KR20080103583A - Multilayer film, laminated body using the multilayer film and laminated body manufacturing method - Google Patents

Abstract

A multilayer film, which is light in weight, thin and flexible, a laminated body including such multilayer film, and a method for manufacturing such laminated body are provided by forming the laminated body to the substrate. The laminated body has excellent adhesiveness to substrates, such as a thin film transistor substrate, and includes an inorganic material layer on the surface. Namely, the multilayer film is provided with a base film (1) formed of a resin (1) having a glass transition temperature (Tg) of 80°C or higher; an inorganic thin film layer, which is arranged on the base film and is formed of an inorganic material (1); and an adhesive resin layer, which is arranged on the inorganic thin film layer, can be bonded with an inorganic material (2) and includes a resin (2) having a polar radical. The laminated body using such multilayer film and the method for manufacturing such laminated body are also provided.

Description

MULTILAYER FILM, LAMINATED BODY USING THE MULTILAYER FILM AND LAMINATED BODY MANUFACTURING METHOD}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer film, a laminate using the same, and a method for producing the laminate. Specifically, the present invention relates to lamination with a substrate having excellent adhesion to substrates such as thin film transistor substrates and having an inorganic material layer on its surface. The present invention relates to a multilayer film capable of realizing weight reduction, thinning, and flexibilization by forming a sieve, a laminate using the same, and a method for producing the laminate.

The demand for weight reduction, thinning, and flexibility in substrate materials is increasing day by day not only in organic substrates but also in inorganic material substrates. By bonding and compounding an organic resin film to an inorganic substrate, the fragility which is a fault of an inorganic material is overcome, and the possibility of thinning and flexible becomes wide. For example, in the case of a thin film transistor (abbreviated as TFT) substrate used for a liquid crystal display or the like, in order to meet the demand of a non-planar display material such as a curved surface, both flexibility and gas barrier properties in which a resin film is laminated on a glass thin film Development of substrates with functions is underway. For example, there exists a method of making a flexible TFT by creating a TFT on the glass thin film laminated | stacked on the flexible substrate, and transferring this glass thin film to a resin film substrate.

As an adhesive agent for laminating | stacking a glass thin film to a resin film and laminating | stacking on a laminated substrate, there exist adhesives, such as a photocuring type and a thermosetting type. However, when the thermosetting adhesive is used, the curing shrinkage during adhesion is large, and it is easy to cause problems such as deformation of the substrate and disconnection of wiring. In addition, when the photocurable adhesive agent is used, there is a risk that the transistor portion of the TFT main body is deteriorated by exposing strong light to the TFT to change the electrical characteristics.

Therefore, the adhesive method which replaces these adhesives has been examined. For example, International Publication No. WO 99/01519 pamphlet discloses that certain ring structure-containing thermoplastic polymers are useful as adhesives for semiconductor materials and describe a method of bonding under heat and press conditions. In Japanese Patent Laid-Open No. 3-95286, an adhesive made of a cyclic olefin resin and a solvent has been proposed, and adhesion under pressure conditions is also recommended.

Disclosure of the Invention

Problems to be Solved by the Invention

However, the above-mentioned conventional techniques are inadequate in adhesiveness, and in particular, in the case where a transparent resin is used for the substrate, there is a case where transparency is lowered under the influence of heating, pressurization, and the like.

Therefore, the present inventors have made a multilayer film as a precoating film produced by superimposing an adhesive resin layer on a base film (film base material) by coating a modified resin having an adhesive function in a varnish state or the like. The knowledge that adhesiveness with respect to board | substrates, such as and a TFT substrate, was excellent was acquired. Thus, when the modified resin which has an adhesive function is directly coated on the resin base film, the solvent of a coating varnish infiltrates and remains in a base film. Since this residual solvent acts as a plasticizer, it has the characteristic of being able to adhere to the substrate at or below the glass transition temperature of the adhesive resin. On the other hand, however, if an unnecessary residual solvent remains in the base film, the thermal expansion coefficient of the multilayer film becomes large, and as a result, in the laminate in which the multilayer film is laminated with the substrate, residual stress occurs in the substrate material after adhesion, resulting in thermal shock of the laminate. There existed a problem that curvature and a crack of a board | substrate generate | occur | produce at the time of a test.

Moreover, in order for a base film and an adhesive resin layer to have sufficient adhesiveness, it is necessary to use resin with high adhesiveness with an adhesive resin layer for resin which comprises a base film, and the problem of narrow selection of a base film is necessary. There was.

In the present invention, a multilayer film which is excellent in adhesion to substrates such as a thin film transistor substrate and which can realize weight reduction, thinning, and flexibility by forming a laminate with a substrate including an inorganic material layer on its surface, and this multilayer film It aims at providing the laminated body containing this, and the manufacturing method of this laminated body.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined in order to achieve the said subject. As a result, by providing an inorganic thin film layer between the base film and the adhesive resin layer such as the adhesive resin coating varnish, the solvent in the adhesive resin layer does not infiltrate the base film, and as a result, the residual solvent can be left only in the adhesive resin layer. It has been found that the thermal expansion coefficient of the multilayer film can be significantly suppressed by reducing the amount of unused residual solvent. As a result of introducing the inorganic thin film layer, it has also been found that the water vapor permeability from the base film can be reduced, thereby significantly suppressing the decrease in adhesion after the high temperature and high humidity resistance test of the adhesive resin layer and the substrate surface.

In addition, by providing an inorganic thin film layer between the base film and the adhesive resin layer, only a resin having a high adhesiveness with the inorganic thin film layer may be used for the resin constituting the adhesive resin layer, and the adhesion with the resin constituting the base film. The problem did not matter, and the selection range of resin of a base film became wide, and it discovered that it was industrially superior because only one type of resin which comprises an adhesive resin layer corresponds.

The present invention is based on such knowledge.

The present invention provides the following inventions.

[1] the base film 1 made of resin 1 having a glass transition temperature (Tg) of 80 ° C. or more,

Inorganic thin film layer which consists of inorganic material 1 provided on this base film 1,

The multilayer film provided on this inorganic thin film layer and provided with the adhesive resin layer containing resin 2 which has a polar group which can be adhere | attached with the inorganic material 2.

[2] The multilayer film according to [1], wherein the base film 1 is a film made of at least one resin selected from the group consisting of polyester resins, alicyclic structure-containing resins, polycarbonate resins, and polyimide resins.

[3] The inorganic thin film layer is [1] or [2] constituted by at least one material selected from the group consisting of metals, semimetals, inorganic oxides, inorganic nitrides, inorganic nitride oxides, and diamond-like carbons. The multilayer film described.

[4] The multilayer film according to any one of [1] to [3], wherein the inorganic thin film layer is an inorganic vapor deposition layer formed on the base film 1.

[5] The multilayer film according to any one of [1] to [4], wherein the resin 2 having the polar group is a resin having an acid anhydride group and / or an epoxy group.

[6] A substrate having an inorganic material layer of inorganic material 2 on the surface thereof, and the multilayer film according to any one of [1] to [5], wherein the adhesive material layer of the inorganic material layer of the substrate and the multilayer film is used. The laminated body formed by laminating so that it may contact | connect.

[7] The laminate according to [6], wherein the substrate includes a base film 3 made of resin 3 having a glass transition temperature (Tg) of 80 ° C. or higher, and the inorganic material layer provided on the base film 3.

[8] The laminate according to [6] or [7], wherein the inorganic material layer is at least one selected from the group consisting of a glass layer, a metal layer, and a metal oxide layer.

