy resin, imide resin, BT resin, PPE resin, tetrafluoroethylene resin, liquid crystal resin, polyester Resin, PEN, aramid resin, polyamide resin, polyethersulfone, triacetylcellulose, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polystyrene, polybutadiene, polyacetylene, ASB resin / AS resin, MBS resin, polystyrene, methacrylic resin, Any resin that can be molded into a desired shape, such as polycarbonate, cyclic olefin resin (for example, norbornene resin), polyvinyl alcohol / EVOH, styrene block copolymer resin, etc. can be used. Kill. Therefore, it is preferably a thermoplastic resin that softens or melts when heat is applied and hardens when cooled.

  In the present application, “flexibility” means that the MIT test described in JIS P 8115: 2001 has a bending resistance of at least 100 times.

  The linear expansion coefficient of the thermoplastic resin alone is 0 to 120 ppm / ° C, preferably 5 to 100 ppm / ° C, and more preferably 10 to 80 ppm / ° C.

(Heat shrink material)
The “heat shrinkable material” according to the present invention refers to a material having a negative linear expansion coefficient (also referred to as “thermal expansion coefficient”).

  In the present invention, a heat-shrinkable material containing a metal element having a valence of 6, a plurality of metal elements having an average valence of 6, or manganese is used. As long as this condition is satisfied, various conventionally known heat shrinkable materials can be used. Of these conventionally known heat-shrinkable materials, in the present invention, it is preferable to use the following composite oxides or manganese nitrides having a reverse perovskite crystal structure.

<Composite oxide>
In the present invention, it is preferable to use a composite oxide represented by the following composition formula I.
Composition formula I: A ^{l +} _n (M ⁶⁺ O ₄ ) _m
(A is a metal element having a valence of 1 or a plurality of metal elements having an average valence of 1; M is a metal element having a valence of 6 or a plurality of metal elements having an average valence of 6; m and n are integers of 1 or more and satisfy the relational expression of l × n = 2 × m.)
In the present invention, the metal element M in the composition formula I is a metal element having a valence of 6 selected from tungsten (W) and molybdenum (Mo), or an average valence of 6 selected from any composition of W and Mo. What is a several metal element is preferable. In particular, tungsten (W) is preferable. The “average valence” means a value obtained by multiplying the valence of an element by its presence ratio and adding it.

The metal element A is a metal element having a valence of 4 selected from zirconium (Zr) and hafnium (Hf), or a plurality of metal elements having an average valence of 4 selected from Zr and Hf in any composition. Yes, a metal element having a valence of 3 selected from scandium (Sc), yttrium (Y), and lutetium (Lu), or a plurality of metal elements having an average valence of 4 selected from any composition of Sc, Y, and Lu Optionally from a valence 2 metal element selected from magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and a valence 4 metal element selected from Zr, Hf A plurality of metal elements having a valence of 3 formed in combination. For example, in addition to the negative thermal expansion oxide described above, HfMg (WO ₄ ) ₃ , ZrMg (WO ₄ ) ₃ , HfCa (WO ₄ ) ₃ , ZrCa (WO ₄ ) ₃ , HfMg (MoO ₄ ) ₃ , ZrMg ( MoO ₄ ) ₃ , ScY (WO ₄ ) ₃ , ScLu (WO ₄ ) ₃ , Zr _x Hf _1-x Mg (WO ₄ ) ₃ (0 <x <1), ZrMg _x Ca _1-x (WO ₄ ) ₃ (0 <x <1), HfMg _x Ca _1-x (WO ₄ ) ₃ (0 <x <1), ZrMg (W _y Mo _1-y O ₄ ) ₃ (0 <y <1), HfMg (W _{y Mo 1-y O 4)} 3 (0 <y <1), Sc 2 (W y Mo 1-y O 4) 3 (0 <y <1), Y 2 (W y Mo 1-y O 4) _{3 (0 <y <1)} , Zr (W y Mo 1-y O 4) 2 (0 <y <1), Hf (W _{Mo 1-y O 4) 2} (0 <y <1) , and the like. Further, among these, since the coefficient of thermal expansion can be controlled by a combination of metal elements, the metal element A includes a positive divalent metal element (preferably Mg) and a positive tetravalent metal. And an element (preferably Zr, Hf or a mixture thereof). The thermal expansion coefficient of these compounds is a negative thermal expansion coefficient, and the linear thermal expansion coefficient is approximately 0 to −10 × 10 in the temperature range from room temperature (about 25 ° C.) to 500 ° C. or higher, preferably 800 ° C. or higher. It has a small value in the range of ^-6 / ° C.

  Note that these oxides having a negative coefficient of thermal expansion have a spatial distance (for example, a crystal) in which a metal element in the compound is arranged by increasing the rotational movement of the bond with an increase in temperature in the metal-oxygen-metal bond. If so, it is thought that the overall thermal expansion becomes negative due to shrinkage of the crystal lattice constant).

In the composition formula I, the metal element A may be a composite oxide including a plurality of metal elements including a valence element, a valence element, and a valence element. For example, it is a compound represented by (HfMg) _1-x Al _2x (WO ₄ ) ₃ (0 <x <1), and this oxide varies from a negative thermal expansion coefficient to a positive thermal expansion coefficient depending on the value of x. Since it has the feature that it can be taken, it can be preferably used. Although this compound has a different thermal expansion coefficient depending on its composition, it can be controlled in the range of + 2 × 10 ⁻⁶ / ° C. to −2 × 10 ⁻⁶ / ° C. depending on the composition. In particular, when the composition x = 0.2 to 0.3, a linear thermal expansion coefficient having an absolute value within 0.5 × 10 ⁻⁶ / ° C. can be obtained in a temperature range from room temperature to about 800 ° C. .

Further, as the oxide, a pseudo multi-element mixed oxide can also be used. Here, the quasi-multielement mixed oxide is a mixed oxide formed by mixing a plurality of oxides. A plurality of oxides constituting the quasi-multielement mixed oxide may be particularly referred to as “unit oxides”. The plurality of unit oxides preferably include a unit oxide composed of a negative thermal expansion oxide and a unit oxide composed of a positive thermal expansion oxide. This is because the unit oxides made of negative thermal expansion oxide and the unit oxides made of positive thermal expansion oxide have similar chemical structures, so the affinity of each unit oxide at the time of production is low. This is because it tends to be improved and a tendency to become mechanically stable is obtained. A porous structure containing such a quasi-multi-element mixed oxide can also obtain a linear thermal expansion coefficient whose absolute value is within 1 × 10 ⁻⁶ / ° C. in the temperature range from room temperature to about 800 ° C. . Furthermore, the combination of the positive and negative unit oxides of the quasi-multi-system mixed oxides, the difference in the linear thermal expansion coefficient due to the material combining the control of the thermal expansion coefficient is approximately + 10 × 10 ⁻⁶ / ° C. to −10 × 10 It can be controlled in the range of ⁻⁶ / ° C.

