JP2018027660A - Functional laminate and method for production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional laminate which does not generate peeling failure or deformation due to bubbles and the like on the boundary face between a carrier substrate and a heat-resistant resin layer at formation of such a peelable heat-resistant resin layer laminated on the carrier substrate, and in which the high gas barrier property and surface smoothness are imparted by a functional layer formed on the upper layer thereof, and to provide a method for production of the laminate.SOLUTION: A functional laminate 1 has a heat-resistant resin layer 3 and a functional layer 4 containing metal compounds on a carrier substrate 2 in this order. The glass transition point (Tg) of the heat-resistant resin layer 3 is in the range of 200-400°C, and the functional layer 4 has the area of a mixture of transition and non-transition metals. Preferably, the heat-resistant resin layer 3 contains polyimide. The non-transition metal is silicon and the transition metal is a fifth group element, preferably niobium.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a functional laminate and a method for producing the same, and more specifically, a peelable heat-resistant resin laminated on a carrier substrate, and the carrier substrate and the heat-resistant resin when the heat-resistant resin layer is formed. The present invention relates to a functional laminate in which peeling failure or deformation due to bubbles or the like does not occur at the interface of a resin layer, and a high gas barrier property and surface smoothness are imparted by a functional layer formed thereon, and a method for producing the same.

  As a resin substrate for flexible devices, application of a polyimide film having good heat resistance has been studied, and a part thereof has been put into practical use. As a technical example that has been put to practical use, a polyimide resin layer is formed as a heat-resistant resin layer on a glass substrate so that it can be applied to a conventional line as a heat-resistant carrier substrate, and used as a heat-resistant laminate. After producing a device on the polyimide resin layer, the polyimide resin layer is peeled from the glass substrate to become a resin substrate for a flexible device (for example, see Patent Document 1).

  However, when peeling from the glass substrate, a certain degree of peeling force is required, and there is a concern that the device may be damaged during peeling. In order to solve this problem, studies have been made to adjust the peeling force between the glass substrate / polyimide resin layers to an appropriate range, that is, to facilitate peeling (for example, see Patent Document 2).

  In addition, a study using a non-thermoplastic resin film as a heat-resistant carrier substrate has been made, and at the same time, a study to adjust the peeling force between the carrier substrate / polyimide resin layer to an appropriate range, that is, a study to facilitate peeling. (For example, refer to Patent Document 3).

  However, the polyimide resin layer that has been studied as a resin substrate for flexible devices has some further problems. A resin substrate for a flexible device is formed by forming a gas barrier layer on the surface of the resin substrate by a vacuum film formation method, and then fabricating a device. At that time, if the surface of the polyimide resin layer is smooth, it is advantageous to form a gas barrier layer, but at present, surface irregularities are formed due to the effect of gas that escapes during firing, etc., and the necessary gas barrier properties In order to obtain a gas barrier layer, it is necessary to laminate a gas barrier layer in multiple layers. In addition, there is a concern that the gas barrier property is lowered due to the influence of outgas generated from the surface of the polyimide resin layer when the gas barrier layer is formed.

  For this reason, a smooth layer having a certain degree of gas barrier property is formed in advance on the surface of the polyimide resin layer, the above-mentioned outgas suppression and surface unevenness are smoothed, and the gas barrier layer is formed by a vacuum film forming method. Consideration has been made to improve performance. Furthermore, studies have been made to impart at least part of the gas barrier properties necessary for the device to the smooth layer.

Specifically, for example, a method of providing a gas barrier property by forming a polysilazane film on the surface of a polyimide film by a coating method and firing it has been studied (for example, see Patent Document 4). Although it is a polyimide film having high heat resistance, it is possible to increase the gas barrier property by raising the baking temperature, but even if the polysilazane baking treatment is performed at 250 ° C. for 30 minutes, the water vapor permeability (Water Vapor) (Transmission Rate: abbreviated as “WVTR”) is about 2 g / m ² · 24 hr in an environment of 40 ° C. and 90% RH. In this method, a gas barrier property required for an electronic device substrate is obtained. It is difficult.

  In addition, a method of improving the gas barrier property by forming a polysilazane film on the polyimide film surface by a coating method and modifying it by vacuum ultraviolet treatment has been studied (for example, see Patent Document 5). Modification of polysilazane by vacuum ultraviolet treatment is effective, and high gas barrier properties can be obtained.

However, in order to improve the gas barrier property, it is necessary to reform with high illuminance of ultraviolet rays and a high energy amount. When such a rapid reforming treatment is performed, NH ₃ and H accompanying the reforming are required. It is known that the generation of _two gases or the like also occurs abruptly. When the polysilazane on the heat-resistant resin layer laminated with a peelable adhesive force on the carrier substrate is modified with high illuminance and high energy amount, the gas generated suddenly causes the carrier substrate / heat resistance. It is a new problem that bubbles are generated between the resin layers and peeled off, and the functional laminate cannot be formed or deformed. Although reforming with low illuminance or low energy amount is less likely to cause peeling, the gas barrier property cannot be improved, and only an insufficient gas barrier property can be obtained.

  As described above, there is a demand for a technique for imparting a high gas barrier property to a heat resistant resin layer laminated with a peelable adhesive force on a carrier substrate without causing peeling.

JP 2010-202729 A JP 2006-062965 A International Publication No. 2014/041816 International Publication No. 2013/069725 JP 2015-127124 A

  The present invention has been made in view of the above-described problems and situations, and a solution to the problem is a peelable heat-resistant resin layer laminated on a carrier substrate, when the heat-resistant resin layer is formed. A functional laminate that does not cause peeling failure or deformation due to bubbles or the like at the interface between the carrier substrate and the heat-resistant resin layer, and that has a high gas barrier property and surface smoothness provided by a functional layer formed thereon, and It is to provide a manufacturing method.

  In order to solve the above-mentioned problems, the present inventor laminated a specific heat-resistant resin layer on the carrier substrate in the process of examining the cause of the above-mentioned problem, and further mixed nontransition metal and transition metal as an upper layer. A heat-resistant resin layer in which the peel strength with respect to the carrier substrate is adjusted to an appropriate range by a functional laminate having a functional layer having a region, and the carrier substrate and the heat-resistant layer are formed when the heat-resistant resin layer is formed. It has been found that a functional laminate having high gas barrier properties and surface smoothness can be obtained by a functional layer formed on the upper layer without causing a peeling failure or deformation due to bubbles or the like at the interface of the resin layer. .

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A functional laminate having, in order, a heat resistant resin layer and a functional layer containing a metal compound on a carrier substrate, wherein the glass transition temperature (Tg) of the heat resistant resin layer is within a range of 200 to 400 ° C. And the functional layer has a mixed region of a non-transition metal and a transition metal.

  2. The functional laminate according to item 1, wherein the heat-resistant resin layer contains polyimide.

  3. The functional laminate according to Item 1 or 2, wherein the non-transition metal is silicon (Si).

  4). The functional laminate according to any one of Items 1 to 3, wherein the transition metal is a Group 5 element in the long-period periodic table of elements.

  5. The functional laminate according to item 4, wherein the transition metal is niobium (Nb).

  6). The functional laminate according to any one of items 1 to 5, wherein the carrier substrate is an inorganic glass substrate.

  7). The functional laminate according to any one of claims 1 to 5, wherein the carrier substrate is a resin film.

  8). The functional laminate according to any one of claims 1 to 7, wherein a peel strength when peeling the heat resistant resin layer from the carrier substrate is 0.2 kN / m or less. body.

9. It is a manufacturing method of the functional layered product which manufactures the functional layered product given in any 1 paragraph from the 1st term to the 8th term, and has the following steps (a)-(c), A method for producing a functional laminate.
(A) A step of applying a heat-resistant resin precursor liquid on the carrier substrate (b) A step of heating the carrier substrate / heat-resistant resin precursor laminate to form a heat-resistant resin layer (c) a heat-resistant resin layer Forming a functional layer thereon

10. The method for producing a functional laminate according to claim 9, wherein the step (c) of forming the functional layer on the heat resistant resin layer includes the following steps (c1) and (c2). .
(C1) forming a layer containing a metal compound of a non-transition metal (c2) forming a mixed region of the non-transition metal and the transition metal

  11. The method for producing a functional layered product according to item 10, wherein the metal compound of the non-transition metal contains polysilazane.

  12 The method for producing a functional laminate according to the tenth aspect, wherein the transition metal is a Group 5 element in the long-period periodic table of elements.

  A peelable heat-resistant resin laminated on a carrier substrate by the above means of the present invention, and when forming the heat-resistant resin layer, peeling failure due to bubbles or the like at the interface between the carrier substrate and the heat-resistant resin layer It is possible to provide a functional laminate and a method for producing the same, which are not deformed and further have high gas barrier properties and surface smoothness provided by a functional layer formed thereon.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  According to the study of the present inventors, an oxygen-deficient composition film containing a compound (for example, an oxide) of a non-transition metal (M1) alone is formed as a functional layer having gas barrier properties, or a transition metal ( When an oxygen-deficient composition film containing the compound (for example, oxide) of M2) alone is formed, the gas barrier property tends to improve as the degree of oxygen deficiency increases. It did not lead to improvement.

  In response to this result, a single composition layer containing a compound (for example, oxide) whose main component is a non-transition metal (M1) and a compound (for example, oxide) whose main component is a transition metal (M2) And a layer containing a non-transition metal (M1) and a transition metal (M2) (hereinafter referred to as “mixed region” in the present application). Then, it discovered that gas barrier property improved remarkably as the grade of oxygen deficiency became large. As described above, this is because electronic bonds (interactions) between the non-transition metal (M1) and the transition metal (M2) rather than the bond between the non-transition metal (M1) and the bond between the transition metal (M2). It is estimated that the oxygen deficient composition in the mixed region forms a high-density structure in the mixed region and exhibits high gas barrier properties.

Therefore, for example, a layer containing polysilazane (Si-containing) as a compound having a non-transition metal (M1) as a main component is formed as a gas barrier layer on a heat-resistant resin layer such as polyimide, and a transition metal (M2) is formed thereon. ), A functional layer having a high gas barrier property can be obtained by forming a layer containing Nb as a main component of the compound so as to have an oxygen deficient composition. Since there is no need to perform firing modification or modification with high illuminance and high energy amount, and generation of the NH ₃ and H ₂ gases can be suppressed, the adhesion between the carrier substrate and the heat-resistant resin layer is improved, and bubbles are generated. It is presumed that peeling or deformation due to the above does not occur and high gas barrier properties and surface smoothness can be imparted.

Schematic sectional view showing the configuration of the functional laminate according to the embodiment of the present invention Graph showing the ratio of the number of atoms to the depth in the thickness direction of the functional layer (gas barrier layer) Schematic sectional view showing an example of vacuum ultraviolet light irradiation apparatus applicable to polysilazane reforming treatment

  The functional laminate of the present invention is a functional laminate having a heat-resistant resin layer and a functional layer containing a metal compound in this order on a carrier substrate, and the glass transition temperature (Tg) of the heat-resistant resin layer is It is within the range of 200 to 400 ° C., and the functional layer has a mixed region of non-transition metal and transition metal. This feature is a technical feature common to or corresponding to the claimed invention.

  As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, it is preferable that the heat-resistant resin layer contains polyimide, which is a resin layer having high heat resistance and high mechanical strength.

  Further, the non-transition metal is silicon (Si), and the transition metal is a Group 5 element of the long-period periodic table of elements and is niobium (Nb). From the viewpoint of expressing

  The carrier substrate is preferably an inorganic glass substrate from the viewpoint of smoothness, and the carrier substrate is preferably a resin film from the viewpoint of enabling roll-to-roll production.