[9] The multilayer film according to any one of [1] to [5], wherein the glass transition temperature of the resin 2 having the polar group in the film is a multilayer film of 40 ° C. or more, and an inorganic material composed of inorganic material 2 on the surface thereof. The manufacturing method of the laminated body including the process of bonding the board | substrate containing a material layer at 40 degreeC or more and the temperature below the glass transition temperature of resin 2 which has the said polar group.

Effects of the Invention

According to the multilayer film of this invention, since solvent infiltration to a resin base film is suppressed, the increase of a thermal expansion rate is suppressed, and when it is provided on the board | substrate which contains an inorganic material layer on the surface, the board | substrate bends, a crack, etc. Can be suppressed. Moreover, when the multilayer film of this invention is provided on the board | substrate which has an inorganic material layer on the surface, and a laminated body is comprised, since the thermal expansion rate of a laminated body hardly rises, residual stress is reduced and crack generation is suppressed, The laminated body excellent in the adhesiveness of an adhesive resin layer and an inorganic thin film layer can be obtained.

1 is a schematic view of a manufacturing apparatus suitable for an embodiment.

Explanation of the sign

1: vacuum chamber 2: unwinding roll

3: guide roll 4: film forming roll

5-1, 5-2: target 6-1, 6-2: film forming cathode

7: winding roll 8: vacuum pump

Invention  Conduct  Best form for

The multilayer film of this invention has the multilayer structure in which the adhesive resin layer was provided on the base film 1 made from resin 1 with an inorganic thin film layer interposed therebetween.

The inorganic thin film layer which comprises the multilayer film of this invention is a layer which consists of the inorganic material (inorganic material 1) provided on the base film 1. The inorganic material is not particularly limited as long as it can provide barrier property against solvent infiltration. For example, it is preferable to consist of a single metal, a semimetal, such as Si, Mg, Ti, Al, In, Sn, Zn, W, Ce, Zr, an inorganic compound, and diamond-like carbon. As the inorganic compound, inorganic oxides, inorganic nitrides, inorganic nitride oxides, and inorganic sulfides are preferable. Among them, metals or semimetals, inorganic oxides, inorganic nitrides, inorganic nitride oxides and diamond-like carbons are particularly preferable, and at least one of them can be selected and used.

Examples of the inorganic oxides include aluminum oxide, silicon dioxide, silicon oxynitride, or mixtures thereof, ITO (indium titanium oxide), IZO (indium zinc oxide), AZO (aluminum zinc oxide), zinc oxide, zinc sulfide, ICO (indium cerium oxide) ), Titanium oxide and the like. Examples of the inorganic nitrides include silicon nitride. Among these inorganic substances, silicon dioxide or silicon oxynitride is preferable. The inorganic film formed using silicon dioxide or silicon oxynitride can be transparent and have a barrier property against high solvent infiltration. Moreover, adhesiveness with the adhesive resin layer which has an adhesive function with the inorganic material 2 mentioned later is also excellent.

The average thickness of the inorganic thin film layer is preferably 5 to 500 nm, more preferably 10 to 250 nm, and more preferably 50 nm to 130 nm. If the average thickness of the inorganic thin film layer is too thin, the barrier property against solvent infiltration may be insufficient. On the contrary, if the thickness is too thick, the film is less flexible and easily cracked.

It is preferable that the crystal state of an inorganic thin film layer is a uniform amorphous structure which does not contain columnar structure or a granular structure. If the columnar structure or the granular structure is included, the grain boundary may become a diffusion path of molecules to solvent infiltration and the barrier property to solvent infiltration may be lowered.

In the multilayer film of this invention, it is preferable that it is an inorganic vapor deposition layer deposited on the base film 1 as an inorganic thin film layer. The formation method of such an inorganic vapor deposition layer is not specifically limited. For example, when the inorganic resin layer is formed on the base film 1 in advance, and then the adhesive resin layer is formed thereon, the inorganic vapor deposition method can be formed in a vacuum vapor deposition method in that an inorganic film having a high film density can be efficiently formed. The sputtering method, the ion plating method, and the CVD method are preferable, and the vacuum deposition method and the CVD method using an arc discharge plasma are particularly preferred in that the organic film or the transparent resin substrate can be damaged and the film density can be increased. desirable. Using arc discharge plasma, evaporated particles with appropriate energy can be produced to form a dense film.

The vacuum deposition method is a method of forming a deposited film by heating and evaporating a deposition material by a method such as resistance heating, electron beam heating, laser light heating, arc discharge, etc. in a vacuum of about 10 ^-2 to 10 ^-5 Pa. Further, the sputtering method sputter evaporates the deposition raw material by colliding positive ions such as Ar ⁺ accelerated by a glow discharge to a target (deposition raw material) in a vacuum of about 1 to 10 ⁻¹ Pa in which an inert gas such as argon is present. To form a vapor deposition film on the surface of the base film or the like. Examples of the evaporation method include DC (direct current) sputtering, RF (high frequency) sputtering, magnetron sputtering, bias sputtering, and the like. The ion plating method is a vapor deposition method such as a combination of the above vacuum deposition method and sputtering method. In this method, a thin film can be formed in a high energy state by ionizing and accelerating an evaporation atom released by heating in a vacuum of about 1 to 10 ⁻¹ Pa in an electric field.

In the CVD method in the formation of the organic film, the CVD method uses a metal or semimetal compound as a deposition raw material, or combines a single metal or semimetal substance with a substance containing an oxygen atom, a nitrogen atom, or a sulfur atom. It is a method of evaporating them, making it react as needed, depositing on a base material, and forming into a film.

Among these inorganic vapor deposition layer forming methods, when forming a wide film, the sputtering method is preferable at the point that the film thickness uniformity, adhesiveness, productivity, and yield of the width direction can be improved.

The base film 1 which comprises the multilayer film of this invention needs to be a resin 1 agent whose glass transition temperature (Tg) is 80 degreeC or more. In the manufacturing process of the multilayer film of this invention, and the manufacturing process of a laminated body, heating is normally performed and when using for an electronic device, a heating process may also be included in the manufacturing process. When the glass transition temperature (Tg) of the said resin 1 is less than 80 degreeC, the heat resistance temperature at the time of these heating processes falls, and the reliability of adhesive strength falls. In order to maintain heat resistance, such as heat resistance of a product and heat resistance of a manufacturing process, the higher the heat resistance of a base film, the better. Therefore, it is preferable that Tg of resin 1 which comprises base film 1 is 120 degreeC or more. In addition, since the glass transition temperature (Tg) of the resin 1 is greater than or equal to the Tg of the resin 2 constituting the adhesive resin layer, it is possible to prevent melting when the multilayer film is heated to a temperature close to the Tg of the adhesive resin layer and laminated on the substrate. It is preferable because there is.

As resin 1 (polymer) used for the base film 1, For example, alicyclic structure containing resin, such as norbornene resin, monocyclic cyclic olefin resin, cyclic conjugated diene resin, vinyl alicyclic hydrocarbon resin, and these hydrogenated substances; Linear olefin resins such as polyethylene and polypropylene; Polycarbonate resins; Polyester resins; Polysulfone resins; Polyethersulfone resins; Polystyrene resins; Polyamide resins; Acrylic resins; Methacrylate resins; Polyimide resin etc. are mentioned. Among them, from the group consisting of polyester resins, polyethersulfone resins, chain olefin resins, alicyclic structure-containing resins, polycarbonate resins, acrylic resins, methacrylate resins, polystyrene resins, polyamide resins, and polyimide resins At least 1 sort (s) of resin chosen is preferable. Among these, high transparency is preferable. Especially, alicyclic structure containing resin, polyester resin, polyimide resin, and polycarbonate resin are especially preferable from a viewpoint of transparency, low hygroscopicity, dimensional stability, light weight, etc.

The thickness of the base film 1 becomes like this. Preferably it is 5-300 micrometers, More preferably, it is 15-200 micrometers.