In the present application, “low thermal expansion” means that the coefficient of thermal expansion, which is a change in dimensions due to the change in heat, is on the order of 10 ⁻⁶ / ° C., and its absolute value is approximately 5 × 10 ⁻⁶ / ° C. or less. It is defined as The thermal expansion coefficient can be measured by measuring a change in geometric dimension with respect to a temperature change by thermomechanical analysis (hereinafter abbreviated as TMA) or laser interferometry. The thermal conductivity can also be measured by a laser flash method.

As the raw material for the oxide represented by the composition formula I, oxides, hydroxides, carbonates, and the like of each constituent metal element can be used. For example, tungsten oxide, molybdenum oxide, magnesium oxide, zirconium oxide, hafnium oxide, calcium oxide, strontium oxide, aluminum oxide, scandium oxide, yttrium oxide, lutetium oxide, vanadium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, Magnesium carbonate, calcium carbonate, and phosphates of each metal. Also, organometallic compounds of each constituent metal element, such as metal alkoxide, metal acetylacetonate, metal acetate, metal methacrylate, metal acrylate, aluminum isopropoxide, aluminum-sec-butoxide, hafnium -T-butoxide, hafnium ethoxide, hafnium-2,4-pentadionate, lutetium-2,4-pentadionate, magnesium ethoxide, magnesium methoxide, magnesium n-propoxide, magnesium methyl carbonate, magnesium-2 , 4-Pentadionate, Magnesium acetate, Magnesium methacrylate, Calcium acetate, Molybdenum oxide bis (2,4-pentadionate), Tungsten hexaethoxide, Zirconium isopropo Side, zirconium butoxide, yttrium isopropoxide, magnesium aluminum alkoxide is magnesium zirconium alkoxide. Further, as raw materials, trivalent tungsten oxides such as MgWO ₄ , CaWO ₄ , and SrWO _{4 that} are divalent tungsten oxides, such as HfW ₂ O ₈ and ZrW ₂ O _{8 that} are tetravalent tungsten oxides. ₂ W ₃ O ₁₂ , Sc ₂ W ₃ O ₁₂ or the like may be used.

  In general, a composite oxide can be produced in the order of preliminary firing, coarse pulverization, molding, and main firing after mixing and kneading or kneading a raw material metal oxide using a method such as a ball mill. The material of the present invention can also be produced by these general production methods. In addition, if the fine pulverization is sufficiently performed in the mixing and pulverizing step, it is possible to produce an equivalent sample without pre-baking. As a method of mixing and coarse pulverization according to the present embodiment, not only a likai machine and a wet ball mill, but also a wet pulverization method can be used as long as it is a mixed pulverization method such as a planetary mill or a medium mill (for example, an attritor or a vibration mill). Therefore, uniform mixing and pulverization is possible, and the effects of the present invention can be obtained.

  In addition, the molding is performed to adjust the form of the complex oxide, and the same effect is obtained regardless of the molding method, such as molding using a green sheet using various sheet coating apparatuses as well as pressure molding. It goes without saying that it can be obtained.

  Moreover, as firing conditions, it can produce on general conditions. As firing conditions, although the firing temperature varies depending on the type of composite oxide to be generated or the type of binder material, it is about 600 ° C. or higher, preferably in the range up to 1600 ° C. The firing atmosphere is performed in air or in an atmosphere containing oxygen, and may be performed in an inert gas atmosphere or under reduced pressure as the case may be. When the tungstic acid compound is formed by solid phase reaction, the firing temperature is preferably 900 ° C. to 1200 ° C. for the tungsten composite oxide, and 700 to 1000 ° C. for the molybdenum oxide. If the calcination temperature is lower than this, the reaction of the oxide is not sufficient and the desired compound cannot be obtained. On the other hand, when the temperature is higher than this, the compound tends to melt or the tungsten oxide or molybdenum oxide in the compound tends to sublimate. These conditions may be determined by selection of raw materials.

  Furthermore, additives can be used for the purpose of improving the density and improving the reproducibility of material properties. Additives include alkaline earth metals, Al, Y, Sc, Lu, Zr, Hf, W, Mo, Fe, Mn, Ni, Si oxides or compounds, such as magnesium oxide, calcium oxide, Aluminum oxide, yttrium oxide, scandium oxide, iron oxide, manganese dioxide, silicon dioxide, nickel oxide, zirconium oxide, hafnium oxide, tungsten oxide and other oxides, magnesium hydroxide, calcium hydroxide, aluminum hydroxide and other hydroxides Further, carbonates such as magnesium carbonate, calcium carbonate, and barium carbonate can be used. These additives are effective at an addition amount of 5% by mass or less with respect to the main raw material, and an addition amount of 0.1 to 2% by mass is particularly preferable. If the addition amount is small, the effect cannot be sufficiently obtained, and if the addition amount is 5% or more, it melts due to a melting point drop or reacts with a part of the main raw material or the main raw material itself to produce a by-product. This is not preferable because it affects the original characteristics of the main raw material. These additives may be used in combination.

<Manganese nitride with inverted perovskite crystal structure>
In the present invention, manganese nitride having a reverse perovskite crystal structure can also be used as the heat shrinkable material.

  Here, “manganese nitride having a reverse perovskite crystal structure” is the same as what is called reverse perovskite-type manganese nitride or interstitial manganese nitride, and the cubic system or cubic system is slightly distorted. Any of those (for example, hexagonal system, monoclinic system, orthorhombic system, tetragonal system, trigonal system, etc.) may be used, but cubic system is preferable.

  The negative thermal expansibility of manganese nitride having an inverted perovskite crystal structure is derived from the magnetovolume effect of manganese nitride. The magnetic volume effect refers to a phenomenon in which the volume changes as the magnetic moment changes. In the manganese nitride, the magnetic moment increases in the low-temperature magnetic ordered phase, and the volume increases as the temperature decreases accordingly. The effect derived from this magnetism overcomes the normal positive thermal expansion, thereby realizing the net negative thermal expansion of the manganese nitride. Therefore, when the manganese nitride is used for thermal expansion control in a composite material, the temperature range in which the linear expansion coefficient α can be kept small is about the magnetic transition temperature of the manganese nitride and lower.

The general chemical formula of the manganese nitride is represented by “Mn _4-x A _x N”. The element A is one element selected from Co, Ni, Cu, Zn, Ga, Rh, Pd, Ag, Cd, and In, and 0 <x <4 (where x is not an integer). is there. Alternatively, the element A is Mg, Al, Si, Sc and any two or more elements of Group 4 to 15 atoms in the 4th to 6th periods of the periodic table, at least one of which is Co, Ni, Cu, Any of Zn, Ga, Rh, Pd, Ag, Cd, and In, and 0 <x <4. Furthermore, a part of nitrogen N may be substituted with any of hydrogen H, boron B, carbon C, and oxygen O, preferably boron B and carbon C, more preferably carbon C.