  Furthermore, when the heat-resistant resin layer is peeled from the carrier substrate, the peel strength is 0.2 kN / m or less, and the carrier substrate and the heat-resistant resin layer functionality are peeled to form a flexible device. From the standpoint of

  The method for producing a functional laminate of the present invention comprises: (a) applying a heat resistant resin precursor liquid on a carrier substrate; (b) appropriately heating the carrier substrate / heat resistant resin precursor laminate; Forming a layer, and then (c) forming a functional layer on the heat-resistant resin layer, and forming a functional laminate having high productivity and high gas barrier properties and surface smoothness. Is possible.

  Further, the step (c) of forming a functional layer on the heat resistant resin layer (c1) forms a layer containing a metal compound of a non-transition metal, and then (c2) a non-transition metal and a transition metal It is preferable to form the mixed region from the viewpoint of imparting high gas barrier properties to the functional layer.

  Moreover, it is preferable that the metal compound of the non-transition metal includes polysilazane, and that the transition metal is a Group 5 element of the long-period periodic table, thereby producing a functional laminate having high gas barrier properties. From this viewpoint, this is a preferred embodiment.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, about the detail of the manufacturing method of the functional laminated body of this invention, it adds to the description in each component suitably, and demonstrates. Moreover, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Functional Laminate of the Present Invention >>
The functional laminate of the present invention is a functional laminate having a heat-resistant resin layer and a functional layer containing a metal compound in this order on a carrier substrate, and the glass transition temperature (Tg) of the heat-resistant resin layer is It is within the range of 200 to 400 ° C., and the functional layer has a mixed region of non-transition metal and transition metal.

  The “non-transition metal” (hereinafter also referred to as non-transition metal (M1)) in the present invention is a metal other than a transition metal and belongs to Groups 12 to 14 of the long-period periodic table of elements. It refers to a metal, and “transition metal (hereinafter also referred to as transition metal (M2))” refers to a metal belonging to Group 3 to Group 11. In particular, it is preferable that the non-transition metal is silicon (Si), the transition metal is a Group 5 element of the long-period periodic table, and is niobium (Nb).

  FIG. 1 shows a cross-sectional configuration of a functional laminate 1 according to an embodiment of the present invention. The functional laminate 1 includes a heat-resistant resin layer 3 on a carrier substrate 2 and a functional layer 4 (a gas barrier layer as a function) having a mixed region according to the present invention. ing. Although the functional laminate 1 is not shown on the functional layer 4, a device (for example, an organic electroluminescence (EL) element, an organic thin film solar cell, a liquid crystal display device, a touch panel, etc.) is formed, and then the heat resistance The resin layer 3 can be peeled from the carrier substrate 2 to form a flexible device.

Moreover, the gas barrier property of the gas barrier layer which is a functional layer according to the present invention is measured by a method based on JIS K 7126-1987 when calculated with a laminate in which the gas barrier layer is formed on a base material. The water vapor transmission rate (25 ± 0.5 ° C., measured by a method in accordance with JIS K 7129-1992, the oxygen transmission rate measured was 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less. The relative humidity (90 ± 2)%) is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less high gas barrier property.

Further, the present invention is characterized in that, as the functional layer, for example, the polysilazane-containing coating film does not need to be subjected to baking modification at a high temperature or modification with high illuminance and high energy amount. ₃ and H ₂ gas and the like can suppress bubbles and deformation, improve the adhesion between the carrier substrate / heat-resistant resin layer and improve the smoothness of the surface of the functional laminate. That is, since the surface roughness Ra on the surface of the functional laminate can be as smooth as 2 nm or less, there are disadvantages to the device such as circuit breakage and layer thickness non-uniformity when the device is formed on the functional layer. Can be reduced. The surface roughness Ra is preferably in the range of 1 to 2 nm from the viewpoint of forming a device on the functional layer.

  The surface roughness Ra specified by JIS B0601: 2001 can be measured using, for example, a non-contact three-dimensional micro surface shape measurement system (WYKO manufactured by Veeco).

<Each component of the functional laminate>
Hereafter, each component of the functional laminated body of this invention is demonstrated in order.

[1] Carrier substrate Examples of the carrier substrate include an inorganic glass substrate, a plastic substrate, and a metal oxide substrate, and a flexible substrate such as a plastic sheet.

  In general, it is preferable to use an inorganic glass substrate, which is preferable from the viewpoint that a conventional line can be used as it is, surface smoothness is high, and there is no foreign matter failure.

  Any suitable inorganic glass substrate may be employed as long as it is plate-shaped. The inorganic glass substrate may be long or a single wafer.

Examples of the inorganic glass substrate include soda-lime glass, borate glass, aluminosilicate glass, and quartz glass according to the classification according to the composition. Moreover, according to the classification | category by an alkali component, an alkali free glass and a low alkali glass are mentioned. The content of alkali metal components (for example, Na ₂ O, K ₂ O, Li ₂ O) in the inorganic glass substrate is preferably 15% by mass or less, and more preferably 10% by mass or less.

  The glass constituting the inorganic glass substrate is preferably a non-alkali glass that does not substantially contain an alkali component, specifically, a glass having an alkali component content of 1000 ppm or less. The content of the alkali component in the glass substrate is preferably 500 ppm or less, and more preferably 300 ppm or less. In a glass substrate containing an alkali component, substitution of cations occurs on the film surface, and soda blowing phenomenon tends to occur. Thereby, the density of the upper layer is likely to be lowered, and the glass substrate is easily damaged.

  The thickness of the glass substrate is preferably in the range of 0.4 to 2 mm from the viewpoints of strength and ease of handling.

  The inorganic glass substrate can be formed by a known method such as a float method, a down draw method, an overflow down draw method or the like. Of these, the overflow downdraw method is preferred because the surface of the glass substrate does not come into contact with the molded member during molding and the surface of the resulting glass substrate is hardly damaged.

  Moreover, such an inorganic glass substrate can also be obtained as a commercial product. For example, “7059”, “1737” or “EAGLE2000” manufactured by Corning, “AN100” manufactured by Asahi Glass Co., Ltd., “manufactured by NH Techno Glass” NA-35 ", Nippon Electric Glass" OA-10 ", Schott" D263 "or" AF45 ".

  The plastic substrate is preferably in the form of a film for production, and is preferably a thermoplastic resin film. Preferred resins include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyimide resin, polyetherimide resin, and cellulose. Acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin, Examples thereof include a base material containing a thermoplastic resin such as a fluorene ring-modified polyester resin and an acryloyl compound. These resins can be used alone or in combination of two or more.

  The carrier substrate is preferably made of a heat resistant material. Specifically, it is preferable to use a substrate having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) in the range of 100 to 400 ° C. As a laminated film for electronic parts and displays, Tg is more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. If the linear expansion coefficient of the base material exceeds 100 ppm / K, the substrate dimensions are not stable when flowing through the temperature process as described above, and the insulative performance deteriorates due to thermal expansion and contraction, or The problem of being unable to withstand the thermal process is likely to occur. If it is less than 15 ppm / K, the film may break like glass and the flexibility may deteriorate.

The Tg and the linear expansion coefficient of the carrier substrate can be adjusted with an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic polyolefin. (For example, ZEONOR (registered trademark) 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyether sulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer ( COC: Compound described in JP-A No. 2001-150584: 162 ° C., polyimide (for example, manufactured by Mitsubishi Gas Chemical Co., Ltd., Neoprim (registered trademark): 260 ° C.), polyimide (manufactured by Ube Industries, Upilex; 340 ° C.) ), Fluorene ring-modified polycarbonate Bonate (BCF-PC: compound described in JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound ( And compounds described in JP-A-2002-80616: 300 ° C. or higher) and the like are indicated in parentheses.
Especially, it is preferable that Tg of the said thermoplastic resin film is 200 degreeC or more, and it is preferable that it is a thermoplastic resin film containing a polyimide.

  The glass transition temperature can be measured according to JIS K7121 (1987). Specifically, it can be measured using a DSC 6220 manufactured by Seiko Instruments Inc. as a measuring device under the conditions of a thermoplastic resin sample of 10 mg and a heating rate of 20 ° C./min.

  The substrate mentioned above may be an unstretched film or a stretched film. The substrate can be manufactured by a conventionally known general method. About the manufacturing method of these base materials, the matter described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.

  The surface of the substrate may be subjected to various known treatments for controlling peelability, such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, etc., and the above treatment is performed in combination as necessary. It may be. In addition, the substrate may be subjected to an easy adhesion process by subbing.

  In addition, when laminating a polyimide film or polyeyerate film, which will be described later, as a heat-resistant resin layer on an inorganic glass substrate, it is advisable that a coupling process be performed on the surface on which the inorganic glass substrate is laminated in advance. And from the viewpoint of heat resistance. Examples of the coupling agent used for the coupling treatment used include an epoxy terminal coupling agent, an amino group-containing coupling agent, a methacryl group-containing coupling agent, a thiol group-containing coupling agent, and a silane coupling agent. A solution obtained by dissolving the coupling agent in an appropriate organic solvent is applied onto an inorganic glass substrate, laminated, and then cured (adhesion curing) by heating at about 200 ° C., thereby obtaining preferable adhesion. it can.

  The substrate may be a single layer or a laminated structure of two or more layers. When the substrate has a laminated structure of two or more layers, the base materials may be the same type or different types.

  In the case where the substrate is the thermoplastic resin film, the thickness (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.

  It is preferable that the peel strength when peeling the heat-resistant resin layer described later from the carrier substrate according to the present invention is adjusted to 0.2 kN / m or less. The peel strength can be adjusted by providing a release agent layer such as an undercoat layer on the carrier substrate, or selecting materials and additives used for the heat resistant resin layer. The peel strength is preferably 0.005 to 020 kN / m, more preferably 0.01 to 0.15 kN / m, and still more preferably 0.05 to 0.10 kN / m. Within the above range, it is possible to peel the heat-resistant resin layer from the carrier substrate without causing a peeling failure in the manufacturing process and without using means such as laser irradiation.

  The peel strength according to the present invention is also referred to as “peel force”, and the measurement is carried out using the 180 ° peel method or 90 ° peel method defined in JIS Z0237: 2009 as a performance evaluation (test) method for adhesive tapes and sheets. Can be used.

<Example of measurement method>
Unless otherwise specified, sample pretreatment is allowed to stand for 24 hours or longer in an atmosphere of a standard condition of a temperature of 23 ± 1 ° C. and a relative humidity of 50 ± 5%.

  The width of the sample is adjusted to 25 mm and the length is 50 mm.

  As the test apparatus, a tensile tester is used, and a tensile tester specified in JIS B 7721 or a tensile tester equivalent thereto is used.

  A part of the end of the heat-resistant resin layer is peeled off from the carrier substrate and is sandwiched between tensile testers, and the force required to peel off from the end peeled off at a pulling speed of 50 m / min in the direction of 90 ° or 180 °. taking measurement. The unit is (kN / m).

[2] Heat-resistant resin layer The heat-resistant resin layer according to the present invention is required to have a glass transition temperature (Tg) in the range of 200 to 400 ° C, and the above-mentioned thermoplastic resin is appropriately selected and used. be able to. Especially, it is preferable to contain a polyimide or a polyarylate as a thermoplastic resin.

[2.1] Polyimide The polyimide according to the present invention is preferably a polyimide containing a repeating unit represented by the following general formula (1).

（式中Ｒ^１は下記一般式（２）から選択される４価の有機基を表す。Ｒ^２は下記一般式（３）から選択される２価の有機基を表す。）

(Wherein R ¹ represents a tetravalent organic group selected from the following general formula (2). R ² represents a divalent organic group selected from the following general formula (3).)