The adhesive resin layer used for the multilayer film of this invention is a layer containing resin 2 which has an adhesive function with the inorganic material (inorganic material 2) which comprises the inorganic material layer of a board | substrate in the laminated body mentioned later. In the present invention, adhesion possible means that the 10-mm width and 90-degree peeling strength at the time of joining with the inorganic material 2 which comprises the inorganic material layer of the board | substrate mentioned later are 400g / 10mm or more.

Specifically, the adhesive resin layer is preferable because it can be made of a resin containing a solvent or dissolved in a solvent, and the adhesiveness with the resin 1 constituting the base film 1 can be improved thereby. In addition, the said adhesive resin layer should just be a layer containing adhesive resin 2 as mentioned above, and may consist of resin which does not contain a solvent.

In the case where the adhesive resin layer is composed of resin 2 containing a solvent, the content of the solvent in the adhesive resin layer is preferably 0.2 to 2.3% by weight, more preferably 0.4 to 1.8% by weight, particularly preferably 0.8 To 1.0% by weight. Solvent content can be measured by internal standard method gas chromatography. That is, a solvent content can be computed by melt | dissolving a multilayer film in the solvent different from the solvent used for the adhesive resin layer, and using the solvent used for the adhesive resin layer as an internal standard liquid.

In this invention, resin 2 which comprises an adhesive resin layer is not specifically limited, Resin which has the structure similar to or similar to resin 1 used for the base film 1 can be used. Specifically, acrylic resin, polyester resin, linear olefin resin, and alicyclic structure containing resin are mentioned. Especially, an alicyclic structure containing resin is preferable from a transparency viewpoint.

The alicyclic structure-containing resin has an alicyclic structure in the main chain and / or the side chain, and preferably has an alicyclic structure in the main chain from the viewpoint of mechanical strength, heat resistance and the like. Examples of the alicyclic structure of the resin include a saturated alicyclic hydrocarbon (cycloalkane) structure, an unsaturated alicyclic hydrocarbon (cycloalkene) structure, and the like, but a cycloalkane structure is preferable from the viewpoint of mechanical strength and heat resistance. Although the number of carbon atoms constituting the alicyclic structure is not particularly limited, the mechanical strength, heat resistance, and moldability of the film in the range of usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 The characteristics are highly balanced and suitable. Although the ratio of the repeating unit which contains the alicyclic structure in alicyclic structure containing resin used suitably for this invention may be suitably selected according to a use purpose, Preferably it is 30 weight% or more, More preferably, 50 weight% or more , Particularly preferably at least 70% by weight, most preferably at least 90% by weight. When the ratio of the repeating unit which has alicyclic structure in alicyclic structure containing resin exists in this range, it is preferable from the viewpoint of transparency and heat resistance of a base film and an adhesive resin layer.

The alicyclic structure-containing resin specifically includes (1) norbornene resin, (2) monocyclic cyclic olefin resin, (3) cyclic conjugated diene resin, (4) vinyl alicyclic hydrocarbon resin, and hydrogenated substances thereof. Can be mentioned. Among these, norbornene resin and cyclic conjugated diene resin are more preferable from a viewpoint of transparency and moldability.

(1) Examples of the norbornene resin include a ring-opening polymer of a norbornene monomer, a ring-opening copolymer of a norbornene monomer and another monomer capable of ring-opening copolymerization with respect to the norbornene monomer, a hydride of these ring-opening copolymers, and a norbornene monomer. The addition polymer, the addition copolymer of a norbornene monomer, and the other monomer copolymerizable with this norbornene monomer, etc. are mentioned. Among these polymers and copolymers, the hydride of the ring-opening (co) polymer of the norbornene monomer is particularly preferable from the viewpoint of the heat resistance and mechanical strength of the alicyclic structural polymer composition obtained.

(2) As monocyclic cyclic olefin resin, the addition polymer of the cyclic olefin monomer which has monocycles, such as cyclohexene, cycloheptene, and cyclooctene, is mentioned.

(3) As cyclic conjugated diene resin, the polymer obtained by cyclizing the addition polymer of conjugated diene monomers, such as 1, 3- butadiene, isoprene, and chloroprene; 1,2- or 1,4-addition polymers of cyclic conjugated diene monomers, such as cyclopentadiene and cyclohexadiene; And these hydrides.

(4) As a vinyl alicyclic hydrocarbon resin, Polymer of vinyl alicyclic hydrocarbon type monomers, such as vinyl cyclohexene and vinyl cyclohexane, and its hydride; Hydride formed by hydrogenating the aromatic ring part contained in the polymer which polymerizes vinyl aromatic hydrocarbon monomers, such as styrene and (alpha) -methylstyrene; And hydrides of aromatic ring portions of copolymers such as random copolymers or block copolymers of vinyl alicyclic hydrocarbon monomers or vinyl aromatic hydrocarbon monomers and other monomers copolymerizable with these vinyl aromatic hydrocarbon monomers. As a block copolymer, a die block, a tri block, or more multiblock, a gradient block copolymer, etc. are mentioned.

Said alicyclic structure containing resin is chosen from the well-known polymer disclosed, for example in Unexamined-Japanese-Patent No. 2002-321302.

The glass transition temperature of resin 2 which comprises an adhesive resin layer becomes like this. Preferably it is 40-190 degreeC, More preferably, it is 50-160 degreeC, Especially preferably, it is 60-145 degreeC.

In this invention, resin 2 which comprises an adhesive resin layer has a polar group. Thereby, adhesiveness with the inorganic material 2 contained in a board | substrate can be improved more. As such a polar group, an acid anhydride group, an epoxy group, a carboxyl group, an acid amide group, an isocyanate group, a hydroxyl group, a cyano group, etc. are mentioned, Among these, an acid anhydride group, an epoxy group, or both have It is preferable. Thereby, adhesiveness with a board | substrate can be improved further. The content of the polar group in the resin 2 constituting the adhesive resin layer is preferably 0.5 to 25 mol%, more preferably 1.2 to 15 mol%, particularly preferably 1.5 to 12 mol% in an amount per 100 g of the resin.

In the multilayer film of this invention, there is no restriction | limiting in particular in the method of forming an adhesive resin layer. For example, after providing an inorganic thin film layer on the base film 1, an adhesive resin layer can be formed on it. In the case where the inorganic thin film layer is formed on the base film 1 and then the adhesive resin layer is formed thereon, it is preferable to perform the coupling agent treatment using aminopropyl trimethoxysilane or the like on the inorganic thin film layer in advance. The height is preferable at the point. It is especially preferable when using resin which has an acid anhydride group as resin 2 which comprises an adhesive resin layer.

There is no restriction | limiting in particular as a method in the case of providing an inorganic thin film layer on the base film 1, and forming an adhesive resin layer thereon, The solution casting method and the melt-extrusion method are mentioned. Among these, the solution casting method is preferable at the point which can coat the thickness of an adhesive resin layer as uniformly as possible, and can make solvent content in a multilayer film into a desired quantity. In the case of forming the adhesive resin layer by the solution casting method, the material constituting the adhesive resin layer is dissolved in a suitable solvent to obtain a varnish, and the inorganic thin film layer is subjected to reverse roll coating, gravure coating, air knife coating, blade coating, or the like. It is good to coat on a phase and to dry after that in order to remove a solvent. Drying conditions are suitably selected according to the kind of solvent to be used. As a solvent which can be used when forming an adhesive resin layer, ketones, ethers, esters, aromatic hydrocarbons, and its hydrogenated substance are mentioned. These may be used individually by 1 type or may combine two or more types.

Preferably the thickness of an adhesive resin layer is 1-50 micrometers, More preferably, it is 3-15 micrometers.