Note that the general chemical formula “Mn _4-x A _x N” of the manganese nitride is a formula based on the assumption that there are no atomic defects or excess, but interstitial manganese nitride is a defect that can normally occur in the crystal lattice. Even if there is an excess, as described above, as long as there is a temperature range exhibiting a negative linear expansion coefficient α, the composite material can be used without any problem.

As a specific composition of the manganese nitride, Mn ₃ Cu _0.5 Sn _0.5 N, Mn _3.1 Cu _0.4 Sn _0.5 N, Mn ₃ Cu _0.5 Sn _0.5 N _{0 .9} C _0.1 , Mn _3.1 Cu _0.4 Sn _0.5 N _0.9 C _0.1 , Mn _2.88 Fe _0.12 Cu _0.4 Sn _0.6 N, Mn ₃ Zn _{0 .5} Sn _0.5 N, Mn _3.1 Zn _0.4 Sn _0.5 N, Mn ₃ Zn _0.5 Sn _0.5 N _0.9 C _0.1 , Mn _3.1 Zn _0.4 Sn _0.5 N _0.9 C _0.1 , Mn _2.88 Fe _0.12 Zn _0.4 Sn _0.6 N and the like can be mentioned.

(Production method of resin substrate)
As a method for producing the flexible resin substrate of the present invention, a usual inflation method, T-die method, calendar method, cutting method, casting method, emulsion method, hot press method and the like can be used. From the viewpoints of suppression, suppression of foreign matter defects, suppression of optical defects such as die lines, and the like, a solution casting method by a casting method and a melt casting method are preferable.

  Hereinafter, as a typical example, a production method in the case of producing the flexible resin substrate of the present invention as a film-like resin substrate will be described in detail.

<Method for producing resin substrate by solution casting method>
(Organic solvent)
When the flexible resin substrate of the present invention is produced by the solution casting method, an organic solvent useful for forming the dope is one that dissolves a thermoplastic resin such as an acrylic resin, a cellulose ester resin, or a polycarbonate. Can be used without limitation.

For example, as the chlorinated organic solvent, methylene chloride, as the non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3
Examples thereof include 3-pentafluoro-1-propanol, nitroethane, ethyl lactate, lactic acid, diacetone alcohol and the like, and methylene chloride, methyl acetate, ethyl acetate, acetone, ethyl lactate and the like can be preferably used.

  In addition to the organic solvent, the dope may contain 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the dissolution of the thermoplastic resin in a non-chlorine organic solvent system is promoted. There is also a role.

  In particular, the thermoplastic resin should be a dope composition in which at least 10 to 45 mass% of the thermoplastic resin is dissolved in methylene chloride and a solvent containing a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. preferable.

  Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.

  Hereinafter, a preferred method for forming a film-like resin substrate (hereinafter also simply referred to as “film”) according to the present invention will be described.

1) Dissolution Step In this step, a thermoplastic resin, a heat-shrinkable material, and other additives are dissolved in an organic solvent mainly composed of a good solvent for the thermoplastic resin while stirring to form a dope.

  For the dissolution of the thermoplastic resin, a method carried out at normal pressure, a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544, JP-A-9-95557 Alternatively, various dissolution methods such as a cooling dissolution method as described in JP-A-9-95538 and a high-pressure method as described in JP-A-11-21379 can be used. The method of pressurizing at a boiling point or higher is preferred.

  Recycled material is a finely pulverized film, which is generated when the film is formed, cut off on both sides of the film, or the original film that has been speculated out due to scratches, etc. Reused.

2) Casting process An endless metal belt, such as a stainless steel belt or a rotating metal drum, which supports the dope is fed to a pressure die through a liquid feed pump (for example, a pressurized metering gear pump) and supported infinitely. This is a step of casting a dope from a pressure die slit to a casting position on the body.

  A pressure die that can adjust the slit shape of the die base portion and can easily make the film thickness uniform is preferable. Examples of the pressure die include a coat hanger die and a T die, and any of them is preferably used. The surface of the metal support is a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.

3) Solvent evaporation step In this step, the web (the dope is cast on the casting support and the formed dope film is called a web) is heated on the casting support to evaporate the solvent.

  To evaporate the solvent, there are a method of blowing air from the web side and / or a method of transferring heat from the back side of the support by a liquid, a method of transferring heat from the front and back by radiant heat, and the like. High efficiency and preferable. A method of combining them is also preferably used. The web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or to heat by means such as infrared rays.

  From the viewpoint of surface quality, moisture permeability, and peelability, it is preferable to peel the web from the support within 30 to 120 seconds.

4) Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position. The peeled web is sent to the next process.

  The temperature at the peeling position on the metal support is preferably 10 to 40 ° C, more preferably 11 to 30 ° C.

  In addition, it is preferable that the residual solvent amount at the time of peeling of the web on the metal support at the time of peeling is peeled in the range of 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like. If the web is peeled off at a time when the amount of residual solvent is larger, if the web is too soft, the flatness at the time of peeling will be lost, and slippage and vertical stripes are likely to occur due to the peeling tension. The amount of solvent is determined.

  The residual solvent amount of the web is defined by the following formula.

Residual solvent amount (%) = (mass before web heat treatment−mass after web heat treatment) / (mass after web heat treatment) × 100
Note that the heat treatment for measuring the residual solvent amount represents performing heat treatment at 115 ° C. for 1 hour.

  The peeling tension at the time of peeling the metal support and the film is usually 196 to 245 N / m. However, when wrinkles easily occur at the time of peeling, it is preferable to peel with a tension of 190 N / m or less. It is preferable to peel at a minimum tension that can be peeled to 166.6 N / m, and then peel at a minimum tension to 137.2 N / m, and particularly preferably peel at a minimum tension to 100 N / m.

  In the present invention, the temperature at the peeling position on the metal support is preferably -50 to 40 ° C, more preferably 10 to 40 ° C, and most preferably 15 to 30 ° C.

5) Drying and stretching step After peeling, a drying device 35 that alternately conveys the web through a plurality of rolls arranged in the drying device and / or a tenter stretching device 34 that clips and conveys both ends of the web with a clip are used. And dry the web.

  Generally, the drying means blows hot air on both sides of the web, but there is also a means for heating by applying microwaves instead of the wind. Too rapid drying tends to impair the flatness of the finished film. Drying at a high temperature is preferably performed from about 8% by mass or less of the residual solvent. Throughout the drying is generally carried out at 40-250 ° C. It is particularly preferable to dry at 40 to 160 ° C.

  When using a tenter stretching apparatus, it is preferable to use an apparatus that can independently control the film gripping length (distance from the start of gripping to the end of gripping) left and right by the left and right gripping means of the tenter. In the tenter process, it is also preferable to intentionally create sections having different temperatures in order to improve planarity.