（式中、Ｒ^３は、水素、ハロゲン、ハロゲン化アルキル、又はＣ１〜Ｃ１６のアルキル基を表す。）
これらの中でも、上記一般式（１）で表される繰り返し単位を含むポリイミドであることが好ましい。一般式（１）中のＲ^１は４価の有機基であり、その具体例としては、後述する各酸二無水物成分に対応する４価の有機基、すなわち、酸二無水物成分からポリイミド鎖の形成に関与する両末端酸無水物基を取り除いた一般式（２）で表される構造が挙げられる。

(In the formula, R ³ represents hydrogen, halogen, alkyl halide, or C1-C16 alkyl group.)
Among these, it is preferable that it is a polyimide containing the repeating unit represented by the said General formula (1). R ¹ in the general formula (1) is a tetravalent organic group, and specific examples thereof include a tetravalent organic group corresponding to each acid dianhydride component described later, that is, an acid dianhydride component to a polyimide. Examples thereof include a structure represented by the general formula (2) in which both terminal acid anhydride groups involved in chain formation are removed.

  Of the tetravalent organic groups listed in the general formula (2), a structure having benzene or biphenyl is particularly preferable. Specific compounds having a benzene or biphenyl structure include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and derivatives thereof. In this case, pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride should be used as the acid dianhydride used to produce the formula (1), respectively. Can do.

  It is preferable to use the compound having a tetravalent organic group listed in the general formula (2) as the total acid component, but other acid dianhydrides should be within a range that can ensure the transparency of the polyimide. 2 or more can be used in combination. Depending on the desired physical properties, the acid dianhydride other than the acid dianhydride having a tetravalent organic group listed in the general formula (2) within a range not exceeding 70 mol%, preferably not exceeding 50 mol%. Acid dianhydride may be used. Two or more of them may be regularly arranged or may be present in the polyimide randomly.

  Examples of other acid dianhydrides that can be used in combination with the acid dianhydride having a tetravalent organic group and / or its derivatives listed in the general formula (2) include, for example, ethylenetetracarboxylic dianhydride, butane Tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3 '-Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1 , 1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 1,3-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis { 4- [4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, Screw {4- [4- (1,2-dicarbo Phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-di) Carboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] Phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} Sulfone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide anhydrous Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl}- 1,1,1,3,3,3-hexaflupropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3 , 3,3-propane dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4 Benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetra Examples thereof include carboxylic dianhydrides.

On the other hand, R ² in the general formula (1) is a divalent organic group. Specific examples thereof include a divalent group corresponding to each diamine component described later, as described in the general formula (3). The structure which remove | eliminated the organic group, ie, the both terminal amino group which participates in formation of a polyimide chain, from a diamine component is mentioned. Of the general formula (3), a phenylene group or a biphenylene group is preferable. In this case, the diamine used to produce the formula (1) is a diamine having a phenylene group and a diamine having a biphenylene group, respectively.

Further, ^{R 3} in the general formula (3), hydrogen, halogen, a monovalent organic group represents an alkyl group of halogenated alkyl, or C1 to C16. From the transparency, heat resistance, and dimensional change rate of the resulting polyimide, an electron withdrawing group such as halogen or alkyl halide is preferred, and a fluorine atom or trifluoromethyl group is particularly preferred.

  In general formula (3), a particularly preferred one is a trifluoromethyl group. Specifically, 2,2′-bis (trifluoromethyl) benzidine and / or a derivative thereof can be mentioned.

  Although it is preferable to use the diamine having the structure of the general formula (3) as the total diamine component, two or more kinds can be used in combination as long as the transparency of the polyimide can be ensured by using other diamines. Depending on the desired physical properties, a diamine other than the diamine having the structure of formula (3) may be used within a range not exceeding 70 mol%, preferably 50 mol% of the total diamine. Two or more of them may be regularly arranged or may be present in the polyimide randomly.

  As other diamines that can be used in combination with the diamine having the structure of the general formula (3), the diamine component to be used is not limited, but examples thereof include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3 , 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone 3,3'-diaminodi Phenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3 3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-amino) Phenoxy Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-amino) Benzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α- Dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3 -Amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dito Fluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-amino) Phenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl Nyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-amino) Phenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4 -(3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α) , Α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diph Noxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'- Bis (3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) -3,3,3', 3 ' -Tetramethyl-1,1'-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3 -Aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) Til) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl ] Ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2 -(2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamy Hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) ) Cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, etc. Is mentioned.

  A diamine obtained by substituting a part or all of the hydrogen atoms on the aromatic ring of the diamine with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group may also be used. it can.

The substituent R ³ may be introduced as a raw material and may be introduced in the state of a diamine, and may be introduced in the state of a polyimide or a polyamic acid by reacting with the diamine. Moreover, it is possible to adjust the wavelength of light to be absorbed by introducing a substituent, and it is also possible to absorb a desired wavelength by introducing a substituent.

  The polyimide used for the heat-resistant resin layer in the present invention preferably has a structure represented by the general formulas (1), (2) and (3) as described in detail, but the polyimide is substantially the above general formula. The structure shown is preferable.

As the amine component, those having an alkyl halide chain, particularly a trifluoromethyl group are preferred. Of these, particularly preferred are those represented by the general formula (3), in which R ³ is a trifluoromethyl group. The tetracarboxylic dianhydride preferably has a biphenyl structure or an unsubstituted benzene / naphthalene structure. Moreover, it is particularly preferable that both the amine component and tetracarboxylic dianhydride have the above structure.

  Specifically, 2,2′-bis (trifluoromethyl) benzidine is preferable as the amine component particularly preferably used. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, among which 3,3 ′, 4,4 ′. -Biphenyltetracarboxylic dianhydride is preferred. It is particularly preferable to use the compounds shown in the above specific examples for both the amine component and tetracarboxylic dianhydride.

  As a method for producing the polyimide in the present invention, for example, a polyamic acid which is a precursor is synthesized from an acid dianhydride and a diamine, and this is applied directly or by adding a dehydration catalyst or an imidizing agent, and a polyimide resin is applied. A typical method is to obtain a layer.

  In the method of molding in the state of polyamic acid and then imidizing by heating without using a dehydration catalyst or imidizing agent, the heating temperature is usually 100 to 500 ° C, preferably 150 to 450 ° C, Preferably, the range of 150 to 300 ° C. can be arbitrarily selected. The heating time is usually in the range of 1 minute to 6 hours, preferably in the range of 3 minutes to 4 hours, more preferably in the range of 15 minutes to 2 hours, and the heating temperature is preferably gradually increased within the range of the time. Moreover, it is preferable to introduce an inert gas during heating from the viewpoint of reducing coloring by oxygen.

  When an imidizing agent is used, the imidizing agent to be used is preferably a tertiary amine, and more preferably a heterocyclic tertiary amine. Specific examples include pyridine, 2,5-diethylpyridine, picoline, quinoline, and isoquinoline. As the dehydration catalyst, acid anhydrides are preferable, and specific examples include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. Of these, acetic anhydride is the most preferred. preferable.

  In this invention, there exists a tendency for the in-plane linear expansion coefficient and dimensional change rate of the film obtained to become favorable, so that the addition molar amount of the imidation agent with respect to the carboxylic acid of a polyamic acid is increased. On the other hand, if imidization proceeds too quickly with a large amount of imidizing agent, it becomes insoluble before filming, which causes problems such as inability to cast. 0.05-2.0 times molar equivalent, and further 0.6-2.0 times molar equivalent is preferable with respect to the carboxylic acid group of the polyamic acid.

  Moreover, although the physical property of the film obtained does not change easily even if the dehydration catalyst is increased, the heat resistant resin layer tends to be peeled off from the substrate. From these tendencies, the addition amount of the dehydration catalyst is 0.05 to 10.0 times molar equivalent, more preferably 3.6 to 10.0 times molar equivalent to the carboxylic acid group of the polyamic acid. Is preferred. In addition, the said preferable range of an imidation agent and a dehydration catalyst can be used in combination as appropriate.

  Next, the method for synthesizing the polyimide according to the present invention will be illustrated more specifically, but the present invention is not limited thereto.

  An example of synthesizing polyimide using the above 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as an acid component and 2,2′-bis (trifluoromethyl) benzidine as an amine component will be described. First, equimolar 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is gradually added to dimethylacetamide in which 2,2'-bis (trifluoromethyl) benzidine is dissolved, and the mixture is stirred at room temperature. To do.

  After stirring for about 1 to 20 hours, a polyamic acid solution is obtained. After the polyamic acid is cooled to 0 ° C. or lower, an imidizing agent such as pyridine, picoline, quinoline or isoquinoline as an imidizing agent, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride as dehydrating agents Product, acid anhydride such as trifluoroacetic anhydride. Thereafter, the solution is vigorously stirred and defoamed under vacuum or using a centrifugal precipitator, and then coated and dried on a substrate such as glass or film to form a coating film. The polyimide coating film is obtained by heating it to, for example, 300 ° C. or higher to remove the solvent.

  The polyimide synthesized in this way preferably has a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible in order to improve the heat resistance and dimensional change rate inherent to the polyimide. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and all of them are aromatic acid components. Most preferred.

  The proportion of the aromatic amine component in the amine component constituting the repeating unit of the imide structure is preferably 40 mol% or more, particularly preferably 60 mol% or more, and most preferably all are aromatic amine components. Polyimide using aromatic components for both the acid component and the amine component is particularly preferred.

  When the acid component and the amine component have a plurality of aromatic rings and the polyimide main chain from which the plurality of aromatic rings is obtained, a component having flexibility is included between the plurality of aromatic rings. Preferably not. Examples of the component having flexibility include those via a carbon atom, an oxygen atom, a sulfur atom, and the like. The plurality of aromatic rings are preferably directly bonded.

  The direct bond includes a case of bonding with a naphthalene structure and a case of bonding with a biphenyl structure, and among these, those having an aromatic ring bonded with a biphenyl structure are preferable.

  The polyimide synthesized in this way preferably has a low in-plane linear expansion as a heat resistant resin layer with transparency. For example, a film sample containing the polyimide is prepared, and a film of 15 mm × 5 mm is formed by a tensile load method. A polyimide film having an in-plane linear expansion coefficient of 40 ppm or less can be obtained when the weight of the sample is 3.0 g and the sample is measured at a temperature increase rate of 10 ° C./min.

  In addition, the amount of imidizing agent used is 0.5 times the molar amount, 1.0 times the molar amount, and 1.5 times the molar amount with respect to the carboxylic acid group of the polyamic acid. It is also possible to obtain a polyimide film having an expansion coefficient of 20 ppm or less, further 10 ppm or less, particularly 5 ppm or less.

  Further, the amount of the imidizing agent used is set to 40 ° C. to 230 ° C. by adjusting the amount to 0.5 times the molar amount, 1.0 times the molar amount, and 1.5 times the molar amount with respect to the carboxylic acid group of the polyamic acid, respectively. It is also possible to obtain a polyimide film having a dimensional change rate before and after heating of 0.1% or less, further 0.05% or less, and particularly 0.03% or less when heated up to 40 ° C. again.

  Although the weight average molecular weight of the polyimide used for the heat resistant resin layer depends on the use, it is preferably in the range of 3000 to 1000000, more preferably in the range of 5000 to 500000, and in the range of 10000 to 500000. More preferably. When the weight average molecular weight is 3000 or less, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, if it is less than 10,000, there are cases where coloring occurs because the number of polymer ends that cause coloring becomes relatively large. On the other hand, when it exceeds 1000000, the viscosity increases and the solubility also decreases, so that it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.

  The molecular weight used here refers to a value in terms of polystyrene by gel permeation chromatography (GPC), may be the molecular weight of the polyimide precursor itself, or after chemical imidization treatment with acetic anhydride or the like. It may be.

  In addition, various organic or inorganic low-molecular or high-molecular compounds may be blended in order to impart processing characteristics and various functionalities to the polyimide. For example, organic solvents, dyes, surfactants, leveling agents, plasticizers, fine particles, sensitizers, and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, which may be porous or hollow. The function or form includes pigments, fillers, fibers, and the like.

  For example, the polyimide according to the present invention is preferably added with a coupling agent such as a silane coupling agent and a titanium coupling agent in order to adjust the adhesion to the carrier substrate. Examples of the coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ -Aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-amino And butyl tributoxysilane.

