WO2014129464A1

WO2014129464A1 - Laminate body, solar cell member, solar cell, display device member, display device, and method for manufacturing laminate body

Info

Publication number: WO2014129464A1
Application number: PCT/JP2014/053791
Authority: WO
Inventors: 友貴須藤; 正和片山; 平石　克文; 拓平太田
Original assignee: 新日鉄住金化学株式会社
Priority date: 2013-02-19
Filing date: 2014-02-18
Publication date: 2014-08-28
Also published as: JP6445965B2; TW201500207A; JPWO2014129464A1

Abstract

In order to provide a laminate body of balanced heat resistance and adhesiveness that has a resin layer and a barrier protective layer comprising an inorganic substance such as a metal, a solar cell member using the laminate body, a solar cell, a display device member, a display device, and a method for manufacturing the laminate body, the present invention is a laminate body in which are layered a first layer comprising an inorganic substance such as a metal, and a second layer comprising a resin, wherein a configuration is adopted in which the thermal weight reduction of the resin at 545°C is no greater than 1.0%, and the peel strength of the boundary between the second layer and the first layer is at least 100 N/m.

Description

LAMINATE, SOLAR CELL MEMBER, SOLAR CELL, DISPLAY DEVICE MEMBER, DISPLAY DEVICE AND LAMINATE MANUFACTURING METHOD

The present invention relates to a laminate, a solar cell member, a solar cell, a display device member, a display device, and a method for manufacturing the laminate.

In recent years, with the increase in functionality, miniaturization, and weight reduction of various electronic devices such as mobile phones, digital cameras, digital video, PDAs, car navigators, hard disks, etc., these substrate materials have flexibility, A flexible substrate that has a high degree of freedom in installation and can be easily thinned is employed.
With respect to flexible substrates used in these increasingly sophisticated electronic devices, there are increasing demands for further miniaturization, higher density, multilayering, finer, and higher heat resistance.

In order to meet such a demand, Patent Document 1 discloses that a polyimide resin layer is directly formed on a conductor to be a circuit wiring by coating (hereinafter abbreviated as a coating method) as a method for manufacturing a polyimide laminate, and heat A method of forming a plurality of polyimide resin layers having different expansion coefficients by multilayering is disclosed. According to this method, it is possible to provide a flexible printed board having excellent reliability in terms of dimensional stability with respect to temperature change, adhesive strength, flatness after etching, and the like.

Here, the coating method means that after applying a polyimide precursor resin solution or a polyimide resin solution to be a polyimide resin layer to the metal layer, the metal layer and the polyimide resin layer are dried only or by heat treatment for drying and imidization. Is a method of adhering.

Patent Document 2 discloses a method of forming a flexible printed circuit board by bonding a conductor layer and a resin substrate by thermocompression bonding, and a copper foil surface as a conductor layer is subjected to a roughening process by plating made of copper-cobalt-nickel. And improving the adhesion by roughening the surface of the copper foil.

Hereinafter, the method of bonding the conductor layer and the resin substrate by thermocompression bonding may be abbreviated as “thermocompression bonding method”.

By the way, in connection with wiring or semiconductor elements on flexible printed circuit boards, lead-free solder material with a melting temperature higher than that of lead solder has been used for environmental considerations. The contacting polyimide resin layer is highly heat resistant.

For this reason, the adhesion of the polyimide to the metal layer is reduced, and when the metal layer and the polyimide resin layer are bonded together by the thermocompression bonding method, peeling between the metal layer and the polyimide resin layer is likely to occur during thermocompression bonding. There's a problem. Due to this peeling, there is a problem that the reliability of adhesion between the metal layer and the polyimide resin layer is lowered, such as wiring peeling due to permeation of the acid cleaning liquid when a circuit is formed on the flexible printed board.

In response to this problem, Patent Document 3 discloses a method of controlling the plating layer on the copper foil roughening treatment surface, which is a metal layer, to suppress the roughening treatment height, that is, the degree of roughening treatment.
However, this method has a problem that the peel strength between the copper foil and the polyimide resin layer is lowered. Thus, the subject of making adhesiveness and heat resistance in a double-sided metal-clad laminate compatible is left.