  It is also preferable to provide a neutral zone between different temperature zones so that the zones do not interfere with each other.

  In addition, extending | stretching operation may be divided | segmented and implemented in multiple steps, and it is also preferable to implement biaxial stretching in a casting direction and a width direction. When biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise.

  In this case, stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible. That is, for example, the following stretching steps are possible.

-Stretch in the casting direction-Stretch in the width direction-Stretch in the casting direction-Stretch in the casting direction-Stretch in the width direction-Stretch in the width direction-Stretch in the casting direction-Stretch in the casting direction Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension. The preferable draw ratio of simultaneous biaxial stretching can be taken in the range of x1.01 to x1.5 times in both the width direction and the longitudinal direction.

  When the tenter is used, the residual solvent amount of the web is preferably 20 to 100% by mass at the start of the tenter, and it is preferable to perform drying while applying the tenter until the residual solvent amount of the web becomes 10% by mass or less. More preferably, it is 5% by mass or less.

  30-160 degreeC is preferable, as for the drying temperature in the case of performing a tenter, 50-150 degreeC is more preferable, and 70-140 degreeC is the most preferable.

  In the tenter process, it is preferable that the temperature distribution in the width direction of the atmosphere is small from the viewpoint of improving the uniformity of the film. The temperature distribution in the width direction in the tenter process is preferably within ± 5 ° C, and within ± 2 ° C Is more preferable, and within ± 1 ° C. is most preferable.

6) Winding process This is a process in which the amount of residual solvent in the web becomes 2% by mass or less, and is taken up by the winder 37 as a film, and the dimensional stability is achieved by setting the residual solvent amount to 0.4% by mass or less. Can be obtained. It is particularly preferable to wind up at 0.00 to 0.10% by mass.

  As a winding method, a generally used method may be used. There are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, and the like.

  The film according to the present invention is preferably a long film. Specifically, the film has a thickness of about 100 m to 5000 m and is usually provided in a roll shape. Moreover, it is preferable that the width | variety of a film is 1.3-4m, and it is more preferable that it is 1.4-2m.

  Although there is no restriction | limiting in particular in the film thickness of the film concerning this invention, It is preferable that it is 20-200 micrometers, It is more preferable that it is 25-150 micrometers, It is especially preferable that it is 30-120 micrometers.

<Manufacturing method of substrate by melt casting film forming method>
A method for producing the flexible resin substrate of the present invention as a film-like resin substrate by a melt casting film forming method will be described.

<Melted pellet manufacturing process>
The composition constituting a film made of a thermoplastic resin and a heat shrinkable material used for melt extrusion is usually preferably kneaded in advance and pelletized.

  The pelletization may be performed by a known method. For example, an additive comprising a dried thermoplastic resin and a heat-shrinkable material is supplied to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder. Can be extruded into strands, cooled with water or air, and cut.

  It is important to dry the raw material before extruding to prevent decomposition of the raw material. In particular, since the cellulose ester easily absorbs moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air dryer or a vacuum dryer to keep the moisture content at 200 ppm or less, and further 100 ppm or less.

  Additives may be fed into the extruder and fed into the extruder, or may be fed by individual feeders. In order to mix a small amount of additives such as an antioxidant uniformly, it is preferable to mix them in advance.

  The antioxidant may be mixed with each other, and if necessary, the antioxidant may be dissolved in a solvent, impregnated with a thermoplastic resin and mixed, or mixed by spraying. May be.

  A vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Moreover, when touching with air, such as an exit from a feeder part or die | dye, it is preferable to set it as atmosphere, such as dehumidified air and dehumidified N2 gas.

  The extruder is preferably processed at as low a temperature as possible so that the shearing force is suppressed and the resin can be pelletized so as not to deteriorate (molecular weight reduction, coloring, gel formation, etc.). For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.

  A film is formed using the pellets obtained as described above. It is also possible to feed the raw material powder directly to the extruder with a feeder and form a film as it is without pelletization.

<Process for extruding molten mixture from die to cooling roll>
First, using a single-screw or twin-screw type extruder, the melt temperature Tm when extruding the pellet is about 200 to 300 ° C., filtered through a leaf disk type filter or the like to remove foreign matters, The film is coextruded into a film, solidified on a cooling roll, and cast while pressing with an elastic touch roll.

  When introducing from the supply hopper to the extruder, it is preferable to prevent oxidative decomposition or the like under vacuum or reduced pressure or in an inert gas atmosphere. Tm is the temperature of the die exit portion of the extruder.

  When foreign matter such as scratches or plasticizer aggregates adheres to the die, streak-like defects may occur. Such defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable to have a structure in which the resin retention portion is minimized in the piping from the extruder to the die. . It is preferable to use a die that has as few scratches as possible inside the lip.

  The inner surface that contacts the molten resin such as an extruder or a die is preferably subjected to surface treatment that makes it difficult for the molten resin to adhere to the surface by reducing the surface roughness or using a material having a low surface energy. Specifically, a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.

  In the present invention, there is no particular limitation on the cooling roll, but it is a roll having a structure in which a heat medium or a refrigerant body whose temperature can be controlled flows through a high-rigidity metal roll, and its size is not limited. It is sufficient that the film is large enough to cool the film, and the diameter of the cooling roll is usually about 100 mm to 1 m.

  Examples of the surface material of the cooling roll include carbon steel, stainless steel, aluminum, and titanium. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to perform a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.

  The surface roughness of the chill roll surface is preferably 0.1 μm or less in terms of Ra, and more preferably 0.05 μm or less. The smoother the roll surface, the smoother the surface of the resulting film. Of course, it is preferable that the surface processed is further polished to have the above-described surface roughness.

  In the present invention, as an elastic touch roll, JP-A-03-124425, JP-A-08-224772, JP-A-07-1000096, JP-A-10-272676, WO97 / 028950, JP-A-11- No. 235747, JP-A 2002-36332, JP-A 2005-172940 and JP-A 2005-280217 can use a thin-film metal sleeve-covered silicon rubber roll.

  When peeling the film from the cooling roll, it is preferable to control the tension to prevent deformation of the film.

<Extension process>
In the present invention, the film obtained as described above can be further stretched 1.01 to 3.0 times in at least one direction after passing through the step of contacting the cooling roll.

  Preferably, the film is stretched 1.1 to 2.0 times in both the longitudinal (film transport direction) and lateral (width direction) directions.

  As a method of stretching, a known roll stretching machine or tenter can be preferably used. In particular, when the optical film also serves as a polarizing plate protective film, it is preferable to stack the polarizing film in a roll form by setting the stretching direction to the width direction.

  By stretching in the width direction, the slow axis of the optical film becomes the width direction.

  Usually, the stretching ratio is 1.1 to 3.0 times, preferably 1.2 to 1.5 times, and the stretching temperature is preferably performed in the temperature range of Tg to Tg + 50 ° C. of the resin constituting the film. .