  Examples of the titanium coupling agent include γ-aminopropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopropyltripropoxytitanium, γ-aminopropyltributoxytitanium, γ-aminoethyltriethoxytitanium. , Γ-aminoethyltrimethoxytitanium, γ-aminoethyltripropoxytitanium, γ-aminoethyltributoxytitanium, γ-aminobutyltriethoxytitanium, γ-aminobutyltrimethoxytitanium, γ-aminobutyltripropoxytitanium, γ -Aminobutyl tributoxy titanium, etc. Two or more of these may be used in combination. The amount used at this time is preferably 0.1% by mass or more and 3% by mass or less with respect to the polyimide precursor (resin component).

  The solution containing the polyimide precursor may contain a release agent. The contained release agent is not particularly limited as long as it can improve the release property between the carrier substrate and the polyimide-containing layer that is the heat-resistant resin layer, and may be a known internal release agent. Examples of the internal release agent include aliphatic alcohols, fatty acid esters, triglycerides, fluorine surfactants, higher fatty acid metal salts, and phosphate ester release agents. From the viewpoint that it is difficult to inhibit the transparency of the obtained polyimide layer, it is preferably a phosphoric ester release agent. Examples of the phosphoric ester release agent include compounds described in JP-A No. 2000-256377.

  The amount of the release agent contained in the solution containing the polyimide precursor is preferably 0.01 to 0.38 parts by mass, more preferably 0.02 to 0.08 parts by mass with respect to 100 parts by mass of the polyimide precursor. 30 parts by mass, more preferably 0.04 to 0.20 parts by mass. When the amount of the release agent is less than 0.01 parts by mass, the peel strength when peeling the polyimide layer from the carrier substrate is increased. On the other hand, when the amount of the release agent exceeds 0.38 parts by mass, it becomes difficult to apply the solution containing the polyimide precursor on the carrier substrate.

  The heat resistant resin layer according to the present invention preferably contains the polyimide component represented by the general formula (1) in a range of usually 50 to 99.9% by mass with respect to the entire coating film or film. Moreover, the blending ratio of other optional components is preferably in the range of 0.1 to 50% by mass with respect to the entire solid content of the polyimide coating film or film. If it is less than 0.1% by mass, the effect of adding the additive is difficult to be exhibited, and if it exceeds 50% by mass, the characteristics of the additive are hardly reflected in the heat-resistant resin layer as the final product.

  The heat-resistant resin layer according to the present invention preferably has a thickness in the range of 10 to 300 μm. When the thickness is less than 10 μm, the strength of the film is low and the rigidity is inferior. On the other hand, when the thickness exceeds 300 μm, the contribution to thinning of the device is reduced. The thickness of the heat resistant resin layer is more preferably 15 to 150 μm.

  The heat-resistant resin layer containing polyimide is preferably formed on the carrier substrate so as to have the layer thickness by coating or casting.

  The polyimide coating composition can be applied regardless of the type as long as it can form a uniform thickness on the carrier substrate. For example, application by die coating, spin coating, or screen printing is possible.

  Moreover, it is also preferable that the polyimide film produced beforehand is used as a heat resistant resin layer, and it is bonded on the carrier substrate using the coupling agent solution as an adhesive layer.

[2.2] Polyarylate The polyarylate contains at least an aromatic dialcohol component unit and an aromatic dicarboxylic acid component unit.

(Aromatic dialcohol component unit)
The aromatic dialcohol for obtaining the aromatic dialcohol component unit is preferably a bisphenol represented by the following general formula (4), more preferably a bisphenol represented by the following general formula (4 ′).

L in the general formulas (4) and (4 ′) is a divalent organic group. The divalent organic group is preferably a single bond, an alkylene group, —S—, —SO—, —SO ₂ —, —O—, —CO— or —CR ₁ R ₂ — (R ₁ and R ₂ are To form an aliphatic ring or an aromatic ring.

  The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, and an isopropylidene group. The alkylene group may further have a substituent such as a halogen atom or an aryl group.

R ₁ and R ₂ of —CR ₁ R ₂ — are bonded to each other to form an aliphatic ring or an aromatic ring. The aliphatic ring is preferably an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, and preferably a cyclohexane ring which may have a substituent. An aromatic ring is a C6-C20 aromatic hydrocarbon ring, Preferably it is a fluorene ring which may have a substituent. Examples of —CR ₁ R ₂ — forming a cyclohexane ring which may have a substituent include cyclohexane-1,1-diyl group, 3,3,5-trimethylcyclohexane-1,1-diyl group and the like. included. Examples of —CR ₁ R ₂ — forming a fluorene ring which may have a substituent include a fluorenediyl group represented by the following formula.

  R in the general formulas (4) and (4 ′) may independently be an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. n is independently an integer of 0 to 4, preferably an integer of 0 to 3.

  Examples of bisphenols in which L is an alkylene group include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-methyl-2 -Hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4- Hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (TMBPA), etc. Is included. Among them, 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC), 2,2-bis (3,5-dimethyl- Isopropylidene-containing bisphenols such as 4-hydroxyphenyl) propane (TMBPA) are preferred.

Examples of bisphenols in which L is —S—, —SO— or —SO ₂ — include bis (4-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4 -Hydroxyphenyl) sulfone (TMBPS), bis (3,5-diethyl-4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, Bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) Sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, 2,4-dihydride Carboxymethyl diphenyl sulfone and the like. Examples of bisphenols where L is —O— include 4,4′-dihydroxydiphenyl ether; examples of bisphenols where L is —CO— include 4,4′-dihydroxydiphenyl ketone. .

Examples of bisphenols in which L is —CR ₁ R ₂ — and R ₁ and R ₂ are bonded to each other to form an aliphatic ring include 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ) And bisphenols having a cyclohexane skeleton such as 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC).

Examples of bisphenols in which L is —CR ₁ R ₂ — and R ₁ and R ₂ are bonded to each other to form an aromatic ring include 9,9-bis (3-methyl-4-hydroxyphenyl) Bisphenols having a fluorene skeleton such as fluorene (BCF) and 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene (BXF) are included.

  The aromatic dialcohol component constituting the polyarylate may be one kind or two or more kinds.

Among these, from the viewpoint of enhancing the solubility of the resin in the solvent or enhancing the adhesion of the film to the metal, for example, a sulfur atom (—S—, —SO— or —SO ₂ —) is present in the main chain. Bisphenols contained are preferred. From the viewpoint of enhancing the heat resistance of the film, for example, bisphenols containing a sulfur atom in the main chain and bisphenols having a cycloalkylene skeleton are preferred. From the viewpoint of reducing the birefringence of the film or improving the wear resistance, bisphenols having a fluorene skeleton are preferred.

  Bisphenols having a cyclohexane skeleton and bisphenols having a fluorene skeleton are preferably used in combination with bisphenols containing an isopropylidene group. In that case, the content ratio of the bisphenol having a cyclohexane skeleton or the bisphenol having a fluorene skeleton and the bisphenol having an isopropylidene group is 10/90 to 90/10 (molar ratio), preferably 20/80 to 80/20 (molar ratio).

  The polyarylate may further contain an aromatic polyhydric alcohol component unit other than the aromatic dialcohol component as long as the effects of the present invention are not impaired. Examples of the aromatic polyhydric alcohol component include the compounds described in paragraph 0015 of Japanese Patent No. 4551503. Specifically, tris (4-hydroxyphenyl) methane, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,3, 4,4'-tetrahydroxybenzophenone, 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, tris (3-methyl-4-hydroxyphenyl) methane and the like are included. The content ratio of these aromatic polyhydric alcohol component units can be appropriately set according to the required characteristics, but is 5 for example with respect to the total of the aromatic dialcohol component unit and the other aromatic polyhydric alcohol component units. It may be less than mol%.

(Aromatic dicarboxylic acid component unit)
The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid component unit may be terephthalic acid, isophthalic acid or a mixture thereof.

  From the viewpoint of enhancing the mechanical properties of the heat resistant resin layer, a mixture of terephthalic acid and isophthalic acid is preferable. The content ratio of terephthalic acid and isophthalic acid is preferably terephthalic acid / isophthalic acid = 90/10 to 10/90 (molar ratio), more preferably 70/30 to 30/70, and still more preferably 50/50. When the content ratio of terephthalic acid is in the above range, a polyarylate having a sufficient degree of polymerization is easily obtained, and a heat-resistant resin layer having sufficient mechanical properties is easily obtained.

  The polyarylate may further contain an aromatic dicarboxylic acid component unit other than terephthalic acid and isophthalic acid as long as the effects of the present invention are not impaired. Examples of such aromatic dicarboxylic acid components include orthophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenic acid, 4,4'-dicarboxydiphenyl ether, bis (p-carboxyphenyl) alkane, 4,4'- Dicarboxyphenyl sulfone and the like are included. The content ratio of aromatic dicarboxylic acid component units other than terephthalic acid and isophthalic acid can be appropriately set according to the required properties, but the total of terephthalic acid component, isophthalic acid component unit and other aromatic dicarboxylic acid component units For example, it may be 5 mol% or less.

(Glass-transition temperature)
The glass transition temperature Tg of polyarylate is preferably in the range of 260 to 350 ° C, more preferably 265 ° C or more and less than 300 ° C, and further preferably 270 ° C or more and less than 300 ° C.

  The glass transition temperature of the polyarylate can be adjusted by the type of aromatic dialcohol component constituting the polyarylate. In order to increase the glass transition temperature, for example, it is preferable to include “units derived from bisphenols containing a sulfur atom in the main chain” as aromatic dialcohol component units.

(Intrinsic viscosity)
The intrinsic viscosity of the polyarylate, at 25 ° C. Measurements is preferably 0.3~1.0cm ³ / g, more preferably 0.4~0.9cm ³ / g, 0.45~0.8cm ³ / G is more preferable, and it is more preferable that it is 0.5 to 0.7 cm ³ / g. When the intrinsic viscosity of polyarylate is 0.3 cm ³ / g or more, the molecular weight of the resin composition tends to be a certain level or more, and a film having sufficient mechanical properties and heat resistance is easily obtained. When the intrinsic viscosity of the polyarylate is 1.0 cm ³ / g or less, an excessive increase in the solution viscosity during film formation can be suppressed.

Intrinsic viscosity can be measured according to ISO1628-1. Specifically, a solution in which a polyarylate sample is dissolved in 1,1,2,2-tetrachloroethane so as to have a concentration of 1 g / cm ³ is prepared. The intrinsic viscosity of this solution at 25 ° C. is measured using an Ubbelohde type viscosity tube.

  The polyarylate production method may be a known method, preferably an interface in which an aromatic dicarboxylic acid halide dissolved in an organic solvent incompatible with water and an aromatic dialcohol dissolved in an alkaline aqueous solution are mixed. The polymerization method (WM EARECKSON, J. Poly. Sci. XL399, 1959, Japanese Patent Publication No. 40-1959) can be mentioned.

  The content of the polyarylate may be 50% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more with respect to the entire heat-resistant resin layer.

  The heat-resistant resin layer containing polyarylate can be formed by coating or casting on a carrier substrate, similarly to the aforementioned polyimide. Or it is also preferable to use the polyarylate film produced beforehand as a heat resistant resin layer. As a commercially available polyarylate film, a polyarylate film M-2000H manufactured by Unitika Ltd. may be mentioned.

[3] Functional layer The functional layer according to the present invention has a mixed region of a non-transition metal and a transition metal, and is a layer having a gas barrier property including a metal compound as a main component. Hereinafter, the functional layer according to the present invention will be described as a “gas barrier layer”.

  The gas barrier layer according to the present invention is characterized by having a mixed region of a non-transition metal and a transition metal as described above, but the first gas barrier layer mainly containing the non-transition metal and the transition metal are mainly used. It is preferable that it is a laminated body of the second gas barrier layer contained in, and the layer order may be reversed. It is also preferable that the entire gas barrier layer is a mixed region of non-transition metal and transition metal. The “mainly contained” means that the content of the metal of the type is 50 atomic% or more with respect to atomic% of all metal elements in the layer.