By the way, for solar cells, CIS (CuInSe) and CIGS (CuInGaSe) solar cells, which are a kind of compound semiconductor solar cells having higher conversion efficiency than thin-film Si (including amorphous Si), are attracting attention.
Patent Document 4 discloses an example in which a metal thin film-resin material laminate is applied as a flexible substrate for a CIS solar cell. In the examples, polyimide resin is used as a resin material. A molybdenum (Mo) film is sputtered as a back electrode on the polyimide resin surface. Usually, after film-forming by sputtering of Mo film used as an electrode, after forming a scribe line required as a solar cell module, a light absorption layer is formed above this Mo film.
The film formation of the light absorption layer represented by CIGS or CIS is performed at about 500 ° C. However, in such a high temperature region, it is desired that the resin material that is an organic substance is a single material or a high-level design of a laminate. Has been.

However, according to the invention described in Patent Document 4, when the constituent components of the CIS solar cell such as the CIGS layer are formed at the above-described high temperature, the heat resistance is not sufficient. Peeling may occur.

In the above laminate, oxygen resistance / water vapor permeability, which is an important characteristic when used as a substrate for a solar cell, is hereinafter referred to as barrier property.

Japanese Patent Publication No. 6-93537 JP-A-8-335775 WO2010 / 010892 Japanese Patent Laid-Open No. 11-135811 JP 2000-160246 A Japanese Patent Laid-Open No. 9-302415

The present invention solves the above-described problems, and the resin layer in contact with the barrier protective layer made of an inorganic material such as metal has high heat resistance, and further, peeling occurs between the barrier protective layer and the heat resistant resin layer. It aims at providing the laminated body which suppressed generation | occurrence | production of this and improved the adhesiveness of a barrier property protective layer and a resin layer.
That is, an object of the present invention is to solve the above-described problems and to achieve both heat resistance and adhesiveness in a laminate of a barrier protective layer-resin layer made of an inorganic material.

As a result of intensive studies to solve the above problems, the present inventors have solved the above problems with a laminate of a combination of a resin layer having specific heat resistance and adhesiveness and a barrier protective layer made of an inorganic material. As a result, the present invention has been completed.

That is, the laminate of the present invention is a laminate in which a second layer made of a resin and a first layer made of an inorganic material are laminated, and the thermal weight loss of the resin at 545 ° C. is 1.0% or less. And the peel strength at the interface between the second layer and the first layer is 100 N / m or more.
With such a configuration, preferable heat resistance of the second layer is obtained, and high adhesion (peeling resistance) between the second layer and the first layer is obtained.

Also preferably, in the laminate of the present invention, the thermal weight loss of the resin at 545 ° C. is 0.7% or less.

In the laminate of the present invention, the linear thermal expansion coefficient in the plane direction of the first layer is preferably 15 ppm / K or less.
According to such conditions, a TFT (Thin formed of a lower electrode layer or a power generation layer for a device formed on a substrate, for example, a compound semiconductor solar cell, or polysilicon or an oxide for a display device, etc. This is because the thermal stress generated between the semiconductor layer for driving such as a film transistor is reduced, and the occurrence of warpage and peeling during heat treatment can be suppressed.

In the laminate of the present invention, it is preferable that the second layer is formed of one or more resin materials selected from the group consisting of polyimide and derivatives thereof.
According to such a condition, the second layer having a small thermogravimetric decrease, heat resistance, and high adhesion to the first layer can be obtained.

In the laminate of the present invention, the first layer is preferably formed of one or two or more metal materials selected from the group consisting of metals, and the group consisting of ferritic stainless steel and titanium. More preferably, it is formed of one or more inorganic materials selected from the above.
According to such conditions, the second layer can be supported and high barrier properties can be ensured.

The laminate of the present invention is preferably obtained by applying a heat treatment at 300 ° C. or higher after applying the resin or its precursor to the surface of the first layer. It is preferably obtained by performing a heat treatment at a concentration of 10% or less.
According to such conditions, the second layer having a small thermogravimetric decrease and heat resistance can be obtained. In particular, when heat treatment is performed under a condition where the oxygen concentration is 10% or less, the resin-inorganic matter in the laminate is obtained. This is because the adhesive strength of the is increased.

Further, the present invention is applicable to a solar cell member or solar cell including the laminate. In addition, the present invention is applicable to a display device member or a display device including the laminate.

Moreover, the manufacturing method of the laminated body of this invention is the surface of this 1st layer by the process of apply | coating resin or its precursor continuously on the surface of the 1st layer which consists of an inorganic substance, and the heat processing in 300 degreeC or more. Alternatively, the step of forming the second layer made of the resin on the side surface is performed by roll-to-roll.
The heat treatment is preferably performed at an oxygen concentration of 10% or less.