  The stretching is preferably performed under a uniform temperature distribution controlled in the longitudinal direction or the width direction. The temperature is preferably within ± 2 ° C, more preferably within ± 1 ° C, and particularly preferably within ± 0.5 ° C.

  When the film-like resin substrate produced by the above method is used as an optical film, the film may be contracted in the longitudinal direction or the width direction for the purpose of adjusting the retardation of the optical film and reducing the dimensional change rate.

  In order to shrink in the longitudinal direction, for example, there is a method of contracting the film by temporarily clipping out the width stretching and relaxing in the longitudinal direction, or by gradually narrowing the interval between adjacent clips of the transverse stretching machine.

  The uniformity in the slow axis direction is also important, and the angle is preferably −5 to + 5 ° with respect to the film width direction, more preferably in the range of −1 to + 1 °, and particularly −0. It is preferably in the range of 5 to + 0.5 °, particularly preferably in the range of −0.1 to + 0.1 °. These variations can be achieved by optimizing the stretching conditions.

  The film-like resin substrate of the present invention is preferably a long film. Specifically, the film-like resin substrate has a thickness of about 100 m to 5000 m and is usually provided in a roll shape. Moreover, it is preferable that the width | variety of a film is 1.3-4m, and it is more preferable that it is 1.4-2m.

  There is no restriction | limiting in particular in the film thickness of the film-form resin substrate which concerns on this invention, It is preferable to change according to the objective. For example, when using for a polarizing plate protective film, it is preferable that it is 20-200 micrometers, It is more preferable that it is 25-150 micrometers, It is especially preferable that it is 30-120 micrometers.

<Flexible resin substrate manufacturing equipment>
FIG. 1 is a schematic flow sheet showing an overall configuration of an example of a flexible resin substrate manufacturing apparatus of the present invention. In FIG. 1, a flexible resin substrate is manufactured by mixing and extruding a film material such as a thermoplastic resin and then extruding from a casting die 4 onto a first cooling roll 5 using an extruder 1. In addition to circumscribing the cooling roll 5, the film 10 is further circumscribed by the total of three cooling rolls, the second cooling roll 7 and the third cooling roll 8, and cooled and solidified to form the film 10. Next, the film 10 peeled off by the peeling roll 9 is then stretched in the width direction by holding both ends of the film by the stretching device 12 and then wound by the winding device 16. In addition, a touch roll 6 is provided that clamps the molten film on the surface of the first cooling roll 5 in order to correct the flatness. The touch roll 6 has an elastic surface and forms a nip with the first cooling roll 5.

  In the present invention, it is preferable to add a device for automatically cleaning the belt and the roll to the manufacturing apparatus. There is no particular limitation on the cleaning device. For example, there are a method of niping a brush roll, a water absorbing roll, an adhesive roll, a wiping roll, an air blowing method for spraying clean air, a laser incinerator, or a combination thereof. is there.

  In the case where the cleaning roll is nipped, the cleaning effect is great if the belt linear velocity and the roller linear velocity are changed.

(Dampproof layer)
The flexible resin substrate of the present invention is characterized by having a moisture-proof layer on at least one surface thereof.

  The moisture-proof layer according to the present invention is intended to prevent humidity fluctuations, in particular, deterioration of the resin substrate and the like due to high humidity. However, the moisture-proof layer may have a special function / use as described later. In addition, various conventionally known moisture-proof layers can be provided.

  The flexible resin substrate of the present invention preferably has at least one gas barrier layer as a moisture-proof layer on both surfaces of the resin film.

  When the gas barrier layer is provided, the gas permeability of the resin film is greatly reduced, so that the permeation of water vapor and oxygen contained in the outside air can be suppressed. For example, in an organic EL substrate, by suppressing gas permeation by the gas barrier layer, damage to the organic EL element can be reduced and the light emission life can be extended. In addition, expansion of the non-lighting area that increases with time during light emission can be suppressed.

  Even in the case of using it for a liquid crystal substrate, if there is no gas barrier layer, gas such as water vapor or oxygen is mixed into the element, which causes the display quality to deteriorate and shorten the life.

  In one embodiment of the present invention, at least one gas barrier layer is provided on each side of the resin film. By having the gas barrier layer on both sides, not only gas permeation can be suppressed, but also dimensional change can be suppressed in the process of contacting the liquid such as cleaning during the process.

The flexible resin substrate of the present invention has a water vapor transmission rate of 0.1 g / m ² · 24 hr or less, preferably 0.01 g / m ² · 24 hr or less, more preferably 0.001 g / m ² as gas barrier performance. -Adjust with a moisture-proof layer (gas barrier layer) so that it is 24 hours or less.

The oxygen permeability is 0.1 ml / m ² · 24 hr · atm or less, preferably 0.001 ml / m ² · 24 hr · atm, more preferably 0.001 ml / m ² · 24 hr · atm or less. It adjusts with a moisture-proof layer (gas barrier layer).

  By having these characteristics, when a display such as an organic EL device is used as a substrate or the like, excellent gas barrier performance can be imparted to the organic EL device.

The water vapor transmission rate (g / m ² / day) is measured by the method described in JIS K 7129B. For measurement, a water vapor transmission rate measuring device PERMATRAN-W 3/33 MG module manufactured by MOCON can be used.

Similarly, oxygen permeability (ml / m ² / day / atm) can be measured using an oxygen permeability measuring device OX-TRAN 2/21 ML module manufactured by MOCON according to JIS K 7126B.

  As the gas barrier layer, it is preferable to provide an inorganic film having transparency. Although not particularly limited thereto, silicon oxide, aluminum oxide, tantalum oxide, silicon oxynitride, aluminum oxynitride, SiAlON, and the like can be used from the viewpoints of transparency and gas barrier properties. Further, from the viewpoint of acid resistance and alkali resistance, it is preferable that the main component is silicon oxide, nitride or oxynitride.

The gas barrier layer can be produced by a physical vapor deposition (PVD) method such as vapor deposition, ion plating or sputtering, a chemical vapor deposition method such as plasma CVD (chemical vapor deposition), or a sol-gel method. Among these, the sputtering method is preferable because a film having high adhesion, a dense and high gas barrier property is easily obtained. The gas barrier layer can be formed by either a single wafer method or a roll-to-roll method. However, since the film is formed on a resin film, productivity is improved by the roll-to-roll method. Sputtering deposition of silicon oxide, nitride, or oxynitride includes DC (direct current) sputtering, RF (radio frequency) sputtering, a combination of magnetron sputtering, and dual using an intermediate frequency range. Conventional techniques such as magnetron (DMS) sputtering can be used alone or in combination. In the sputtering atmosphere, an inert gas such as He, Ne, Ar, Kr, and Xe, at least one process gas among oxygen and nitrogen can be used. When sputtering silicon oxide, nitride, or oxynitride by DC sputtering or DMS sputtering, Si can be used as the target. By introducing oxygen or nitrogen into the process gas, a thin film of silicon oxide, nitride or oxynitride can be formed. When these are formed by RF (high frequency) sputtering, a ceramic target such as SiO ₂ or Si ₃ N ₄ can also be used. From the viewpoint of productivity, it is preferable to form a film using Si target and introducing oxygen or nitrogen by DC sputtering or DMS sputtering.