  Details of preferred embodiments of the “mixed region” in the present invention will be described later. Further, in the present invention, the “region” is a plane that is substantially perpendicular to the thickness direction of the gas barrier layer (that is, a plane parallel to the outermost surface of the gas barrier layer), and the gas barrier layer is fixed or arbitrary. This refers to a three-dimensional range (region) between two opposing surfaces formed when divided by thickness. Even if the composition of components in the region is constant in the thickness direction, it is gradually increased. It may change to.

  The non-transition metal (M1) selected from the group 12 to group 14 metals is not particularly limited, and any group 12 to group 14 metal may be used alone or in combination. , Si, Al, Zn, In, and Sn. Especially, it is preferable that a non-transition metal (M1) contains Si, Sn, or Zn, it is more preferable that Si is included, and it is especially preferable that it is Si alone.

  The transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination. Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y , Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W , Re, Os, Ir, Pt, and Au.

  Among these, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, etc. are mentioned as a transition metal (M2) from which a favorable gas barrier property is obtained. Among these, Nb, Ta, and V, which are Group 5 elements, are considered to be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer. be able to.

  In particular, when the transition metal (M2) is a Group 5 element (particularly Nb) and the above-described non-transition metal (M1) is Si, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal (M2) is particularly preferably Nb and Ta, which are compounds with good transparency.

<Mixed area>
The mixed region according to the present invention includes a non-transition metal (M1) selected from Group 12 to Group 14 metals and a transition metal (Group 3 to Group 11) selected from the metals of Group 12 to Group 14 of the long-period periodic table. M2) is a region where the ratio of the number of atoms of the transition metal M2 to the non-transition metal M1 (M2 / M1) is in the range of 0.02 to 49. In the thickness direction, it is preferably a region having 5 nm or more continuously.

  The mixed region may be formed as a plurality of regions having different chemical compositions of the constituent components, or may be formed as a region in which the chemical compositions of the constituent components are continuously changed.

  In the present invention, it is preferable that a part of the composition contained in the mixed region according to the present invention has a non-stoichiometric composition (oxygen deficient composition) in which oxygen is deficient.

  In the present invention, the oxygen deficient composition is defined by the following relational expression (2) when at least a part of the composition of the mixed region is expressed by the following chemical composition formula (1). It is defined as satisfying the condition. In addition, as the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the certain mixed region is used. Details will be described later.

Chemical composition formula (1): (M1) (M2) _x O _y N _z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
In the above formulas, M1 represents a non-transition metal, M2 represents a transition metal, O represents oxygen, N represents nitrogen, and x, y, and z represent stoichiometric coefficients, respectively. a represents the maximum valence of M1, and b represents the maximum valence of M2.

As described above, the composition of the mixed region of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) _x O _y N _z which is the formula (1). As is clear from this composition, the composition of the mixed region may partially include a nitride structure, and it is more preferable to include a nitride structure from the viewpoint of gas barrier properties.

  Here, the maximum valence of the non-transition metal (M1) is a, the maximum valence of the transition metal (M2) is b, the valence of O is 2, and the valence of N is 3. When the composition of the mixed region (including a part of the nitride) is a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N. In this case, non-transition metal (M1) And the transition metal (M2) are bonded to either O or N. In the present invention, when two or more kinds are used together as the non-transition metal (M1), or when two or more kinds are used together as the transition metal (M2), the maximum valence of each element is set to The composite valence calculated by performing the weighted average according to the existence ratio is adopted as the values of a and b of each “maximum valence”.

  On the other hand, in the mixed region according to the present invention, when (2y + 3z) / (a + bx) <1.0 shown by the relational expression (2), a bond between the non-transition metal (M1) and the transition metal (M2) This means that the total number of O and N bonds is insufficient with respect to the total, and such a state is the above-mentioned “oxygen deficiency”.

  In the oxygen deficient state, the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are improved.

  In the present invention, the mixed region is a region where the value of x satisfies 0.02 ≦ x ≦ 49 (0 <y, 0 ≦ z). This is the same definition as previously defined as a region in which the value of the number ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 49. .

  In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, the mixed region satisfying this condition has a thickness of a predetermined value or more (preferably, 5 nm or more). It is thought that it contributes to the improvement of gas barrier property. In addition, since it is considered that the closer the abundance ratio of the non-transition metal (M1) and the transition metal (M2), the more the gas barrier property can be improved, the mixed region is a region satisfying 0.1 ≦ x ≦ 10. It is preferable to include a thickness of 5 nm or more, more preferably include a region satisfying 0.2 ≦ x ≦ 5 at a thickness of 5 nm or more, and a region satisfying 0.3 ≦ x ≦ 4 to a thickness of 5 nm or more. It is further preferable to contain.

  Here, as described above, if there is a region satisfying the relationship of (2y + 3z) / (a + bx) <1.0 represented by the relational expression (2) within the range of the mixed region, the effect of improving the gas barrier property is obtained. Although it was confirmed that the mixed region exhibits at least a part of the composition, (2y + 3z) / (a + bx) ≦ 0.9, and (2y + 3z) / (a + bx) ≦ 0.85 in the mixed region. It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill (2y + 3z) / (a + bx) <= 0.8. Here, the smaller the value of (2y + 3z) / (a + bx) in the mixed region, the higher the gas barrier property, but the greater the absorption in visible light. Therefore, in the case of a gas barrier layer used for applications where transparency is desired, 0.2 ≦ (2y + 3z) / (a + bx) is preferable, and 0.3 ≦ (2y + 3z) / (a + bx). Is more preferable, and 0.4 ≦ (2y + 3z) / (a + bx) is still more preferable.

In the present invention, the thickness of the mixed region that provides good gas barrier properties is preferably 5 nm or more as the sputtering thickness in terms of SiO ₂ in the XPS analysis method described later, and this thickness is 8 nm or more. Is more preferably 10 nm or more, and particularly preferably 20 nm or more. The thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.

Specifically, the element concentration distribution (hereinafter referred to as depth profile) in the thickness direction of the gas barrier layer according to the present invention includes a non-transition metal (M1) distribution curve (for example, a silicon distribution curve) and a transition metal (M2). ) Distribution curves (for example, niobium distribution curves), oxygen (O), nitrogen (N), carbon (C) distribution curves, etc. are measured by X-ray photoelectron spectroscopy (XPS) and noble gases such as argon. By using together with ion sputtering, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside from the surface of the gas barrier layer. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time). In addition, in the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction, As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement Can be adopted. Further, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  An example of specific conditions for XPS analysis applicable to the present invention is shown below.

・ Analyzer: QUANTERA SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).

  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI. The analyzed elements are non-transition metal M1 (for example, silicon (Si)), transition metal M2 (for example, niobium (Nb)), oxygen (O), nitrogen (N), and carbon (C).

The composition ratio is calculated from the obtained data, the non-transition metal M1 and the transition metal M2 coexist, and the value of the number ratio of transition metal M2 / non-transition metal M1 is 0.02 to 49. The range was determined, this was defined as the mixed region, and the thickness was determined. The thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO ₂ .

  FIG. 2 shows a schematic graph of an element profile when the composition distribution of the non-transition metal M1 and the transition metal M2 in the thickness direction of the gas barrier layer including the mixed region is analyzed by the XPS method.

  FIG. 2 shows the elemental analysis of M1, M2, O, N, and C in the depth direction from the surface of the gas barrier layer (the left end of the graph), and the horizontal axis indicates the sputtering depth (film thickness: nm). It is the graph which showed the content rate (atom%) of M1 and M2 on the vertical axis | shaft.

  In FIG. 2, the element composition of the second gas barrier layer containing the oxide of the transition metal (M2), the element composition of the mixed region, and the first gas barrier containing the oxide of the non-transition metal (M1) from the left side. The element composition profile in a layer is shown, and the value of the atomic ratio of M2 / M1 is within the range of 0.02 to 49 in the mixed region. The mixed region is preferably 5 nm or more in thickness from the viewpoint of obtaining good gas barrier properties.

  A gas barrier layer having a mixed region having a specific configuration as described above exhibits a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.

<Method for forming mixed region>
As a method for forming a mixed region, a region containing a non-transition metal (M1) selected from metals of Group 12 to Group 14 of the long-period periodic table (non-transition metal-containing region: first gas barrier layer) And a region containing a transition metal (M2) selected from Group 3 to Group 11 metals (transition metal-containing region: corresponding to the second gas barrier layer) are adjacent to each other. When forming, it is preferable to adjust each forming condition appropriately to form a mixed region between the non-transition metal-containing region and the transition metal-containing region.

  When the non-transition metal-containing region is formed by a vapor deposition method, for example, the ratio of the non-transition metal (M1) and oxygen in the film forming raw material, the ratio of the inert gas and the reactive gas during film formation, A mixed region by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Can be formed.

  When forming a non-transition metal-containing region by a coating method, for example, a film-forming raw material species (polysilazane species, etc.) containing a non-transition metal (M1), a catalyst species, a catalyst content, a coating film thickness, a drying temperature / time The mixed region can be formed by adjusting one or more conditions selected from the group consisting of a reforming method and reforming conditions.

  When the transition metal-containing region is formed by vapor phase growth, for example, the ratio of transition metal (M2) and oxygen in the film forming raw material, the ratio of inert gas to reactive gas during film formation, and during film formation The mixed region is formed by adjusting one or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation. can do.

  In addition to this, a method of directly forming a mixed region of a non-transition metal and a transition metal is also preferable.

  As a method for directly forming the mixed region, it is preferable to use a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite of a non-transition metal (M1) and a transition metal (M2). One-way sputtering using a composite target made of an oxide as a sputtering target may be used.

  In addition, the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be.

  The film forming conditions for performing the co-evaporation method include the ratio of transition metal (M2) and oxygen in the film forming raw material, the ratio of inert gas to reactive gas during film formation, Examples include one or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation, and these film formation conditions (preferably oxygen partial pressure) ) Can be adjusted to form a thin film made of a complex oxide having an oxygen-deficient composition. That is, by forming the gas barrier region using the co-evaporation method as described above, most of the region in the thickness direction of the formed gas barrier region can be a mixed region. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a mixing area | region.

  Hereinafter, a preferred method for forming a layer containing a non-transition metal (M1) and a transition metal (M2) will be described.

<Formation of Layer Containing Polysilazane or Modified Polysilazane as Non-Transition Metal (M1)>
As the first gas barrier layer formed on the heat-resistant resin layer, it is preferable to form polysilazane containing Si as a non-transition metal (M1) or a modified polysilazane.

  In this method, a polysilazane layer-containing coating liquid containing polysilazane is applied and dried to form a precursor layer, and then the precursor layer is subjected to a modification treatment with vacuum ultraviolet light to form a gas barrier layer. It is.

  In the formation of the gas barrier layer, any appropriate wet coating method can be applied as a coating method for coating the gas barrier region-forming coating solution containing a polysilazane compound. Examples thereof include a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The thickness of the coating film can be set according to the purpose of use of the gas barrier layer and is not particularly limited. For example, the thickness of the coating film is in the range of 10 to 1000 nm as the thickness after drying. Preferably, it is in the range of 20 to 500 nm, more preferably in the range of 50 to 300 nm.

In a preferred use "polysilazane compound" present invention, the silicon in the structure - a polymer with a nitrogen bonds, Si-N, Si-H , SiO 2 consisting of N-H or the like, _Si 3 _{N 4} and both the intermediate It is a ceramic precursor inorganic polymer such as solid solution SiO _x N _y .

  As such a polysilazane compound, those having the following structure are preferably used.

—Si (R ₁ ) (R ₂ ) —N (R ₃ ) —
In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, from the viewpoint of the denseness of the resulting gas barrier layer as a film, perhydropolysilazane (abbreviation: PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable.

  As an organic solvent for preparing a coating solution containing a polysilazane compound, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. Examples of the organic solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, or ethers such as aliphatic ethers or alicyclic ethers. Can be used.