The laminate of the present invention is suitable for various applications that require flexibility and heat resistance.
Therefore, it is suitable for flexible substrates such as display members such as organic EL having TFT semiconductors that require high-temperature processing, power semiconductor-mounted inverter members characterized by high-temperature operation, and compound semiconductor solar cells typified by chalcopyrites. Applicable to.

In the prior art laminates, problems such as a decrease in electrical insulation and oxygen / water vapor permeability (hereinafter referred to as “barrier property”) occur, so that sufficient conversion efficiency or durability as a solar cell cannot be obtained. Although there was a profit, according to the present invention, it is possible to provide a flexible laminate substrate for a compound semiconductor solar cell that can withstand practical use.

In the laminate of the present invention, the resin layer has high heat resistance and not only exhibits excellent dimensional stability, but also suppresses peeling between the inorganic layer and the resin layer in contact therewith and has high adhesiveness.

The method for producing a laminate of the present invention is a laminate in which the resin layer has high heat resistance and not only exhibits excellent dimensional stability but also suppresses peeling between the inorganic layer and the resin layer in contact therewith and has high adhesion. The body can be easily manufactured.

It is sectional drawing of the laminated body of embodiment of this invention. It is a flowchart which shows the manufacturing method of the laminated body of embodiment of this invention. It is sectional drawing of the flexible solar cell of embodiment of this invention. It is a flowchart which shows the manufacturing method of the flexible solar cell of embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail.

FIG. 1 is a cross-sectional view of the laminate according to the embodiment.
The laminate 10 of the present embodiment is a polyimide layer-containing flexible substrate, and is a laminate obtained by laminating a second layer 2 made of resin and a first layer 1 made of an inorganic substance. The thermal weight loss at 545 ° C. is 1.0% or less, and the peel strength at the interface between the second layer 2 and the first layer 1 is 100 N / m or more.

Here, the thermal weight loss at 545 ° C. is a weight reduction rate when heating is performed at a temperature rising rate of 10 ° C./min under a temperature rising range from room temperature to 545 ° C. in a nitrogen stream. When the thermal weight reduction is 1.0% or less, the heat resistance of the second layer 2 is high. For example, a flexible substrate used for a compound semiconductor solar cell including CIGS (CuInGaSe) or CIS (CuInSe) In addition, it can be preferably applied to a flexible substrate used in a display device or the like on which a driving semiconductor layer such as a TFT formed of polysilicon or oxide is mounted. In order to further improve the heat resistance, the thermal weight reduction at 545 ° C. is preferably 0.7% or less, more preferably 0.4% or less.

The peel strength at the interface between the second layer 2 and the first layer 1 is a test piece having a processing line width suitable for the purpose of measurement by patterning and etching the laminate to a line width of 1 to 10 mm. This is the peel strength when the second layer is peeled off in the 180 ° direction using.
The higher peel strength is preferably 300 N / m or more, and more preferably 700 N / m or more.
Further, the peel strength after heat treatment at 500 ° C. for 60 minutes is preferably 100 N / m or more, more preferably 300 N / m or more, and even more preferably 700 N / m or more.

When the thermal weight loss exceeds 1.0 or the peel strength is less than 100 N / m, for example, when forming a CIGS solar cell, which is a kind of compound semiconductor solar cell, or for a display device, the TFT There is a possibility that the high temperature condition during the formation of the driving semiconductor layer cannot be endured, or the handling property during the processing process is not sufficiently ensured, and the resin layer-inorganic layer interface peels off.

When the laminate is commercially produced using a substrate of a specific product, such as a display device or a solar cell, it is accompanied by conveyance before and after various processes and treatments required in the production line. In order to meet the demand when transport agility that matches the practical transport time above is required, and when mass production is realized in actual production and the merits of industrial use are realized by supplying the product, a peel of 100 N / m or more is required. By ensuring the strength, the substrate does not peel off as an interlayer adhesion.