  Two or more gas barrier layers may be provided. In that case, an organic coat layer is preferably provided between the gas barrier layers. Providing this organic coating layer in the intermediate layer is preferable because the gas permeability is reduced as compared with the case where two barrier layers are provided in succession. This is because the organic coating layer covers and smoothes the defects of the barrier layer provided earlier, and the barrier layer provided next is triggered by the defects of the previous barrier layer. It is thought to make it difficult to make. The organic coat layer may also be provided between the resin film and the gas barrier layer. Each organic coat layer may be the same material or a different material.

  In particular, when this composite material substrate with a transparent electrode is used as a substrate for a color filter, B (black) R (red) G (green) B (formed by a photolithographic method or the like as one of the organic coating layers. A blue colored pattern can also be inserted.

  The organic coating layer is usually a compound having transparency, adhesion and heat resistance, and examples thereof include thermosetting resins such as thermoplastic resins and epoxy resins, and ultraviolet / electron beam crosslinking resins such as acrylic crosslinking resins. However, it is not limited to these. The organic coat layer can be formed by a method such as wire bar, extrusion, microgravure, reverse roll, etc. while keeping the raw material compound in solution, latex or no solvent. The thickness of the organic coating layer is preferably in the range of 0.5 μm to 5 μm from the balance of defect coverage, adhesion, and transparency.

  Usually, as described in Examples of Japanese Patent Application Laid-Open No. 2008-216541, dimensional stability that can be used as a substrate can be satisfied by mixing resin and glass fiber at a mass percentage of 1: 1.

  However, in this method, the surface becomes rough by adding a large amount of fibers. If an inorganic gas barrier layer is formed directly on this rough surface, a dense film will not be formed and the barrier property will be reduced. Further, since a dense film cannot be formed, cracks are likely to occur and the barrier property will be significantly reduced. There was a problem.

  The resin substrate of the present invention can be made of a small amount of material that reduces the linear expansion, and can be produced with a flat surface roughness. As a result, even when the gas barrier layer is formed, a dense film is formed, which can prevent the barrier property from being lowered.

  Further, a smoothing layer may be provided between the resin substrate and the barrier layer. The smoothing layer can be produced by using a general UV curable resin or the like.

  In the present invention, a moisture-proof layer comprising a metal atom-containing film is particularly preferable.

As the metal atom-containing film, it is preferable to use a metal atom-containing film formed by a method based on the forming method disclosed in Japanese Patent Application Laid-Open No. 2008-258211. That is, the metal is discharged by supplying a high-frequency voltage exceeding 100 kHz and a power of 1 W / cm ² or more between two opposing electrodes under atmospheric pressure or near atmospheric pressure. It is preferable that the forming method has a mode in which a metal atom-containing film is formed on the substrate by putting the reactive gas contained in a plasma state and exposing the substrate to a reactive gas in a plasma state. Here, the vicinity of atmospheric pressure represents a pressure of 20 to 110 kPa, and 93 to 104 kPa is more preferable.

  In the above forming method, the metal atom-containing film is formed under a pressure close to atmospheric pressure, but the temperature of the substrate at that time is not particularly limited. In the present invention, since a resin film is used as the substrate, 300 ° C. or lower is preferable.

  The metal atom-containing film is preferably formed on the substrate surface with a thickness of about 1 to several hundred nm.

  The gas used in the method for forming a metal atom-containing film according to the present invention will be described. The gas to be used varies depending on the type of film to be provided on the substrate, but is basically a discharge gas and a reactive gas that is in a plasma state to form the film.

  Examples of the discharge gas include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, nitrogen, and the like, and argon, helium, or nitrogen is particularly preferably used. The discharge gas is contained in an amount of 90 to 99.9% by volume with respect to the total amount of gas supplied to the discharge space.

  It is preferable to contain 0.01-10 volume% of reactive gas with respect to the whole quantity of gas. The reactive gas is in a plasma state in the discharge space and contains a component that forms a film, and is an organometallic compound, an organic compound, an inorganic compound, or the like. Metal hydride compounds, metal halide compounds, metal hydroxide compounds, metal peroxide compounds and the like are also possible. Among these, an organometallic compound and an organic compound are preferable. Furthermore, as an organometallic compound, a metal alkoxide, an alkylated metal, and a metal complex are preferable. The reactive gas may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it is introduced into the discharge space as it is. In the case of a liquid or solid, it is used after being vaporized by means such as heating, decompression or ultrasonic irradiation. Also, it may be mixed and dissolved in a solvent, and since such a solvent is decomposed into molecular and atomic forms during plasma discharge treatment, it affects the formation of a thin film on a substrate, the composition of the thin film, etc. Is almost negligible.

  Moreover, a moisture-proof layer can be provided by using a reactive gas containing a silicon compound.

  Examples of the silicon compound described above include organic metal compounds such as dimethylsilane and tetramethylsilane, metal hydrogen compounds such as monosilane and disilane, metal halogen compounds such as silane dichloride and silane trichloride, tetramethoxysilane, and tetraethoxy. An alkoxysilane such as silane (TEOS) or dimethyldiethoxysilane, an organosilane, or the like can be used. Moreover, these can be used in combination as appropriate.

  In addition, depending on the type of metal atom-containing film of interest, oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, hydrogen sulfide, nitrogen, nitrogen monoxide, carbon dioxide are introduced into the gas introduced into the discharge space. By containing 0.01 to 5% by volume of a component selected from nitrogen, the reaction is promoted and a dense and high-quality thin film can be formed.

  Furthermore, in the present invention, after the metal atom-containing film is formed under a pressure near atmospheric pressure, it is possible to adjust the characteristics by applying heat. The heat treatment temperature is preferably in the range of 50 to 300 ° C. Preferably it is the range of 100-200 degreeC. The atmosphere for heating is not particularly limited. An air atmosphere, a reducing atmosphere containing a reducing gas such as hydrogen, an oxidizing atmosphere containing an oxidizing gas such as oxygen, or a vacuum or a discharge gas atmosphere is selected as appropriate according to the type and use of the film. It is possible. When taking a reducing or oxidizing atmosphere, it is preferable to use a reducing gas or an oxidizing gas diluted with a discharge gas such as a rare gas or nitrogen. In such a case, the concentration of the reducing gas and the oxidizing gas is preferably 0.01 to 5% of the total gas, and more preferably 0.1 to 3%.

  Next, the metal atom containing film formed by the above method will be described.