  The concentration of the polysilazane compound in the polysilazane compound-containing coating solution is about 0.2 to 35% by mass, although it depends on the thickness of the target gas barrier region and the pot life of the coating solution.

  An amine or a metal catalyst may be added to the coating solution in order to promote modification to the silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. The addition amount of these catalysts is preferably adjusted to 2% by mass or less with respect to the polysilazane compound in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like.

  In addition to the polysilazane compound, the coating liquid containing the polysilazane compound can contain an inorganic precursor compound. The inorganic precursor compound other than the polysilazane compound is not particularly limited as long as the coating liquid can be prepared. For example, paragraphs 0140 to 0142 of International Publication No. 2012/090644, paragraphs of International Publication No. 2013/002026 Examples thereof include silicon-containing compounds and polysilsesquioxanes described in 0112 to 0114 and paragraphs 0072 to 0074 of JP-A-2015-33764.

  The modification treatment of polysilazane in the present invention refers to a reaction in which a part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.

  For this modification treatment, a known method based on the conversion reaction of polysilazane can be selected. Formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound requires a high temperature of 450 ° C. or more, and is difficult to adapt to a flexible substrate using a resin film as a base material. Therefore, in the case of using a resin base material, a method using ultraviolet light that can be converted at a lower temperature is preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.

Modification of polysilazane by ultraviolet treatment is effective, and high gas barrier properties can be obtained. However, in order to improve the gas barrier property, it is necessary to reform with a high illuminance of ultraviolet rays and a high energy amount. When such a rapid reforming process is performed, NH ₃ and H ₂ accompanying the reforming are necessary. It is known that the generation of gas or the like also occurs abruptly. When the polysilazane on the heat-resistant resin layer laminated with a peelable adhesive force on the carrier substrate is modified with high illuminance and high energy amount, the gas generated suddenly causes the carrier substrate / heat resistance. In some cases, bubbles are generated between the resin films and peeled off, so that a functional laminate cannot be formed.

  In the present invention, the gas barrier property is remarkably improved by forming a mixed region of a non-transition metal and a transition metal, so that high temperature heating, high illuminance of ultraviolet rays, and a high energy amount are used for polysilazane modification. There is no need for reforming. Therefore, a known method can be applied as appropriate to the modification of polysilazane, but it is not necessary to set rapid modification conditions.

  In the present invention, modification by vacuum ultraviolet light irradiation treatment is most effective, but in that case, a commonly used ultraviolet ray generator can be used. In addition, the ultraviolet light as used in the field of this invention means the ultraviolet light containing the electromagnetic wave which has a wavelength of 10-200 nm generally called vacuum ultraviolet light.

  For irradiation with vacuum ultraviolet light, set the irradiation intensity and irradiation time within the range where the substrate carrying the pre-modified polysilazane layer and other areas constituting the gas barrier unit are not damaged. It is preferable to do.

  Examples of such ultraviolet ray generating means include, but are not limited to, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and a UV light laser. In addition, when the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. When the substrate having the polysilazane modified layer is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. Can do. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although depending on the base material used and the composition and concentration of the polysilazane modified layer.

  Moreover, it is preferable that oxygen concentration at the time of irradiating vacuum ultraviolet light (VUV) is 300-10000 volume ppm (1 volume%), More preferably, it is 500-5000 volume ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the generation of a gas-barrier region with excessive oxygen and to prevent the deterioration of the gas barrier property.

  A dry inert gas is preferably used as a gas other than oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is particularly preferable from the viewpoint of cost.

  Further, the gas barrier region can be formed by a wet method using a vacuum ultraviolet irradiation apparatus 100 shown in FIG.

In FIG. 3, the apparatus chamber 101 supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside, and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. Can be maintained at a predetermined concentration. In the apparatus chamber 101, an Xe excimer lamp (excimer lamp light intensity: 130 mW / cm ² ) 102 having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, an excimer lamp holder 103 that also serves as an external electrode, a sample stage 104, and A light shielding plate 106 and the like are provided. The sample stage 104 is configured to be movable in the apparatus chamber 101 horizontally (at a V direction in FIG. 3) at a predetermined speed by a moving means (not shown), and can return to the original position again. The sample stage 104 can be maintained at a predetermined temperature by a heating means (not shown). A sample 105 on which a polysilazane compound coating layer is formed is placed on the sample stage 104. When the sample stage 104 moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the coating layer surface of the sample 105 and the excimer lamp tube surface is 3 mm. The light shielding plate 106 prevents the coating layer of the sample 105 from being irradiated with vacuum ultraviolet rays while the Xe excimer lamp 102 is aged.

  The amount of irradiation energy irradiated to the coating layer surface of the sample 105 with the vacuum ultraviolet irradiation apparatus 100 is measured using a 172 nm sensor head using an ultraviolet integrated light meter (C8026 / H8025 UV POWER METER) manufactured by Hamamatsu Photonics Co., Ltd. can do. In the measurement, the sensor head is installed in the center of the sample stage 104 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 101 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen are supplied so that the oxygen concentration becomes the same as the time, and the sample stage 104 is moved at a speed of 0.5 m / min to perform measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 102, an aging time of 10 minutes is provided after the Xe excimer lamp is turned on, and then the sample stage is moved to start the measurement. Based on the irradiation energy obtained by this measurement, the amount of irradiation energy can be adjusted by adjusting the moving speed of the sample stage.

  For details of these reforming treatments, for example, paragraphs 0055 to 0091 of JP2012-086394A, paragraphs 0049 to 0085 of JP2012-006154A, paragraphs 0046 to 0074 of JP2011-251460A, for example. Etc. can be referred to.

<Formation of layer containing transition metal (M2)>
A region (second gas barrier layer) containing a transition metal (M2) selected from a Group 3 element to a Group 11 metal is a vapor deposition layer having a gas barrier property formed by a vapor deposition method. It is preferable from the viewpoint of accurately forming the mixed region according to the present invention.

  Examples of the method for forming the vapor deposition layer include physical vapor deposition and chemical vapor deposition.

  Physical vapor deposition (PVD (Physical Vapor Deposition)) is a method of depositing a thin film of a target substance (for example, a carbon film) on a substrate surface by a physical method in a gas phase. Examples thereof include vapor deposition methods (resistance heating method, electron beam vapor deposition method, molecular beam epitaxy method), ion plating method, sputtering method and the like.

  On the other hand, chemical vapor deposition (chemical vapor deposition (CVD)) is performed by mixing a source gas containing a target thin film component with an excited discharge gas on a substrate surface in a gas phase. In this method, a thin film is deposited on the surface of the substrate or on the substrate by a chemical reaction in the gas phase. In particular, there is a method of generating plasma etc. for the purpose of activating a chemical reaction, and known CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method, etc. Etc.

  The layer thickness of the second gas barrier layer varies depending on the composition and formation method, but is preferably in the range of 2 to 50 nm, more preferably in the range of 4 to 25 nm, and more preferably in the range of 5 to 15 nm. More preferably, it is the range.

  Each of the second gas barrier layers may be a plurality of layers, all of which may have the same configuration / formation method, or at least one of these may be a different configuration / formation method. Also good.

(Sputtering method)
As a preferable method for forming the vapor deposition layer (vapor deposition film), there is a sputtering method which is one of vacuum film formation methods.

  Sputtering is a method in which an inert gas such as argon gas is ionized (plasmaized) using an electric field or magnetic field, and the target atoms are knocked out by the kinetic energy obtained by accelerating the ionized ions. It is a physical process for depositing on a substrate to form a target film. In the sputtering method, a sputtering gas such as argon is ionized (plasmaized) using an electric field or a magnetic field and accelerated to collide with the target surface. Then, target atoms are ejected from the target with which the plasma particles collide, and the ejected atoms are deposited on the object to be processed to form a sputtered film.

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and any of DC (direct current) sputtering, DC pulse sputtering, AC (alternating current) sputtering, and RF (high frequency) sputtering may be used.

  A reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable.

  As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, thin films of non-transition metal (M1) and transition metal (M2) composite oxides, nitride oxides, oxycarbides, etc. are formed. can do. Examples of film forming conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, and these can be appropriately selected according to the sputtering apparatus, the material of the film, the layer thickness, and the like.

  The sputtering method may be a multi-source simultaneous sputtering method using a plurality of sputtering targets including a single transition metal (M2) or an oxide thereof. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The methods and conditions described in JP 2013-047361 A can be referred to as appropriate.

(Plasma CVD method)
As a method for forming a vapor deposition layer (vapor deposition film) as a gas barrier layer, it is also preferable to use a vacuum or atmospheric pressure plasma CVD method from the viewpoint of film formation speed and processing area.

  The excited gas as used in the present invention means that at least part of the molecules in the gas move from the existing state to a higher energy state by obtaining energy, and the excited gas molecules, radicalized gas This includes molecules and gas containing ionized gas molecules.

  A method for forming a gas barrier layer, which is a vapor-deposited layer containing metal oxide, metal nitride, or metal oxynitride, includes a raw material containing a metal element such as silicon in a discharge space in which a high-frequency electric field is generated. A plasma CVD method in which an inorganic film (ceramic film) is formed on a base material by forming a secondary excitation gas by mixing the gas with an excited discharge gas and exposing the base material to the secondary excitation gas is preferable. That is, a discharge gas is introduced between the counter electrodes (discharge space), a high-frequency voltage is applied between the counter electrodes to bring the discharge gas into a plasma state, and then the discharge gas and the raw material gas that are in the plasma state are moved outside the discharge space. Then, the substrate is exposed to this mixed gas (secondary excitation gas) to form a vapor deposition layer on the substrate.

  Note that the vapor deposition layer containing metal oxide, metal nitride, and metal oxynitride formed by the plasma CVD method in the present invention includes at least one of metal oxide, metal nitride, and metal oxynitride. It is a deposited film, and may be a composite compound such as metal oxide, metal nitride, metal oxynitride, metal carbide.

  As a raw material of such an inorganic film (ceramic film), it may be in a gas, liquid, or solid state at normal temperature and pressure as long as it has a transition metal element. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and can use organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence on the film formation can be almost ignored.

  In addition, as a decomposition gas for decomposing a raw material gas containing a metal element to obtain an inorganic compound, for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, suboxide Examples thereof include nitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  A ceramic film of a mixture of a metal oxide, a metal oxide and a metal carbide, a metal nitride, a metal oxynitride, a metal halide, a metal sulfide, etc., by appropriately selecting a source gas containing a metal element and a decomposition gas Can be obtained.

  When forming the vapor deposition layer, a discharge gas that is likely to be in a plasma state can be mixed with the reactive gas of the raw material gas and the decomposition gas, and the mixed gas can be sent to the plasma discharge processing apparatus.

  As such a discharge gas, nitrogen gas and / or Group 18 atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  A vapor deposition layer is formed by supplying a mixed gas obtained by mixing a discharge gas and a reactive gas to a plasma discharge treatment apparatus. Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, it is preferable to supply the reactive gas with the ratio of the discharge gas being 50% by volume or more with respect to the entire mixed gas.

[4] Electronic Device The functional laminate of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, the functional laminate of the present invention can be applied to an electronic device including an electronic device body.

  Examples of the electronic device main body used in the electronic device having the functional laminate of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and the sun. A battery (PV) etc. can be mentioned. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

  The functional laminate of the present invention is preferably applied to an organic EL element. For the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A and JP2013-168552A. JP, 2013-177361, JP 2013-187221, JP 2013-191644, JP 2013-191804, JP 2013-225678, JP 2013-235994, JP 2013-243234, JP 2013-243236, JP 2013-242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014 -003299, JP2014-013910A, JP 014-017493 JP include a configuration described in JP-2014-017494 Patent Publication.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

<Preparation of functional laminate 101>
<Preparation of carrier substrate>
As the carrier substrate, an inorganic glass substrate (non-alkali glass manufactured by Asahi Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm was used.