In the multilayer film of the present invention, it is preferable that the thermal expansion coefficient measured in the temperature range of 80 to 120 ° C. of the multilayer film is the same as the thermal expansion ratio of the base film 1 or exhibits a large value in the range of 30 ppm or less. By making the difference of thermal expansion coefficient into the said range, while maintaining sufficient adhesiveness of the board | substrate containing the multilayer film of this invention and an inorganic material layer, the residual stress of the board | substrate after adhesion can be suppressed. As a result, effects such as reduction of warpage of the substrate after adhesion, prevention of peeling of the adhesive interface, and prevention of cracking of the inorganic material layer can be obtained. In addition, the thermal expansion rate in this invention is a linear expansion rate unless it is specifically determined.

The thermal expansion coefficient is measured by the following method using a commercial thermomechanical analyzer (TMA). The multilayer film is cut to a predetermined size. And the cut multilayer film is set to a thermomechanical analysis apparatus, and it heats up at a speed | rate of 5 degreeC per minute from room temperature under nitrogen atmosphere, applying a load of 0.1N, and measures a thermal expansion rate in the temperature range of 80-120 degreeC. Although this measurement is performed normally, in that case, it is preferable that the measured value of the thermal expansion coefficient of the 1st time especially in the 1st time and the 2nd time becomes the said range especially. The reason is that the solvent evaporates and scatters by the first thermal expansion coefficient measurement, so even if the second measurement is performed after cooling the adhesive resin after the first measurement, the measured value is the original value of the resin regardless of the amount of the solvent. This is because the coefficient of thermal expansion is close to.

When laminating | stacking the multilayer film of this invention to the board | substrate etc. which contain an inorganic material layer, it is common to heat up normally, and since the one part of the solvent in an adhesive resin layer evaporates and scatters at that time, the obtained laminated body is a solvent of an adhesive resin layer. It disappears and the thermal expansion rate of resin in an adhesive resin layer approaches the resin original thermal expansion rate. As a result of quantitative examination, the multilayer film whose thermal expansion rate measured in the temperature range of 80-120 degreeC is equal to the thermal expansion rate of the base film 1 or shows a large value in 30 ppm or less is laminated | stacked on the board | substrate containing an inorganic material layer. In one case, good adhesion was confirmed.

The multilayer film of this invention has adhesiveness with the inorganic material of a board | substrate, maintaining the characteristic of a base film. The total light transmittance of a multilayer film can be maintained at 85% or more by using the base film whose total light transmittance in wavelength 400-650 nm is 88% or more. This becomes a film with high light transmittance, and is useful as optical materials, such as liquid crystal TFT. In addition, the total light transmittance in wavelength 400-650 nm can be measured using a commercially available turbidimeter based on JISK7361-1. Moreover, by using the base film of a low thermal expansion rate, the thermal expansion rate of a multilayer film can also be suppressed low, and the residual stress with respect to the board | substrate containing an inorganic material layer can be reduced.

Such a multilayer film of the present invention can be used as a material of a laminate useful for a TFT substrate and the like, and the present invention also provides such a laminate. That is, this invention is a laminated body which laminates the board | substrate which has the said inorganic material layer which consists of inorganic material 2 on the surface, and the said multilayer film so that the said inorganic material layer of the said board | substrate and the said adhesive resin layer of the said multilayer film may contact. To provide.

The board | substrate used for the laminated body of this invention should just be a board | substrate which has the inorganic material layer which consists of inorganic materials 2. That is, the substrate which consists only of an inorganic material layer may be sufficient, and the board | substrate which has an inorganic material layer as one of the structural layers may be sufficient. In addition, the inorganic material layer may not be one, or may contain two or more different inorganic material layers. An inorganic material layer can be made into a glass layer, a metal layer, a metal oxide layer, etc., for example. In particular, the glass layer is useful because it is used for many TFT substrates and the like.

There is no restriction | limiting in particular in the thickness of a board | substrate, According to the use and a characteristic of a laminated body, the material which comprises an inorganic material layer, etc., it can determine suitably.

In the case where the laminate is flexible, when the substrate is made of only an inorganic material layer, the thickness can be 0.1 to 500 µm, and preferably 1 to 200 µm. Moreover, when a board | substrate is a structure provided with an organic material layer and the inorganic material layer provided on this organic material layer, the thickness of an inorganic material layer can be 0.05-10 micrometers, and it is preferable that it is 0.1-2 micrometers. And the thickness of an organic material layer can be 5-300 micrometers normally, and it is preferable that it is 15-200 micrometers.

On the other hand, when a laminated body is rigid, the thickness of a board | substrate is not specifically limited.

Here, as said organic material layer, it can be set as the base film 3 made from resin 3 whose glass transition temperature (Tg) is 80 degreeC or more. In this case, it is preferable that the above-mentioned inorganic material layer is an inorganic thin film layer deposited on at least one surface of the base film 3 made of the said resin 3. Here, an inorganic thin film layer is the same as what was mentioned in the description part of the inorganic thin film layer in the multilayer film of the said invention. Moreover, the thing similar to what was said by the description part of resin 1 which comprises the base film 1 in the multilayer film of this invention also the base film 3 made from resin 3 whose glass transition temperature (Tg) is 80 degreeC or more.

While the laminated body of this invention adhere | attaches the board | substrate containing the multilayer film of this invention and an inorganic material layer with good adhesiveness, it is required to hold | maintain transparency by suppressing peeling and deformation of the laminated body after adhesion | attachment. Therefore, such a small amount of solvent is usually contained in the adhesive resin layer of a multilayer film, and a residual solvent acts as a plasticizer at the time of adhesion | attachment, and reduces adhesive temperature. As a result, the residual stress on the substrate after adhesion is reduced. Therefore, the method of adhering the multilayer film and the substrate has an important influence on the adhesion at the time of adhesion and also the durability after the adhesion. This invention also provides the manufacturing method of such a laminated body.

The manufacturing method of the laminated body of this invention is a multilayer film of the said invention, Comprising: The board | substrate containing the multilayer film which is resin whose glass transition temperature of resin 2 which has the said polar group in this film is 40 degreeC or more, and the said inorganic material layer, 40 It includes the step of adhering at a temperature equal to or lower than the glass transition temperature of the resin 2 having a polar group, which constitutes the adhesive resin layer of the multilayer film.

In the manufacturing method of this invention, it is necessary to make adhesive temperature into 40 degreeC or more. When the temperature is lower than 40 ° C, the adhesion between the adhesive resin layer of the multilayer film and the inorganic material layer of the substrate is poor, and peeling easily occurs. Moreover, the solvent in an adhesive resin layer remains as it is, and the thermal expansion rate of the adhesive resin layer of the manufactured laminated body becomes large, and there exists a possibility of foaming by vaporization of a solvent by the temperature change in use.

In the manufacturing method of this invention, it is also necessary to adhere | attach at the temperature below the glass transition temperature of resin 2 which has a polar group in a multilayer film. When bonding at a temperature higher than the glass transition temperature, there is a fear that the adhesive resin layer melts at the time of adhesion, causing a large expansion or deformation of the multilayer film. As mentioned above, in the manufacturing method of this invention, since adhesive temperature needs to be 40 degreeC or more, the glass transition temperature of resin 2 which has a polar group needs to be 40 degreeC or more, Preferably it is 40-190 degreeC, More preferable Preferably it is 50-160 degreeC, Especially preferably, it is 60-145 degreeC. On the other hand, it is not preferable to also make resin 1 used for the base film 1 at the time of adhesion more than glass transition temperature. In addition, in this invention, an adhesion temperature refers to the temperature of the machine used for adhesion | attachment, for example, a laminator.