  In the metal atom-containing film formed by the method using the atmospheric pressure plasma method according to the present invention, the hydrogen concentration obtained by dynamic secondary ion mass spectrometry (dynamic SIMS) is H, and the metal atom concentration derived from the main metal When M is M, the variation coefficient of the H / M value in the film thickness direction is within 5%. Depending on the use of the membrane, the coefficient of variation is preferably within 3% or within 1%.

  Thus, the variation coefficient of the H / M value in the film thickness direction is within 5%, that is, the film is homogeneous in the thickness direction.

  Here, dynamic SIMS will be described. Regarding dynamic SIMS, the practical surface analysis secondary ion mass spectrometry (2001, Maruzen) edited by the Surface Science Society can be referred to.

In this embodiment, preferable dynamic SIMS measurement conditions are as follows. Apparatus: ADEPT 1010 or 6300 type secondary ion mass spectrometer manufactured by Physical Electronics Inc. Primary ion: Cs ion Primary ion energy: 5.0 KeV
Primary ion current: 200 nA
Primary ion irradiation area: 600 μm square secondary ion uptake ratio: 25%
Secondary ion polarity: Negative
Secondary ion species detected: H ion and M ion Mass spectrometry is performed while performing sputtering in the depth direction of the metal atom-containing film under the above conditions. The intensity ratio H / M between the hydrogen concentration H and the metal atom concentration M derived from the main metal is determined from the obtained depth profile. The measurement points are preferably 50 points or more, more preferably 75 points or more with respect to 100 nm. After obtaining the H / M ratio in the depth direction, the average of the H / M ratio and the relative standard deviation are obtained for 15 to 85% in the depth direction, the relative standard deviation is divided by the average, and the result is multiplied by 100. The coefficient of variation of the M ratio, that is, the variation is obtained.

  Moreover, the metal atom containing film | membrane which concerns on this invention which has the characteristics of the above fluctuation coefficients has the said H / M value 0.001-50, More preferably, it is 0.01-20. In this case as well, the H / M ratio is obtained based on the results of measurement under the above conditions in the depth direction using dynamic SIMS, and the average of the H / M ratio is defined as the H / M ratio for 15 to 85% in the depth direction. To do.

  Further, the hydrogen concentration obtained by dynamic secondary ion mass spectrometry is preferably 0.001 to 10 atomic%, more preferably 0.01 to 5 atomic%, and more preferably 0.5 to 1 atomic%. The hydrogen concentration is preferably evaluated by dynamic SIMS.

  The measurement conditions are as described above. Actually, first, the hydrogen concentration in the reference metal atom-containing film is obtained by Rutherford backscattering spectroscopy, the dynamic SIMS measurement of this reference product is performed, and the relative sensitivity coefficient is determined based on the detected hydrogen ion intensity. Then, dynamic SIMS measurement is performed on the metal atom-containing film that is actually used, and the hydrogen concentration in the sample is calculated using the signal intensity obtained from the measurement and the relative sensitivity coefficient obtained previously. The hydrogen concentration in the present invention is a depth profile obtained over the entire thickness direction of the metal atom-containing film, and the average of 15 to 85% depth of the metal atom-containing film is defined as the hydrogen concentration.

  Moreover, the metal atom containing film | membrane of this invention may contain a trace amount carbon, when using organic substance as reactive gas. In this case, the carbon content is preferably in the range of 0.001 to 5.0 atom concentration, particularly 0.01 to 3 atom concentration. A slight content is preferable because it gives flexibility to the film and improves adhesion to the substrate. However, if it exceeds 5% by mass, physical properties such as the refractive index of the film may change over time. Yes, not preferred.

  This carbon content depends mainly on the frequency of the power supply and the supply power, and decreases as the high frequency of the voltage applied to the electrode increases and the supply power increases. Further, when hydrogen gas is injected into the mixed gas, carbon atoms are easily consumed, and the content in the film can be reduced, which can also be controlled.

  Hereinafter, although an example is given and the present invention is explained, the present invention is not limited to these.

(Preparation of flexible resin substrate 1)
<Dope solution>
Triacetyl cellulose was added to a dissolution tank in which 5 parts by mass of a heat-shrinkable material (Mn ₃ Cu _0.5 Sn _0.5 N) was dispersed in the following solvent, and was heated and completely dissolved.

  A main dope solution was prepared using 12.5 parts by mass of triacetylcellulose (acetyl group substitution degree 2.8, number average molecular weight 80000, weight average molecular weight 220,000) and methylene chloride solution containing 8% by mass of ethanol. .

  The main dope solution was thoroughly mixed with an in-line mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then uniformly cast onto a stainless steel band support having a width of 2 m using a belt casting apparatus. On the stainless steel band support, the solvent was evaporated until the residual solvent amount became 110%, and the stainless steel band support was peeled off. Then, it dried at 120 degreeC for 30 minutes.

(Preparation of flexible resin substrate 2)
<material>
Mn ₃ Cu _0.5 Sn _0.5 N 40 parts by mass Panlite AD-5503 (manufactured by Teijin Chemicals) 100 parts by mass (antioxidant)
IRGANOX-1010 (manufactured by Ciba Japan) 1.0 part by mass Sumitizer GP (manufactured by Sumitomo Chemical) 0.5 part by mass (production of a masterbatch)
The materials excluding the heat-shrinkable material were mixed with a V-type tumbler for 30 minutes and then supplied at 100 kg / hr from the first supply port of an automatic twin screw kneading extruder ZCM53 / 60. Panlite was used after vacuum drying at 110 ° C. for 12 hours.

  The heat shrinkable material was supplied at 23 kg / hr from the second supply port (downstream from the first supply port) of the kneading extruder. The screw design has more kneading discs so that the kneading effect is strong. The screw rotation speed was 500 rpm, the temperature setting from the barrel to the die was 150 ° C. to 250 ° C., and a vent port was provided near the tip to remove volatile matter. The die was a strand die, and the discharged strand was guided into cooling water, cut with a pelletizer, and formed into a pellet having a diameter of about 3 mm and a length of about 3 mm.

(Melt extrusion film formation)
100 parts by mass of the above-mentioned Panlite was dried at a hot air temperature of 150 ° C. and a dew point of −36 ° C. using a dehumidifying hot air dryer manufactured by Matsui Seisakusho Co., Ltd., and then mixed with a V-type tumbler for 30 minutes together with the antioxidant. Subsequently, it supplied at 100 kg / hr to the twin screw extruder manufactured by Technobel. The screw design uses fewer kneading discs to suppress heat generation from resin kneading. On the other hand, after drying the master batch produced above, it was supplied to the same supply port at 20 kg / hr. The temperature setting from the barrel to the die was 150 ° C. to 250 ° C., and a vent port was provided near the tip to remove volatile matter. The film was extruded from a coat hanger type T die, dropped between two chrome-plated mirror rolls adjusted to 120 ° C., passed through the three rolls, slit the edge, and wound around a winder. The extrusion amount and the rotation speed of the take-up roll were adjusted so that the wound film had a thickness of 120 nm.