Moreover, the laminated body of this invention may arrange | position the 2nd layer 2 on both surfaces or side surfaces of the 1st layer 1, and is the multilayered structure by which the 2nd layer 2 and the 1st layer 1 were laminated | stacked alternately. There may be.
When the second layer 2 is arranged on both surfaces of the first layer 1, for example, occurrence of warpage of the laminate due to a difference in linear expansion between the first layer and the second layer due to a change in surrounding environment such as temperature. It can also be a suppression means against

Furthermore, if the linear thermal expansion coefficient in the plane direction of the first layer 1 is 15 ppm / K or less, the laminate of the present invention has a lower electrode layer or a device formed on a substrate, for example, a compound solar cell. In the case of a power generation layer or a display device, thermal stress generated between the driving semiconductor layer such as a TFT formed of polysilicon or oxide is reduced. For example, a solar cell member or display during high-temperature heat treatment Since generation | occurrence | production of the peeling and curvature of an interlayer in the apparatus member can be suppressed, it is preferable. The linear thermal expansion coefficient in the surface direction of the first layer 1 is more preferably 13 ppm / K or less.

Here, the linear thermal expansion coefficient means that the first layer 1 is removed from the produced laminate and only the second layer 2 is taken out as a measurement specimen, and the measurement specimen is 200 ° C. in a nitrogen stream. The temperature of the test piece (second layer 2) is lowered at a constant rate after the temperature is raised to a high temperature range exceeding 50 ° C., and is obtained from the relationship between the temperature difference at that time and the measurement length of the test piece.

Moreover, the 2nd layer 2 will not have a restriction | limiting in the kind, if the performance as a laminated body can be ensured, For example, it is 1 type, or 2 or more types of resin materials selected from the group which consists of a polyimide and those derivatives. Can be formed. These are preferable from the viewpoints of heat resistance and adhesion to the first layer 1.

The thickness of the second layer 2 is not particularly limited, but the average film thickness is preferably 1 to 100 μm, more preferably 2 to 8 μm, and even more preferably 2 to 4 μm. When the average film thickness is less than 1 μm, the electric insulation tends to be insufficient, and when the average film thickness exceeds 100 μm, the productivity tends to be impaired.

Further, the surface roughness of the second layer 2 on the opposite side of the interface with the first layer 1 is not particularly limited, but preferably there is a problem with the electrode layer formed on the resin layer, such as a crack. Ra (average roughness) is 20 nm or less, and more preferably 10 nm or less, for the purpose of suppressing conduction failure due to or fault.

Hereinafter, polyimide and their derivatives which are particularly preferable examples as the second layer 2 will be described in detail.

The polyimide used as the second layer and derivatives thereof are obtained by reacting an aromatic diamino compound represented by NH ₂ —Ar ¹ —NH ₂ with a tetracarboxylic acid compound, and are said to be easy to synthesize. Preferred for reasons.
Here, the first aryl group Ar ¹ substituted with two amino groups can be selected from any ^one , but because it has both heat resistance and a low linear thermal expansion coefficient, the following formula (1) to It is preferable that it is selected from the group represented by (3).

The following formula (1) shows bonds and side chains composed of primary to tertiary carbons that are expected to have low heat resistance, and elements other than carbon and carbon that are also expected to have low heat resistance (BC, O— An example of Ar ¹ constituting a monomer for polyimide excluding a monomer that yields a polyimide structure having a bond (excluding an imide ring bond) consisting of C, S—C, N—C, P—C, Se—C) Examples include fluorene-9,10-bisaniline.

(1)

The following formula (2) shows an example of Ar ¹ constituting a monomer for polyimide in which a halogeno group, a trihalogenomethyl group, a dihalogenomethylene group, or a hexahalogenoisopropylidene group is directly bonded to an aromatic ring. Specific examples include diaminobistrihalogenomethylbiphenyl. These groups may have a plurality of bonds directly bonded to the aromatic ring. Here, X represents a halogen element, preferably fluorine.

(X is a halogen element)
(2)

Also, the following formula (3) shows an example of Ar ¹ constituting a monomer that provides a polyimide that does not contain a structure other than an aromatic ring and an imide ring. Specifically, terphenyldiamine, diaminodiphenylbiphenyl, and the like Can be mentioned.

(3)

Of the Ar1 represented by the above formulas (1) to (3), a structure represented by the formula (3) is more preferred, and a structure constituting a phenylenediamine compound is more preferred. The phenylenediamine compound has a plurality of isomers, and may be the same isomer or a combination of a plurality of isomers.

Ar ¹ may have a substituent, but preferably has no substituent or is substituted with a halogeno group. One or more of these aromatic diamino compounds may be used.

Examples of the tetracarboxylic acid compound to be reacted with the diamino compound include aromatic tetracarboxylic acid and acid anhydrides, esterified products, halides, etc., but aromatic tetracarboxylic acid compounds are preferred and are precursors of polyimide resins. In terms of ease of synthesis of the polyamic acid (polyamic acid), the acid anhydride is preferable. As the aromatic tetracarboxylic acid _{^{compound, O (CO) 2 Ar 2}} (CO) a compound represented by ₂ O is mentioned as suitable.