By bonding the thin film of 200 micrometers or less in thickness as a board | substrate to the multilayer film of this invention, the flexible and transparent laminated body of this invention which has complete glass barrier property can be produced. A conductive flexible thin film transparent glass substrate can be provided by forming a transparent conductive material such as an ITO vapor deposition layer onto the glass surface of the laminate before or after bonding.

The laminate of the present invention can be applied to flexible electronic devices, FPD substrates, IC card substrates, solar cell substrates, and the like using TFTs.

Although this invention is demonstrated further in detail, showing an Example and a comparative example, this invention is not limited only to a following example.

Parts and percentages, on the other hand, are by weight unless otherwise specified.

(1) Evaluation method of resin which comprises base film, resin which comprises adhesive resin layer, multilayer film, or laminated body

Glass transition temperature (called Tg):

Based on JISK7211, it measures by heating up at 10 degree-C / min by the differential scanning calorimetry (called a DSC method).

Maleization rate:

It calculates as mol% in resin conversion (per 100 g) by a titration method.

Epoxidation Rate:

^It calculates as mol% in resin conversion (per 100 g) from 1H-NMR measurement value.

Resin solution viscosity:

It measures at 25 degreeC using the E-type viscosity meter of the Tokyo Keiki company.

Thermal expansion coefficient of base film and multilayer film:

Using a thermomechanical analyzer (TMA), measurement is carried out under conditions of a sample shape of 20 mm x 10 mm, a temperature increase rate of 5 ° C per minute, and a load of 0.1 N. The measurement procedure is shown below. The thermal expansion rate of 80-120 degreeC is measured at the time of 1st heating, and it cools to room temperature after a measurement. At the time of 2nd heating, the thermal expansion rate of 80-120 degreeC is measured again. Subtracting the second measured value from the first measured value is calculated as the rising value.

Solvent content (residual solvent) in a multilayer film:

The multilayer film is cut out (about 200 mg) and weighed accurately. 5 ml of tetrahydrofuran containing toluene as an internal standard is precisely weighed, and the multilayer film cut out to this is added and dissolved to obtain a solution for measurement. The obtained solution is measured by internal standard method by gas chromatography with a frame ion detector.

(2) Synthesis of Adhesive Resin

Synthesis Example 1: Preparation of Adhesive Resin M1

6-methyl-1,4: 5,8-dimethano-1,4,4a, 5, which is an alicyclic structure-containing resin, in a reactor equipped with a cooling tube, a nitrogen gas introduction tube, and a dynamic pressure dropping funnel; 201 parts of a hydrogenated substance of the ring-opened polymer of 6,7,8,8a-octahydronaphthalene (Tg = 140 degreeC, hydrogenation rate 100%, Mn = about 28000, "hydrogenated MTD resin") 201 parts, maleic anhydride 6.37 parts of acids and 470.4 parts of t-butylbenzene were put, and it heated at 135 degreeC under nitrogen gas atmosphere, and melt | dissolved resin uniformly. The homogeneous solution which melt | dissolved 1.76 parts of dicumyl peroxides in 33.4 parts of cyclohexanone was dripped at this resin solution over 2 hours, maintaining reaction liquid temperature at 135 degreeC. Furthermore, after continuing reaction for 3 hours at 135 degreeC, the reaction liquid was cooled to room temperature. 2000 parts of toluene was added to this reaction liquid to make a homogeneous dilution solution. The homogeneous dilution solution was added dropwise into the mixed solution of 7000 parts of isopropyl alcohol and 2000 parts of acetone to solidify the resin. The obtained resin was separated by filtration, followed by vacuum drying at 105 ° C. for 12 hours to obtain maleic acid-modified hydrogenated MTD resin. This resin was referred to as adhesive resin M1. The physical properties of the obtained adhesive resin M1 are summarized in Table 1 and described.

Synthesis Example 2: Preparation of Adhesive Resin E1

After 50 parts of hydrogenated MTD resin, 10 parts of allyl glycidyl ether, 1.5 parts of dicumyl peroxide, and 200 parts of cyclohexane were reacted at 150 DEG C for 3 hours in an autoclave, the reaction solution was poured into 500 parts of acetone. The product solidified. The obtained resin was separated by filtration and then vacuum dried at 105 ° C. for 12 hours to obtain an epoxy-modified hydrogenated MTD resin. This was set as adhesive resin E1. The physical properties of adhesive resin E1 are summarized in Table 1 and described.

Synthesis Example 3: Production of Adhesive Resin MIR-1

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 83% cis-1,4-structure isoprene unit and 15%, 3,4-trans-1,4-structure isoprene unit 2 parts of structural isoprene units, 100 parts of polyisoprene having a weight average molecular weight of 136,000, and 1570 parts of toluene were added. After nitrogen replacement of the flask, the polyisoprene was completely dissolved by heating to 85 ° C in an oil bath and then stirring. And 3.9 parts of p-toluenesulfonic acid were added to this solution, stirring was continued and the cyclization reaction was performed, maintaining solution temperature at 85 degreeC. Five hours after the start of the cyclization reaction, 400 parts of ion-exchanged water was added to this solution to stop the cyclization reaction. 30 minutes after adding ion-exchanged water, the oil layer was separated. The oil layer was washed three times with 400 parts of ion-exchanged water, and then centrifuged at 300 rpm to remove water. The remaining oil layer was heated to 130 ° C. to completely remove moisture. After adding 3.5 parts of maleic anhydride to the oil layer from which this water was completely removed, stirring and homogenizing, the reaction temperature was raised to 160 degreeC and dilution of toluene was carried out. Then, addition reaction was performed at 160 degreeC for 4 hours. Subsequently, the temperature of the oil layer was cooled to 110 degreeC, 1000 ppm of antioxidants (Irganox 1010 by Chiba Specialty Chemicals Co., Ltd.) were added to resin, it was homogenized, and it cooled to room temperature, and obtained maleic acid modified cyclization isoprene. This was made into adhesive resin MIR-1. The physical properties of the obtained adhesive resin MIR-1 are summarized in Table 1 and described.

In Table 1, a cyclization rate shows the cyclization rate of cyclized isoprene. The cyclization rate was computed from the peak area of the proton derived from the double bond before and after the cyclization reaction of a conjugated diene double bond by proton NMR. On the other hand, the detailed measurement method is (i) m. A. Golub and J. Heller., Can. Reference was made to the method described in J. Chem., 41, 937 (1963).

Production Example-1 Preparation of Inorganic Deposition Layer on Norbornene Resin Film

As a saturated hydrocarbon resin having an alicyclic structure, a norbornene resin film (manufactured by OPTES Co., Ltd., Zeonoa film ZF-16, 100 µm thick, 91% total light transmittance at a wavelength of 400 to 650 nm, and the base film are described as 1B). 1B was loaded on the unwinding roll 2 of the continuous vacuum sputtering apparatus (direct current magnetron sputtering apparatus) shown in FIG. 1, and vacuum exhaust was started until the pressure of a vacuum chamber reached 1 * 10 <^-5> Pa. On the other hand, silicon was used as the material constituting the inorganic vapor deposition layer, and oxygen was used as the reactive gas for this target. Silicon was charged to the target 5-1.

After the pressure in the vacuum chamber reached 1 × 10 ^-5 Pa, the film forming roll 4 was set to 40 ° C., and a silicon oxide (SiO _x , x = 2) layer having a refractive index of 1.46 was formed to a film thickness of 100 nm, It wound up by the winding roll 7 and obtained resin film 1E with an inorganic vapor deposition layer.

Sputtering was performed on condition of the following.