<Formation of heat-resistant resin layer>
To a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, 360 g of N-methyl-2-pyrrolidone was added as a solvent, and 36 g of 4,4′-diaminodiphenyl ether (ODA) was added thereto. 4492 g (0.1820 mol) and 53.5508 g (0.1820 mol) of s-3,3 ′, 4,4′-biphenyltetracarboxylic acid (s-BPDA) were added and stirred at 50 ° C. A polyamic acid solution having a solid content concentration of 18.2% and a logarithmic viscosity of 0.65 cm ³ / g was obtained (denoted as PI varnish A in the table).

  To the obtained polyamic acid solution, 9.0000 g (0.02758 mol, 15.2 mol%, 10.0 mass%) of triphenyl phosphate (TPP) was added and stirred to obtain a polyamic acid solution composition ( In the table, indicated as PI varnish B).

  The obtained polyamic acid solution composition is applied onto the glass substrate by a spin coater, and heated to 400 ° C. and held for 10 minutes to form a polyimide film having a thickness of 15 μm on the glass substrate. A polyimide laminate (indicated as glass / PI varnish B in Table 1) was obtained.

  The Tg of the polyimide film was 260 ° C. when measured by a conventional method using a differential scanning calorimeter: Diamond DSC (manufactured by Perkin Elmer).

  Hereinafter, this laminate was used as a substrate for a sample using glass / PI varnish B in Table 1 as a carrier substrate (functional laminate 106 uses glass / PI varnish A).

A SiO ₂ -containing layer having a layer thickness of 100 nm is formed on the produced laminate by an RF sputtering method (indicated in the table as RF sputtering), which is a vapor phase method, using the following target. Produced. As the sputtering apparatus, a magnetron sputtering apparatus (manufactured by Osaka Vacuum Co., Ltd., magnetron sputtering apparatus) was used. Hereinafter, although this apparatus is used for sputtering film formation, conditions such as power source type and power may be adjusted as appropriate.

As a target, a commercially available polycrystalline silicon target was used, Ar and O ₂ were used as process gases, and film formation was performed by an RF method using a magnetron sputtering apparatus. The sputtering power source power was 150 W and the film forming pressure was 0.5 Pa. In the film formation, the oxygen partial pressure was adjusted to 20%. It should be noted that, after film formation using a glass substrate in advance, data on the layer thickness change with respect to the film formation time was obtained under each film formation condition, and after calculating the layer thickness formed per unit time, the set layer thickness The film formation time was set so that

<Preparation of functional laminate 102>
In the same manner as the functional laminate 101, an NbO _x layer having a layer thickness of 10 nm is formed on the heat-resistant resin layer by RF sputtering using a commercially available metal Nb target under an oxygen partial pressure of 20%. A functional laminate 102 was produced.

<Preparation of functional laminate 103>
Using perhydropolysilazane (PHPS) containing Si as the non-transition metal (M1), a non-transition metal (M1) -containing layer is formed by a coating / modification method according to the following procedure, and the functional laminate 103 Was made.

  A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a perhydropolysilazane 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) at a ratio of 4: 1 (mass ratio), and further for adjusting the dry layer thickness A coating solution was prepared by appropriately diluting with dehydrated dibutyl ether.

  The above coating solution was applied by spin coating so that the dry layer thickness was 120 nm, and dried at 80 ° C. for 1 minute. Subsequently, the baking modification for 1 hour was performed at 350 degreeC.

<Preparation of functional laminate 104>
Using a polysilazane containing Si as the non-transition metal (M1), a non-transition metal (M1) -containing layer was formed by the coating / modifying method in the following procedure, and the functional laminate 104 was produced.

  A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 20% by mass of perhydropolysilazane in a ratio of 4: 1 (mass ratio), and further for adjusting the dry layer thickness A coating solution was prepared by appropriately diluting with dehydrated dibutyl ether.

The above coating solution was applied by spin coating so that the dry layer thickness was 120 nm, dried at 80 ° C. for 1 minute, and then aged for 10 minutes. Next, the sample on which the non-transition metal (M1) -containing layer was formed was placed in the vacuum ultraviolet irradiation apparatus shown in FIG. 3 having a Xe excimer lamp having a wavelength of 172 nm, and vacuum ultraviolet light was applied under the condition of irradiation energy of 3.0 J / cm ^2. Irradiation treatment was performed. At this time, nitrogen and oxygen were supplied into the chamber, and the oxygen concentration in the irradiation atmosphere was adjusted to 0.1% by volume. The stage temperature for installing the sample was set to 80 ° C.

<Preparation of functional laminate 105>
In the production of the functional laminate 104, the functional laminate 105 was produced in the same manner except that the vacuum ultraviolet irradiation treatment was performed under the condition of irradiation energy of 6.0 J / cm ² .

<Preparation of functional laminate 106>
In the production of the functional laminate 105, a functional laminate 106 was produced in the same manner except that a polyamic acid solution (PI varnish A) to which triphenyl phosphate (TPP) was not added was used.

<Preparation of functional laminate 107>
In the production of the functional laminate 101, a layer thickness of 50 nm was formed on the heat-resistant resin layer produced above by using the RF sputtering method and targeting the following mixture of Si and Nb under an oxygen partial pressure of 6%. A functional laminate 107 was produced in the same manner except that a Si and Nb oxide (SiO _x —NbO _y ) -containing layer was formed.

  Si and Nb powder pulverized so that Si was 80 atomic% and Nb was 20 atomic% were mixed, and subjected to hot pressing in an Ar atmosphere to perform sintering. After the sintered mixed material was mechanically molded, bonding was performed on a copper back plate to obtain a target.

As a sputtering apparatus, a magnetron sputtering apparatus (manufactured by Osaka Vacuum, magnetron sputtering apparatus) was used, and Ar and O ₂ were used as process gases, and film formation was performed by a DC method using a magnetron sputtering apparatus. The sputtering power source power was 150 W, the film forming pressure was 0.5 Pa, and the oxygen partial pressure was 6%.

<Preparation of functional laminate 108>
In the production of the functional laminate 103, after applying the polysilazane-containing layer, the firing modification is not performed, and a commercially available oxygen-deficient niobium oxide target (Nb ₁₂ O ₂₉ ) is used, and an RF sputtering method is used. A functional laminated body 108 was produced by forming an NbO _x layer having a layer thickness of 10 nm under an oxygen partial pressure of 8%.

<Preparation of functional laminate 109>
In the production of the functional laminate 108, the functional laminate 109 was produced in the same manner except that the polysilazane-containing layer was applied and then baked and modified in the air at 250 ° C. for 1 hour.

<Preparation of functional laminate 110>
In the production of the functional laminate 109, the same procedure was applied except that after the polysilazane-containing layer was applied, it was calcined and modified in a nitrogen (N ₂₎ atmosphere (both oxygen and water concentrations were 100 ppm or less) at 250 ° C. for 1 hour. A functional laminate 110 was produced.

<Preparation of functional laminate 111>
In production of the functional laminate 109, KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd., acrylic equivalent 210 g / mol) is diluted with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1% on a glass substrate. After the applied coating solution was applied with a wet film thickness of 2 μm, a polyimide film (UPILEX-50SGA manufactured by Ube Industries) was bonded and cured at 200 ° C. for 1 hour to form a heat resistant resin layer. A functional laminate 111 was produced in the same manner except for the above.

<Preparation of functional laminate 112>
In the production of the functional laminate 105, a polyimide film (UPILEX-125S manufactured by Ube Industries, Ltd.) was used instead of the glass substrate of glass / PI varnish B, and the following polyimide solution was cast onto the polyimide film. A heat-resistant resin layer is formed by film / polyimide solution film formation, and then a polysilazane coating layer is subjected to vacuum ultraviolet irradiation treatment under the condition of irradiation energy of 6.0 J / cm ² similarly to the functional laminate 105, A functional laminate 112 was produced.

(Polyimide solution film formation)
A predetermined amount of diamine and N-methylpyrrolidone (NMP) were charged into a 300 mL separable flask. The amount of NMP was adjusted so that the concentration of the resulting polyamic acid was 20%. After stirring at room temperature to completely dissolve the diamine, a predetermined amount of tetracarboxylic dianhydride was added little by little so that the internal temperature did not exceed 30 ° C. Stirring was continued for 3 hours under a nitrogen atmosphere to obtain a polyamic acid solution. Next, xylene was added as an azeotropic solvent, and imidation was performed by heating at 180 ° C. for 5 hours while continuously distilling water out of the system. Thereafter, xylene was completely distilled off at 200 ° C. to obtain a polyimide solution. The coating thickness of the obtained polyimide solution was adjusted on the polyimide film so that the cured heat-resistant resin layer had a thickness of 20 to 30 μm. After the application, it was dried at 80 ° C. for about 2 hours using a blow dryer to form a heat resistant resin layer.

<Preparation of functional laminate 113>
In the production of the functional laminate 104, a polyimide film (UPILEX-125S manufactured by Ube Industries, Ltd.) is used instead of the glass substrate of glass / PI varnish B, and the polyimide solution is cast onto the polyimide film thereon. A heat-resistant resin layer is formed by film / polyimide solution film formation, and then a polysilazane coating layer is subjected to vacuum ultraviolet irradiation treatment under the condition of irradiation energy of 3.0 J / cm ^{2 in} the same manner as the functional laminate 104, Next, an NbO _x layer having a thickness of 10 nm is formed by RF sputtering using a commercially available oxygen-deficient niobium oxide target (Nb ₁₂ O ₂₉ ) under an oxygen partial pressure of 8%. Produced.

<Preparation of functional laminate 114>
Similar to the production of the functional laminate 104, the polysilazane coating layer was modified by vacuum ultraviolet irradiation treatment under the irradiation energy of 3.0 J / cm ² , and then the RF sputtering method was applied on the polysilazane modified layer. Thus, a TaO _x layer having a layer thickness of 10 nm was formed using a commercially available Ta target under an oxygen partial pressure of 20%, and a functional laminate 114 was produced.

<Preparation of functional laminate 115>
Similarly to the production of the functional laminate 104, the polysilazane coating layer is modified by vacuum ultraviolet irradiation treatment under the irradiation energy of 3.0 J / cm ² , and then the RF sputtering method is applied to the polysilazane modified layer. Thus, using a commercially available oxygen-deficient niobium oxide target (Nb ₁₂ O ₂₉ ) under an oxygen partial pressure of 8%, an NbO _x layer having a thickness of 10 nm was formed, and a functional laminate 115 was produced.

<Preparation of functional laminate 116>
In the production of the functional laminate 115, a layer thickness is obtained by using a commercially available oxygen-deficient niobium oxide target (Nb ₁₂ O ₂₉ ) by a DC sputtering method instead of the RF sputtering method under an oxygen partial pressure of 20%. A functional laminate 116 was produced in the same manner except that a 10 nm NbO _x layer was formed.

<Preparation of Functional Laminate 117>
In the production of the functional laminate 115, a functional laminate 117 was produced in the same manner except that instead of the glass / PI varnish B, a glass / PA varnish laminate coated with the following polyarylate solution was used.

(Synthesis of polyarylate)
After adding 2514 parts by mass of water to a reaction vessel equipped with a stirrer, 22.7 parts by mass of sodium hydroxide and 9,9-bis (3,5-dimethyl-4-hydroxyphenyl as an aromatic dialcohol component ) Fluorene (BCF) 35.6 parts by mass, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (TMBPA) 18.5 parts by mass, p-tert-butylphenol (PTBP) as a molecular weight regulator 0.049 part by mass was dissolved, and 0.34 part by mass of a polymerization catalyst (tributylbenzylammonium chloride) was added and stirred. On the other hand, 26.8 parts by mass of an equal mixture of terephthalic acid chloride and isophthalic acid chloride as an aromatic dicarboxylic acid component was weighed and dissolved in 945 parts by mass of methylene chloride. This methylene chloride solution was added to the alkaline aqueous solution prepared above with stirring to initiate polymerization. The polymerization reaction temperature was adjusted to be 15 ° C. or higher and 20 ° C. or lower. The polymerization was carried out for 2 hours, and then acetic acid was added to the system to stop the polymerization reaction, and the organic phase and the aqueous phase were separated.