Here, the second aryl group Ar ² substituted with _two (CO) ₂ O groups can be selected from any one, but for the reason that it has both heat resistance and a low linear thermal expansion coefficient, the following formula: Preferred are those selected from the groups represented by (4) to (6). The substitution position of the acid anhydride group [(CO) ₂ O] is arbitrary, but a symmetric position around Ar ² is preferable.

The following formula (4) shows bonds and side chains composed of primary to tertiary carbons that are expected to have low heat resistance, and elements other than carbon and carbon that are also expected to have low heat resistance (BC, O— Constructs a monomer for polyimide as shown in the following formula (7) excluding a monomer that gives a polyimide structure having a bond (excluding an imide ring bond) consisting of C, S—C, N—C, P—C, and Se—C) Specific examples of Ar ² include fluorene-9,10-bisphthalic anhydride.

(4)

The following formula (5) shows an example of Ar ² constituting a monomer for polyimide in which a halogeno group, a trihalogenomethyl group, a dihalogenomethylene group, or a hexahalogenoisopropylidene group is directly bonded to an aromatic ring. Specific examples include halogenopyromellitic anhydride and 4,4′-hexahalogenoisopropylidenebisphthalic anhydride. These groups may have a plurality of bonds directly bonded to the halogenoaromatic ring. Here, X represents a halogen element, preferably fluorine.

(X is a halogen element)
(5)

Further, the following formula (6) is an example of Ar ² constituting a monomer that provides a polyimide that does not contain a structure other than an aromatic ring and an imide ring. Specifically, pyromellitic anhydride, 1, 6, Examples include 7,12-perylenetetracarboxylic dianhydride.

(6)

Of the Ar ² represented by the above formulas (4) to (6), more preferably the structure represented by the formula (6), more preferably a biphenyltetracarboxylic dianhydride or a naphthalenetetracarboxylic dianhydride. It is a structure to do. Biphenyltetracarboxylic dianhydride and naphthalenetetracarboxylic dianhydride each have a plurality of isomers, both of which may be the same isomer or a combination of isomers, biphenyltetracarboxylic dianhydride and A combination of naphthalenetetracarboxylic dianhydrides may be used.

Ar ² may have a substituent, but preferably does not have a substituent or is substituted with a halogeno group. One or more of these aromatic acid anhydride compounds may be used.

In the polyimide used as the second layer 2 and derivatives thereof, a more preferable combination of the aromatic diamino compound and the tetracarboxylic acid compound is a combination of a biphenyltetracarboxylic acid compound and a phenylenediamine compound, or biphenyltetracarboxylic acid. Acid compound, phenylenediamine compound and 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl combination, biphenyltetracarboxylic acid compound, naphthalenetetracarboxylic acid compound and phenylenediamine compound combination and biphenyltetracarboxylic acid A combination of an acid compound, a naphthalenetetracarboxylic acid compound, a phenylenediamine compound and 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, and a copolymer thereof.
Here, the content of 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl is preferably 5% or less with respect to the total amount of the aromatic diamino compound, more preferably 2. 5% or less.

The polyimide resin constituting the second layer 2 is prepared by reacting, for example, the aromatic diamino compound and the tetracarboxylic acid compound in an approximately equimolar amount in a solvent, and polyamic acid (polyamic acid) which is a polyimide resin precursor. ) And an imidization reaction.

Until the synthesis of the polyamic acid, which is a precursor of the polyimide resin, is performed in a reaction vessel or the like before application to the first layer 1. Or it is good also as imidation, and it is good also as a polyimide resin solution. And the polyamic-acid solution or polyimide resin solution which is a precursor is apply | coated to the 1st layer 1, and it is set as a pre polyimide resin layer. Here, the coating layers of the polyamic acid solution and the polyimide resin solution, which are precursors, are collectively referred to as a pre-polyimide resin layer. Of course, it may be applied to the pre-polyimide resin layer or the polyimide resin layer that has already been applied.

The polyimide used as the second layer 2 can be manufactured by the following method, for example. That is, the aromatic diamino compound and tetracarboxylic dianhydride are mixed in a solvent at an approximately equimolar ratio, and reacted in a reaction temperature range of 0 to 200 ° C., preferably in a range of 0 to 100 ° C. There is a method for obtaining a polyimide resin by obtaining a polyamic acid solution as a precursor and imidizing the solution.