<Sputtering condition>

Vacuum Reach: 1 × 10 ^-5 Pa

Working vacuum degree: 0.3Pa

Discharge gas: 150SCCM

Power density: 4 ㎾ / ㎠

Production Example-2 Preparation of Inorganic Deposited Layer on Polyester Resin Film

A polyester resin film (PEN Q51-50 µm: manufactured by Teijin DuPont Film Co., Ltd., 60% total light transmittance at a wavelength of 400 to 650 nm, and the base film is described as 2B) instead of a norbornene resin film as a resin film. Similarly, the silicon oxide layer was formed at 100 nm and the resin film 2E with an inorganic vapor deposition layer was obtained.

Production Example-3 Preparation of Inorganic Deposition Layer on Low Thermal Expansion Polyimide Film

The low thermal expansion type polyimide varnish was manufactured by the method of Example 1 of Unexamined-Japanese-Patent No. 2004-285129. This varnish was coated on a 20 cm silicone using a spin coater, prebaked at 100 ° C. for 3 minutes on a hot plate, and then baked at 400 ° C. in an oven under nitrogen stream for 1 hour to prepare a polyimide film. The film thickness of this film formed into a film (this base film is described as 3B. 75% of the total light transmittance in wavelength 400-650 nm) was 18 micrometers. Moreover, it was 3.2 ppm when the film was peeled off from the silicon wafer and the thermal expansion coefficient of the film | membrane was measured. Similarly-prepared polyimide film / (to be fixed on a silicon wafer) by a sputtering method on the surface to form a SiO ₂ layer 100㎚ inorganic vapor deposition layer adhered to obtain a resin film 3E.

Sputtering in this manufacture example was performed on condition of the following using the sputter apparatus CFS-4EP-LL by the Shivaura Mechatronics company.

Sputtering Conditions: Rf 400 W, Pressure 0.5 MPa, SiO ₂ Target, 60 Seconds

Production Example-4 Preparation of Inorganic Deposition Layer on Polycarbonate Film

A polycarbonate film (Sumilite FS-1650H, 100 micrometers film thickness, Tg = 145 degreeC, this base film is described as 4B instead of the norbornene resin film as a resin film. Total light in wavelength 400-650 nm. Using a transmittance of 90%), a silicon oxide layer was formed at 100 nm under the same conditions as in Production Example 1 to obtain a resin film 4E with an inorganic vapor deposition layer.

In addition, in manufacture example-1-manufacture example-4, the measurement of the total light transmittance in wavelength 400-650 nm was performed with the turbidimeter (The Nippon Denshoku Industries Co., Ltd., haze meter NDH2000) based on JISK7361-1.

Production Example-5: Preparation of Silicon Metal Deposition Layer on Norbornene Resin Film]

Under the conditions of Preparation Example 1, a silicon metal deposited thin film having a film thickness of 110 nm was formed on the film by sputtering without using silicon as a material constituting the deposition layer and introducing a reactive gas (oxygen) to deposit metal. The resin film 5E with a layer was obtained. Although the silicon metal deposited thin film was colored in dark brown, it was possible to form a uniform and adherent metal thin film on the film. Sputtering conditions were made into the conditions similar to the conditions of manufacture example 1 except not introducing a reactive gas.

Production Example-6 Preparation of Silicon Metal Deposition Layer on Norbornene Resin Film

In the manufacture example-3, the resin film 6E with a metal vapor deposition layer was similarly obtained except having used aluminum as a target using the norbornene resin film used by manufacture example-1 instead of the base film 3B.

Example 1 Preparation of Multilayered Film (Multilayer Film) 1F

The silicon oxide surface of the resin film 1E with an inorganic vapor deposition layer produced in Production Example-1 was soaked in a silane coupling agent (aminopropyltrimethoxysilane) vapor for 120 seconds to perform a surface treatment. The uniform varnish (resin concentration of 24 Wt%) in which the adhesive resin M1 synthesized in Synthesis Example-1 was dissolved in cyclopentyl methyl ether on the silicon oxide layer was uniformly coated using a doctor blade. After coating, it dried for 15 minutes at 105 degreeC in the clean oven, and manufactured multilayered film 1F. The film thickness of the adhesive resin layer was 10 micrometers. The properties of the multilayered film 1F are shown in Table 2.

Example 2 Preparation of Multilayered Film 2F

Under the conditions of Example 1, a multilayer film 2F was produced in the same manner except that the adhesive resin E1 synthesized in Synthesis Example-2 was used instead of the adhesive resin M1 synthesized in Synthesis Example-1. In this Example 2, the adhesive resin varnish was directly coated and dried without the coupling agent treatment to the inorganic vapor deposition layer. The properties of the multilayered film 2F are shown in Table 2. As shown in Table 2, it became clear that multilayer film 2F showed high adhesiveness similarly to the film 1F of Example 1 which performed the said process although the coupling agent process was not performed.

Example 3 Preparation of Multilayered Film 3F

In the conditions of Example 1, instead of the adhesive resin M1 synthesized in Synthesis Example-1, the adhesive resin MIR-1 synthesized in Synthesis Example-3 was used, and the others were manufactured under the same conditions as in Example 1 to produce a multilayered film 3F. . The properties of the multilayer film 3F are shown in Table 2.

Example 4 Preparation of Multilayered Film 4F

In the conditions of Example 1, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 2E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 4F on the same conditions as Example 1. FIG. The properties of the multilayered film 4F are shown in Table 2.

Example 5 Preparation of Multilayered Film 5F

In the conditions of Example 2, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 2E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 5F under the same conditions as Example 2. The properties of the multilayered film 5F are shown in Table 2.

Example 6 Preparation of Multilayered Film 6F

In the conditions of Example 3, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 2E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 6F under the same conditions as Example 3. FIG. The properties of the multilayered film 6F are shown in Table 2.

Example 7 Preparation of Multilayered Film 7F

In the conditions of Example 1, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 3E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 7F under the same conditions as Example 1. FIG. The properties of the multilayered film 7F are shown in Table 2.

Example 8 Preparation of Multilayered Film 8F

In the conditions of Example 2, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 3E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 8F under the same conditions as Example 2. The properties of the multilayered film 8F are shown in Table 2.

Example 9 Preparation of Multilayered Film 9F

In the conditions of Example 3, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 3E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 9F under the same conditions as Example 3. FIG. The properties of the multilayered film 9F are shown in Table 2.

Example 10 Preparation of Multilayered Film 10F

In the conditions of Example 1, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 4E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 10F under the same conditions as Example 1. FIG. The properties of the multilayered film 10F are shown in Table 2.

Example 11

In the conditions of Example 2, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 4E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 11F under the same conditions as Example 2. The properties of the multilayered film 11F are shown in Table 2.

Example 12

In the conditions of Example 3, instead of the resin film 1E with an inorganic vapor deposition layer, the resin film 4E with an inorganic vapor deposition layer was used, and the others produced the multilayered film 12F under the same conditions as Example 3. FIG. The properties of the multilayered film 12F are shown in Table 2.

Example 13

In the conditions of Example 1, instead of the resin film 1E with an inorganic deposition layer, the resin film 5E with a metal deposition layer was used, and instead of the adhesive resin M1 synthesized in Synthesis Example-1, the adhesive resin E1 synthesized in Synthesis Example-2 was used. In the other conditions, the multilayer film 13F was manufactured on the conditions similar to Example 1. The properties of the multilayered film 13F are shown in Table 2.

Example 14

In the conditions of Example 1, instead of the resin film 1E with an inorganic deposition layer, the resin film 6E with a metal deposition layer was used, and instead of the adhesive resin M1 synthesized in Synthesis Example-1, the adhesive resin E1 synthesized in Synthesis Example-2 was used. In addition, the multilayer film 14F was manufactured on the other conditions and the same conditions as Example 1. The properties of the multilayered film 14F are shown in Table 2.