(Preparation of flexible resin substrate 3)
A flexible resin substrate 3 was produced in the same manner as the flexible resin substrate 1 except that Arton (manufactured by JSR) was used as the resin and methylene chloride containing 4% by mass of ethanol was used as the solvent.

(Preparation of flexible resin substrate 4)
A flexible resin substrate 4 was produced in the same manner as the flexible resin substrate 2 except that acrylic resin (BR85; manufactured by Mitsubishi Rayon) was used as the resin.

(Production of flexible resin substrates 5 to 8)
The flexible resin substrates 1 to 4 were similarly manufactured except that the heat-shrinkable material was ZrW ₂ O ₈ and the addition amount was 30 parts by mass with respect to the resin.

(Production of flexible resin substrates of Comparative Examples 1 to 4)
(Comparative Example 1)
30 parts by mass of glass fiber with respect to triacetyl cellulose was produced in the same manner as for flexible resin substrate 1.

(Comparative Example 2)
30 parts by mass of SiO ₂ particles (manufactured by Aerosil) with respect to triacetyl cellulose were produced in the same manner as for the flexible resin substrate 1.

(Comparative Example 3)
An epoxy resin, which is a curable resin, was impregnated with 30 parts by mass of glass fiber and cured to prepare a substrate.

(Comparative Example 4)
A substrate was prepared by mixing 30 parts by mass of SiO ₂ particles with an epoxy resin, which is a curable resin, and curing.

(Production of gas barrier layer)
The above-mentioned flexible resin substrate is loaded into a sputter roll coater and processed by DC magnetron sputtering using Si as a target at an ultimate vacuum of 1.0 × 10 ⁻⁴ Pa or less and a film forming temperature of 180 ° C. Argon gas and oxygen gas were introduced as gases, and a film of SiO _x (x = 1.8, by XPS) with a film thickness of 70 nm was formed on the resin film (1) by reactive sputtering, and the gas barrier layer (2) was formed. Formed.

[Evaluation]
About the flexible resin substrate (sheet-like transparent laminated body) produced by the said method, various characteristics were measured with the evaluation method shown below.

a) Average linear expansion coefficient After increasing the temperature from 30 ° C. to 150 ° C. at a rate of 5 ° C. per minute in a nitrogen atmosphere using an EXSTAR TMA / SS6000 type thermal stress strain measuring device manufactured by Seiko Electronics Co., Ltd. Once cooled to 0 ° C., the temperature was increased again at a rate of 5 ° C. per minute, and the value at 30 ° C. to 150 ° C. was measured and determined. The load was 5 g, the measurement was performed in the tension mode, and the evaluation was performed based on the following criteria. In addition, CTE (Coefficient of thermal expansion) of Table 1 is a linear expansion coefficient computed by the said measurement.
○: 25 ppm / ° C. or less ×: greater than 25 ppm / ° C. b) Flexibility Flexibility is evaluated by a method based on the MIT test described in JIS P 8115: 2001, and cracks are generated in a 90 ° C. bending test. This was confirmed and evaluated visually.
○: No crack is generated in a bending test of 100 times or more.
X: A crack occurs in a bending test less than 100 times.

c) Domain ratio and light weight The content (percentage) of the heat shrinkable material (also referred to as “inorganic domain”) is the domain ratio with respect to the total mass of the flexible resin substrate. evaluated.
○: Mass of 2.4 times or less per 1 m ^{3 with} respect to the resin-only film x: Mass exceeding 2.4 times per 1 m ^{3 with} respect to the resin-only film d) Gas barrier property For each of the prepared samples, JIS K The water vapor permeability (g / m ² · 24 hr) (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) was measured by a method based on 7129-1987.

  In addition, the water vapor permeability measuring device PERMATRAN-W 3/33 MG module manufactured by MOCON was used for the measurement.

Moreover, according to the method based on JISK7126B, oxygen permeability measurement was performed using the oxygen permeability measuring apparatus OX-TRAN 2/21 ML module manufactured by MOCON, and evaluation was performed based on the following criteria.
○: The water vapor transmission rate is 0.1 g / m ² · 24 hr or less and the oxygen transmission rate is 0.1 ml / m ² · 24 hr · atm or less.
X: Water vapor permeability is larger than 0.1 g / m ² · 24 hr, and oxygen permeability is larger than 0.1 ml / m ² · 24 hr · atm.

e) Local quality degradation resistance In order to evaluate the degradation resistance of display quality during use against local strain, the above-mentioned gas barrier flexible resin substrate having a thickness of 10 μm is used. After placing a PET film, applying a weight of 200 g to a cylinder of 10 mmφ from the top, and performing an impact test by allowing it to fall freely from above 100 mm and performing an impact, the water vapor transmission rate was measured to determine the barrier performance. The presence or absence of the decrease was evaluated according to the following criteria.
○: Change rate of water vapor transmission rate before and after dropping is less than 10%.
X: Change rate of water vapor permeability before and after dropping is 10% or more.

  The above evaluation results are summarized in Table 1.

  As is clear from the results shown in Table 1, the flexible resin substrate of the present invention has a low linear expansion coefficient while maintaining the characteristics of the flexible resin substrate such as lightness, transparency, and heat resistance. It can be seen that there is almost no deterioration in display quality with respect to locally applied distortion.

  As described above, the flexible resin substrate of the present invention has a high gas barrier property, a low linear expansion coefficient, excellent transparency and heat resistance, a transparent plate, an optical lens, a plastic substrate for liquid crystal display elements, and a color filter. It can be suitably used for substrates, plastic substrates for organic EL display elements, solar cell substrates, touch panels, light guide plates, optical elements, optical waveguides, LED sealing materials, and the like.

DESCRIPTION OF SYMBOLS 1 Extruder 2 Filter 3 Static mixer 4 Casting die 5 Rotating support body (1st cooling roll)
6 Nipping pressure rotating body (touch roll)
7 Rotating support (second cooling roll)
8 Rotating support (3rd cooling roll)
DESCRIPTION OF SYMBOLS 9 Peeling roll 10 Film 11, 13, 14 Conveyance roll 12 Stretching machine 15 Slitter 16 Winding machine F Film-like flexible resin substrate of this invention

Claims (5)

  A flexible resin substrate having a moisture-proof layer on at least one surface, and containing a heat-shrinkable material containing a metal element having a valence of 6, a plurality of metal elements having an average valence of 6, or manganese in the resin A flexible resin substrate.   The flexible resin substrate according to claim 1, wherein the resin is thermoplastic.   The flexible resin substrate according to claim 1, wherein the heat shrinkable material is a complex oxide of tungstic acid.   3. The flexible resin substrate according to claim 1, wherein the heat shrinkable material is manganese nitride having a reverse perovskite crystal structure.   A display device using the flexible resin substrate according to any one of claims 1 to 4.