  The obtained organic phase was washed with ion exchange water twice as much as the organic phase for each washing, and then the operation of separating the organic phase and the aqueous phase was repeated. The washing was terminated when the electric conductivity of the washing water became less than 50 μS / cm. The organic phase after washing was put into a hot water tank equipped with a homomixer at 50 ° C., and methylene chloride was evaporated to obtain a powdery polymer. Furthermore, dehydration and drying were performed to obtain polyarylate.

(Application of polyarylate solution)
14 parts by mass of the obtained polyarylate and 100 parts by mass of dichloromethane were put in a sealed container, and gradually heated to 45 ° C. with stirring to be completely dissolved. The obtained solution was used as Azumi filter paper No. manufactured by Azumi Filter Paper Co., Ltd. Filtration using 244 gave a polyarylate solution.

  A polyarylate resin layer in which the polyarylate solution is applied on a glass substrate by a spin coater, heated to 400 ° C. and held for 10 minutes, and a polyarylate film having a thickness of 15 μm is formed on the glass plate Got.

  The Tg of the polyarylate film was 210 ° C. when measured by a conventional method using a differential scanning calorimeter: Diamond DSC (manufactured by Perkin Elmer).

<Preparation of functional laminate 118>
In the production of the functional laminate 111, KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd., acrylic equivalent 210 g / mol) is diluted with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1% on a glass substrate. After applying the applied coating liquid with a wet film thickness of 2 μm, a polyarylate film (polyarylate film M-2000H manufactured by Unitika Co., Ltd.) is bonded, and curing is performed at 200 ° C. for 1 hour to form a heat resistant resin layer Formed.

On top of that, the polysilazane coating layer is subjected to a vacuum ultraviolet ray irradiation treatment under the condition of irradiation energy of 3.0 J / cm ^{2 in} the same manner as the functional laminate 115, and then subjected to an RF sputtering method under a condition where the oxygen partial pressure is 20%. Using a commercially available oxygen-deficient niobium oxide target (Nb ₁₂ O ₂₉ ), an NbO _x layer having a thickness of 10 nm was formed, and a functional laminate 118 was manufactured.

<Preparation of functional laminate 119>
In the production of the functional laminate 111, KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd., acrylic equivalent 210 g / mol) is diluted with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1% on a glass substrate. After the applied coating solution was applied with a wet film thickness of 2 μm, a polyimide film (UPILEX-50SGA manufactured by Ube Industries) was bonded and cured at 200 ° C. for 1 hour to form a heat resistant resin layer. .

On top of that, the polysilazane coating layer is subjected to a vacuum ultraviolet ray irradiation treatment under the condition of irradiation energy of 3.0 J / cm ^{2 in} the same manner as the functional laminate 115, and then subjected to an RF sputtering method under a condition where the oxygen partial pressure is 20%. Using a commercially available oxygen-deficient niobium oxide target (Nb ₁₂ O ₂₉ ), an NbO _x layer having a thickness of 10 nm was formed, and a functional laminate 119 was manufactured.

≪Evaluation≫
[1] Presence or absence of generation of bubbles between carrier substrate / heat-resistant resin layer The presence / absence of generation of bubbles between the carrier substrate and the heat-resistant resin layer was visually evaluated.

[2] Measurement of composition distribution in thickness direction of functional layer The composition distribution profile in the thickness direction of the functional layer was measured by XPS analysis for the produced functional laminates 101 to 119. The XPS analysis conditions are as follows.

<XPS analysis conditions>
・ Device: QUANTERA SXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement was repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data for every 1 nm is obtained in the depth direction)
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used. The analyzed elements are Si, Nb, Ta, Al, O, N, and C.

<Measurement of mixing area thickness>
Taking the case where the transition metal is Nb as an example, the composition of the functional layer can be represented by (Si) (Nb) xOyNz from the data obtained from the XPS composition analysis. In the aspect in which the first layer and the second layer are laminated, Si as a non-transition metal and Nb as a transition metal coexist in the interface region between the first layer and the second layer, and the transition metal Nb / Si. The region where the value x of the atomic number ratio in the range of 0.02 ≦ x ≦ 49 was defined as “mixed region”, and the presence / absence of the region and its thickness (nm) were measured and listed in the table. The same measurement is performed in the case where the functional layer is formed as a complex oxide layer of non-transition metal Si and transition metal Nb (or Ta), and the thickness (nm) of the mixed region is 5 nm or more. In the table, “Yes” is indicated.

<Calculation of oxygen deficiency index in mixed region>
Using the XPS analysis data, a value of (2y + 3z) / (a + bx) at each measurement point was calculated. Here, since the non-transition metal is Si, a = 4, and since the transition metal is Nb or Ta, a = 5. The minimum value of the value of (2y + 3z) / (a + bx) was determined and listed in the table as an oxygen deficiency index. When (2y + 3z) / (a + bx) <1.0, this is an oxygen deficient state, which is indicated as “<1.0” in the table.

[3] Peel strength between carrier substrate and heat-resistant resin layer Peel strength was measured using the 90 ° peel method defined in JIS Z0237: 2009 as a performance evaluation (test) method for adhesive tapes and sheets.

<Measurement method>
The sample was pretreated for 24 hours or longer in an atmosphere of a standard state where the temperature was 23 ± 1 ° C. and the relative humidity was (50 ± 5)%.

  The width of the sample was adjusted to 25 mm and the length was 50 mm.

  As the test apparatus, a tensile tester is used, and a tensile tester specified in JIS B 7721 or a tensile tester equivalent thereto is used.

  A part of the end portion of the heat-resistant resin layer is peeled off from the substrate and is sandwiched between tensile testers, and the force required to peel off from the peeled end portion in the 90 ° direction at a pulling speed of 50 m / min is measured. The unit is (kN / m).

○: Peel strength is 0.2 kN / m or less Δ: Peel strength exceeds 0.2 kN / m ×: Heat-resistant resin layer is broken and cannot be peeled When the carrier substrate is a resin film, the resin film itself is an adhesive. After pasting on a glass substrate, the peel strength was measured.

[4] Evaluation of water vapor barrier property After forming each functional layer, a sample using a glass substrate peels off the laminate of the heat resistant resin layer / functional layer (gas barrier layer) from the glass substrate, and heat resistant resin The water vapor permeability was measured by the following method using the layer / functional layer (gas barrier layer). In addition, when the heat resistant resin layer / functional layer could not be peeled from the glass substrate, the laminate of the heat resistant resin layer / functional layer was separated from the glass substrate by laser irradiation from the glass surface side.

  As a method for measuring the water vapor transmission rate, the following Ca method was used.

(Preparation of water vapor barrier property evaluation cell)
On the gas barrier layer surface of each sample sample, use a vacuum deposition device (JEOL-made vacuum deposition device JEE-400) to mask the portions other than the portion of the sample sample to be deposited (9 locations of 12 mm x 12 mm), Evaporated. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

The obtained sample with both sides sealed was stored at 60 ° C. and 90% RH under high temperature and high humidity, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water (g / m ² · 24 h) was calculated.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier layer surface of the sample sample, a sample obtained by depositing metallic calcium using a quartz glass substrate having a thickness of 0.2 mm instead of the sample sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 60 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

  The water vapor permeability of each sample sample measured as described above was evaluated according to the following criteria.

(Devices and materials used)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (3-5mmφ, granular)
(Evaluation scale)
A: Water vapor permeability is 1 × 10 ⁻⁵ g / m ² · 24 hr or less ○: Water vapor permeability exceeds 1 × 10 ⁻⁵ g / m ² · 24 hr, 1 × 10 ⁻³ g / m ² · 24 hr or less Δ: Water vapor permeability exceeds 1 × 10 ⁻³ g / m ² · 24 hr, 1 × 10 ⁻² g / m ² · 24 hr or less ×: Water vapor permeability is 1 × 10 ⁻² g / m Exceeding ² · 24 hr, 1 × 10 ⁻¹ g / m ² · 24 hr or less XX: Water vapor permeability exceeding 1 × 10 ⁻¹ g / m ² · 24 hr, 1.0 g / m ² · 24 hr or less XX: Water vapor transmission rate exceeding 1.0 g / m ² · 24 hr The water vapor transmission rate is desirably ◯ or more.

[5] Measurement of surface roughness of functional layer The surface roughness Ra defined by JIS B0601: 2001 of the surface of the functional layer was measured using a non-contact three-dimensional micro surface shape measurement system (WYKO manufactured by Veeco). .

○: Surface roughness Ra is 2 nm or less. Δ: Surface roughness Ra exceeds 2 nm. Tables 1 and 2 show the configuration of the functional laminate produced and the evaluation results.

  From Tables 1 and 2, the functional laminates 107 to 111 and 113 to 119 of the present invention can peel the heat-resistant resin layer from the carrier substrate without laser irradiation, and bubbles are generated or deformed during polysilazane modification. The water vapor permeability is small, and the smoothness is good. From the above, it can be seen that the electronic device has gas barrier properties and smoothness that can be suitably applied to organic EL elements and the like.

  Comparative Examples 101-104 are inferior in gas barrier property and smoothness. In Comparative Examples 105, 106 and 112, the gas barrier property is slightly improved by abruptly modifying polysilazane, but the glass substrate is insufficient. The heat resistant resin layer can no longer be peeled off or bubbles are generated.

DESCRIPTION OF SYMBOLS 1 Functional laminated body 2 Carrier substrate 3 Heat resistant resin layer 4 Functional layer 100 Vacuum ultraviolet light irradiation apparatus 101 Apparatus chamber 102 Xe excimer lamp 103 Excimer lamp holder 104 Sample stage 105 Polysilazane compound coating layer formation sample 106 Light shielding plate

Claims (12)

  A functional laminate having, in order, a heat resistant resin layer and a functional layer containing a metal compound on a carrier substrate, wherein the glass transition temperature (Tg) of the heat resistant resin layer is within a range of 200 to 400 ° C. And the functional layer has a mixed region of a non-transition metal and a transition metal.   The functional laminate according to claim 1, wherein the heat-resistant resin layer contains polyimide.   The functional laminate according to claim 1, wherein the non-transition metal is silicon (Si).   The functional laminate according to any one of claims 1 to 3, wherein the transition metal is a Group 5 element of a long-period periodic table of elements.   The functional laminate according to claim 4, wherein the transition metal is niobium (Nb).   The functional laminate according to any one of claims 1 to 5, wherein the carrier substrate is an inorganic glass substrate.   The functional laminate according to any one of claims 1 to 5, wherein the carrier substrate is a resin film.   The functional laminate according to any one of claims 1 to 7, wherein a peel strength when peeling the heat resistant resin layer from the carrier substrate is 0.2 kN / m or less. body. It is a manufacturing method of the functional laminated body which manufactures the functional laminated body as described in any one of Claim 1- Claim 8, Comprising: It has the following (a)-(c) step, It is characterized by the above-mentioned. A method for producing a functional laminate.
(A) A step of applying a heat-resistant resin precursor liquid on the carrier substrate (b) A step of heating the carrier substrate / heat-resistant resin precursor laminate to form a heat-resistant resin layer (c) a heat-resistant resin layer Forming a functional layer thereon The method for producing a functional laminate according to claim 9, wherein the step (c) of forming the functional layer on the heat resistant resin layer includes the following steps (c1) and (c2). .
(C1) forming a layer containing a metal compound of a non-transition metal (c2) forming a mixed region of the non-transition metal and the transition metal   The method for producing a functional laminate according to claim 10, wherein the metal compound of the non-transition metal contains polysilazane.   The method for producing a functional laminate according to claim 10, wherein the transition metal is a Group 5 element in the long-period periodic table of elements.

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