Comparative Example 1

Instead of the 1E film used in Example 1, the varnish which melt | dissolved adhesion function resin M1 was directly coated to the base film 1B. After coating, it dried for 15 minutes at 105 degreeC in the clean oven, and manufactured multilayered film R1. The results are shown in Table 2.

When the adhesive resin varnish was coated on the base film without the inorganic vapor deposition layer, a solvent infiltrated the base film and the residual solvent increased. As a result, the coefficient of thermal expansion (at the time of the first measurement) was large.

Comparative Example 2

Instead of the 1E film used in Example 2, the varnish which melt | dissolved adhesion function resin E1 was directly coated to the base film 1B. After coating, it dried for 15 minutes at 105 degreeC in the clean oven, and manufactured multilayered film R2.

When the adhesive resin varnish was coated on the base film without the inorganic vapor deposition layer, a solvent infiltrated the base film and the residual solvent increased. As a result, the coefficient of thermal expansion (at the time of the first measurement) was large. The results are shown in Table 2.

Comparative Example 3

Instead of the 2E film used in Example 5, the varnish which melt | dissolved adhesive function resin E1 was coated directly on the base film 2B. After coating, it dried for 15 minutes at 105 degreeC in the clean oven, and manufactured multilayered film R3. The adhesiveness of the base film 2B which does not have an inorganic vapor deposition layer, and an adhesive resin layer was bad, and it turned out that an inorganic vapor deposition layer is needed for adhesive expression. The results are shown in Table 2.

[Comparative Example 4]

After the base film 2B surface was corona-treated and the coupling agent process, the varnish which melt | dissolved adhesive resin E1 was coated. After coating, it dried for 15 minutes at 105 degreeC in the clean oven, and manufactured multilayered film R4. Although the adhesiveness of a coating adhesive resin layer and a base film improved, it was insufficient. The results are shown in Table 2.

[Comparative Example 5]

Instead of the 3E film used in Example 8, the varnish which melt | dissolved adhesive function resin E1 was coated directly on the polyimide base film 3B. After coating, it dried for 15 minutes at 105 degreeC in the clean oven, and manufactured multilayered film R5. The adhesiveness of a coating adhesive resin layer and base film 3B was bad. The results are shown in Table 2.

In Table 2, "1B", "2B", "3B", and "4B" are a norbornene resin film (100 micrometers thick), a polyester resin film (50 micrometers thick), and a low thermal expansion polyimide film (18 micrometers thick, respectively). ) And a polycarbonate film (Semilite FS-1650H, 100 µm film thickness). About these base films, the thermal expansion rate in single was measured twice at 30-130 degreeC, and the average thermal expansion rate of the temperature range of 80-120 degreeC was shown.

In addition, the procedure and the criterion of the adhesive test in Table 2 are as follows.

Adhesive test

After washing and drying the white glass (made by Dow Corning) surface of thickness 0.7mm, it dipped in the silane coupling agent (aminopropyl trimethoxysilane) steam for 120 second, and surface-treated. The glass which performed this surface treatment and the adhesive resin layer of a multilayer film were put together, and the laminated laminated body was obtained by the vacuum laminator. Joining conditions were vacuum suction 60 second, the bonding temperature of 80 degreeC, the bonding time of 300 second, and the bonding pressure of 0.9 Mpa. The obtained laminated body was 90 degree peeling test on the conditions of width 10mm and peeling speed 5mm / min, and it judged on the following references | standards.

(Circle): Peeling strength is 400 g / 10 mm or more.

X: Peeling strength is less than 400 g / 10 mm.

Example 15 Preparation of Laminate 1

A 50-micrometer-thick glass film (manufactured by Matsunami Glass Co., Ltd.) was immersed in 0.1% aminopropyltriethoxy aqueous solution for 2 minutes, and then dried at room temperature for 24 hours. The laminated body 1 was obtained by bonding this glass film and the adhesive resin layer of the multilayered film 1F obtained in Example 1, and vacuum-laminating so that a bubble may not be produced using a vacuum laminator. Vacuum lamination conditions were 15 seconds of vacuum suction, the bonding temperature of 80 degreeC, the bonding time of 360 seconds, and the bonding pressure of 0.8 Mpa. The results are shown in Table 3.

Although the obtained laminated body 1 was curved to the multilayered film side by the difference in the thermal expansion rate of glass and a multilayered film at room temperature, even if it fixed mechanically flat, there was no peeling at the interface of a glass film and a multilayered film, and the crack of the thin film glass film did not generate | occur | produce. Moreover, the total light transmittance in wavelength 400-650 nm was 90%, and was excellent in transparency.

Example 16 Preparation of Laminate 2

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 2F was used instead of the multilayered film 1F to produce the laminate 2. The results are shown in Table 3. Laminate 2 also exhibited good properties similar to laminate 1. Moreover, the laminated body 2 was also excellent in transparency similar to the laminated body 1.

Example 17 Preparation of Laminate 3

In the conditions of Example 15, the laminated body 3 was manufactured similarly to Example 15 except having used the multilayered film 3F instead of the multilayered film 1F, and making adhesive temperature 60 degreeC. The results are shown in Table 3. Laminate 3 also exhibited good properties similar to laminate 1. Moreover, the laminated body 3 was also excellent in transparency similar to the laminated body 1.

Example 18 Preparation of Laminate 4

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 4F was used instead of the multilayered film 1F to produce the laminate 4. The results are shown in Table 3. The obtained laminated body 4 had little difference in the thermal expansion rate of glass and a multilayered film, and as a result, the curvature of the board | substrate at normal temperature was significantly reduced.

Example 19 Preparation of Laminate 5

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 5F was used instead of the multilayered film 1F, and the laminate 5 was manufactured. The results are shown in Table 3. The laminated body 5 also showed the favorable property similarly to the laminated body 4.

Example 20 Preparation of Laminate 6

Under the conditions of Example 15, the laminated body 6 was manufactured similarly to Example 15 except having used the multilayered film 6F instead of the multilayered film 1F, and making adhesive temperature 60 degreeC. The results are shown in Table 3. Laminate 6 also exhibited good properties similar to laminate 4.

Example 21 Preparation of Laminate 7

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 7F was used instead of the multilayered film 1F to produce a laminate 7. The results are shown in Table 3. Since the thermal expansion rate of the base film used by the laminated body 7 was smaller than glass, and the difference is small by several ppm, the curvature of the laminated body after adhesion was hardly at room temperature or 80 degreeC overheating.

Example 22 Preparation of Laminate 8

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 8F was used instead of the multilayered film 1F to produce the laminate 8. The results are shown in Table 3. Laminate 8 also exhibited good properties similar to laminate 7.

Example 23 Preparation of Laminate 9

In the conditions of Example 15, the laminated body 9 was manufactured similarly to Example 15 except having used the multilayered film 9F instead of the multilayered film 1F, and making adhesive temperature 60 degreeC. The results are shown in Table 3. Laminate 9 also exhibited good properties similar to laminate 7.

Example 24 Preparation of Laminate 10

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 10F was used instead of the multilayered film 1F to produce the laminate 10. The results are shown in Table 3. Although the curvature of the laminated body 10 was equivalent to the laminated body 1, the surface hardness of the used base film was high and the usefulness was anticipated.

Example 25 Preparation of Laminate 11

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 11F was used instead of the multilayered film 1F to produce the laminate 11. The results are shown in Table 3.

Example 26 Preparation of Laminate 12

In the conditions of Example 15, the laminated body 12 was produced like operation 15 except having used the multilayered film 12F instead of the multilayered film 1F, and making adhesive temperature 60 degreeC. The results are shown in Table 3.

Example 27 Preparation of Laminate 13

The inorganic vapor deposition layer of the film 1E with the inorganic vapor deposition layer produced by the manufacture example 1, and the adhesive resin layer of the multilayered film 2F produced in Example 2 were combined, and it bonded using the vacuum laminator. The bonding conditions used the same conditions as when the laminated body 1 was manufactured. The inorganic vapor deposition layer and adhesive resin layer E1 deposited on the base film showed sufficient adhesiveness. There was little curvature of the laminated body 13 which adhered the same base film 2 sheets.

Example 28 Preparation of Laminate 14

The inorganic vapor deposition layer of the film 2E with the inorganic vapor deposition layer produced by the manufacture example 2, and the adhesive resin layer of the multilayered film 2F produced in Example 2 were combined, and it bonded using the vacuum laminator. The bonding conditions used the same conditions as when the laminated body 1 was manufactured. The inorganic vapor deposition layer and adhesive resin layer E1 deposited on the base film showed sufficient adhesiveness. The curvature of the laminated body 14 which adhered the other two base films was small, and was a level without a problem.

Example 29 Preparation of Laminate 15

In the conditions of Example 15, the laminated body 15 was produced similarly to Example 15 except having used the multilayered film 13F produced in Example 13 instead of the multilayered film 1F. Compared with the SiO ₂ thin film, oxidative deterioration of the surface of the norbornene resin film does not occur during deposition of the silicon metal thin film, thereby obtaining a laminate having excellent interfacial adhesion strength.

Example 30 Preparation of Laminate 16

Under the conditions of Example 15, the same procedure as in Example 15 was carried out except that the multilayered film 14F produced in Example 14 was used instead of the multilayered film 1F to produce a laminate 16. Since an aluminum thin film layer has a light reflection function, when a light emitting element is manufactured on the opposite side (opposite side of the surface which laminated | stacked the multilayered film) to thin film glass, it can be set as the glass substrate which has the outstanding light reflection function.

Comparative Example 6

In the conditions of Example 15, except having used multilayer film R1 instead of multilayer film 1F, operation similar to Example 15 was performed and the laminated body R1 was manufactured. The results are shown in Table 3. The obtained laminated body R1 curved largely toward the multilayered film side by the difference in the thermal expansion rate of glass and a multilayered film at room temperature. Although it fixed mechanically flat, generation | occurrence | production of the big crack was confirmed in the center part of the thin film glass film.

Comparative Example 7

In the conditions of Example 15, except having used multilayer film R2 instead of multilayer film 1F, operation similar to Example 15 was performed and the laminated body R2 was manufactured. The results are shown in Table 3. The obtained laminated body R2 curved largely toward the multilayered film side by the difference in the thermal expansion rate of glass and a multilayered film at room temperature. Although it fixed mechanically flat, generation | occurrence | production of the big crack was confirmed in the center part of the thin film glass film.

Evaluation of each test and comprehensive judgment (next process reliability) in Table 3, and its standard are as follows.

Initial adhesion test (also called peel test) and moisture resistance test (also called peel test):

The initial adhesiveness of the laminated body which adhere | attached the glass substrate and the multilayer film, and the adhesiveness after a moisture resistance test are evaluated by the following checkerboard eye peeling tests. According to the JIS K5400 method, a cutout was made in the form of a checkerboard eye of 1 mm x 1 mm from the multilayer film side of the sample piece, and a peel test was performed with a cellophane adhesive tape (24 mm width, specified in JIS Z1522) to obtain a resin of the multilayer film. The number of eyes (per 100 grids) the component moved to the cellophane tape side is measured.

In addition, the conditions of a moisture proof test are as follows.

Test apparatus: `` EHS-211MD '' (product made in SPECK Corporation)

Temperature: 60 ℃

Humidity: 90% RH

Pressure: normal pressure (101kPa)

Exposure time: 200 hours

Heat test (adhesiveness, peeling, interfacial foaming, fractured, cracks test):

After leaving the laminated body which bonded the glass substrate and the multilayer film for 30 minutes in 130 degreeC oven, it cools to room temperature. After repeating this operation 3 times, the adhesiveness of glass and a multilayer film, the interface peeling, the presence or absence of interfacial foaming, the rupture of an adhesion site | part (wrinkle of a film by a difference in thermal expansion rate), and the presence or absence of a crack are observed.

Peeling test (Initial adhesion test, adhesion test after moisture resistance test)

A: No peeling off / 100 pieces

AB: 1 to 5 of 100 peels

B: 6 or more of 100 peels

The presence or absence of cracks at the time of forced flattening (the presence or absence of cracks in the thin film glass when the substrate is mechanically fixed at room temperature)

A: No crack in thin glass

B: Cracks in Thin Film Glass (Evaluation of B in Any Place)

Deformation of the laminated body (degree of warpage of the substrate at room temperature and bonding temperature of 80 ℃)

A: Good laminate with little warpage at room temperature and adhesion temperature (80 ° C.)

AB: Slight warpage at room temperature, but flattened by jig

B: The warpage of the laminate at room temperature is large, and the plane fixation by the jig is difficult.

Comprehensive judgment (next process reliability)

A: laminated body which can be used as a thin glass substrate

B: When used as a thin film glass substrate, the occurrence of defects is large. Unusable Laminates

From the results of this example, it was found that by forming the inorganic vapor deposition layer on the base film in the present invention, the coating of the varnish of the solvent when coating the adhesive resin layer is small, and the thermal expansion coefficient of the multilayer film is reduced. In addition, polyester, low-expansion polyimide, and the like, which had been difficult to coat the conventional adhesive resin layer, can be used as the base film, and it has been found that the degree of freedom of selection of the material as the base film is greatly improved and the application range is expanded.

Claims (9)

Base film 1 made of resin 1 whose glass transition temperature (Tg) is 80 degreeC or more, Inorganic thin film layer which consists of inorganic material 1 provided on this base film 1, The multilayer film provided on this inorganic thin film layer and provided with the adhesive resin layer containing resin 2 which has a polar group which can be adhere | attached with the inorganic material 2. The method of claim 1, The said base film 1 is a multilayer film which is a film which consists of at least 1 sort (s) of resin chosen from the group which consists of polyester resin, alicyclic structure containing resin, polycarbonate resin, and polyimide resin. The method of claim 1, The said inorganic thin film layer is a multilayer film comprised from at least 1 sort (s) of material chosen from the group which consists of a metal, a semimetal, an inorganic oxide, an inorganic nitride, an inorganic nitride oxide, and diamond-like carbon. The method of claim 1, The said inorganic thin film layer is a multilayer film which is an inorganic vapor deposition layer deposited on the said base film 1. The method of claim 1, Resin 2 which has the said polar group is a multilayer film which is resin which has an acid anhydride group and / or an epoxy group. The laminated body formed by laminating | stacking the board | substrate which has the inorganic material layer which consists of inorganic materials 2 on the surface, and the multilayer film of Claim 1 so that the said inorganic material layer of the said board | substrate and the said adhesive resin layer of the said multilayer film may contact. The method of claim 6, The said board | substrate is a laminated body provided with the base film 3 made of resin 3 whose glass transition temperature (Tg) is 80 degreeC or more, and the said inorganic material layer provided on this base film 3. The method of claim 6, The said inorganic material layer is a laminated body which is at least 1 chosen from the group which consists of a glass layer, a metal layer, and a metal oxide layer. The multilayer film of Claim 1 WHEREIN: The board | substrate which contains the multilayer film which is resin whose glass transition temperature of resin 2 which has the said polar group in this film is 40 degreeC or more, and the inorganic material layer which consists of inorganic material 2 on the surface are 40 degreeC. The manufacturing method of the laminated body including the process of bonding at the temperature below the glass transition temperature of resin 2 which has the said polar group above.

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