As the solvent, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol, halogenated phenol, cyclohexanone, Examples include dioxane, tetrahydrofuran, diglyme, and triglyme.

As described above, imidization may be performed after applying the precursor polyamic acid solution to the first layer 1.

The pre-polyimide resin layer applied to the first layer 1 may be either the polyamic acid solution that is the precursor or the polyimide resin solution that has been imidized, but if the polyimide is not solvent-soluble, a viscosity adjustment viewpoint. Therefore, a polyamic acid solution as a precursor is preferable.

In addition, the first layer 1 is an inorganic substance, and the type of the first layer 1 is not limited as long as the performance as a laminate can be ensured. For example, copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, It is formed of one or more metal materials or glass selected from the group consisting of molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, silicon, bismuth, indium or alloys thereof. From the viewpoints of heat resistance and adhesiveness to the second layer 2, it is preferable. More preferably, it is one or two or more kinds of metal materials selected from the above group in that the base material is difficult to break, and particularly preferably at the time of preparing a laminate or assembling a display device or a solar cell or Austenitic stainless steel, martensitic stainless steel, duplex stainless steel, precipitation hardened stainless steel, ferritic stainless steel and titanium in terms of resistance to rust during use, and more preferably ferritic stainless steel in terms of low linear thermal expansion And titanium.

The layer thickness of the first layer 1 is preferably 5 to 300 μm, more preferably 20 to 200 μm. When the layer thickness exceeds 300 μm, continuous processes such as roll-to-roll tend to be difficult, and when the layer thickness is less than 20 μm, the self-supporting property tends to decrease.

In addition, for the first layer 1, sizing, chromium plating, nickel plating, chromium − are applied to the surface for the purpose of adjusting and modifying the suitability of the surface properties and improving the adhesive strength with the second layer 2. Nickel plating, copper-zinc alloy plating, copper oxide deposition or aluminum alcoholate, aluminum chelate, silane coupling agent, titanate coupling agent, titanium compounds such as alkoxy titanium, silane compounds such as alkoxy silane, triazine thiols, benzotriazole , Acetylene alcohols, acetylacetones, catechols, o-benzoquinones, tannins, quinolinols and other chemical surface treatments or mechanical surface treatments such as surface roughening treatments.

Next, the laminate manufacturing method of the present invention will be described below by taking a laminate in which the second layer is polyimide as an example of the embodiment, but the present invention is not limited to the embodiment.

FIG. 2 is a flowchart showing the method for manufacturing the laminate according to the present embodiment.
In the manufacturing method of the laminate according to the present embodiment, first, a polyamic acid solution or a polyimide resin solution that is a precursor to be the second layer 2 is applied to an inorganic material to be the first layer 1, and a pre-polyimide resin is then applied. A layer is formed (S1). Here, the polyamic acid solution and the polyimide resin solution which are precursors are collectively referred to as a pre-polyimide resin layer.

Next, the second layer 2 and the pre-polyimide resin layer are bonded together by drying [heat removal of the solvent] (S2) and imidization [heat curing treatment] (S3), and the second layer 2 is formed. Polyimide is formed on the inorganic material. Here, drying and imidization are performed when a polyamic acid solution as a precursor is applied, and only drying is performed when a polyimide resin solution is applied. As described above, a laminate made of polyimide and an inorganic material is formed. A detailed manufacturing method will be described later.
Applying the above-mentioned precursor polyamic acid solution or polyimide resin solution to form a pre-polyimide resin layer (S1), drying [solvent heat removal] step (S2) and imidization step [heat curing treatment] (S3) can be performed continuously.
For example, a step (S1) of continuously applying a resin or a precursor thereof to the surface of the first layer made of an inorganic substance, and a second step made of the resin on the surface of the first layer by heat treatment at 300 ° C. or higher. Steps (S2, S3) for forming the layer can be performed roll-to-roll.

Next, the method for producing a laminate of the present invention will be described in detail by taking polyimide as the second layer 2 as an example.

To manufacture the laminate of the present invention, first, a pre-polyimide resin layer is applied to the first layer 1. At this time, the pre-polyimide resin layer applied to the first layer 1 becomes the second layer 2. In addition, an arbitrary method can be selected as a coating method for forming a plurality of pre-polyimide resin layers on the first layer 1, but the following three methods are preferable from the viewpoint of coating accuracy.

1) Two or more kinds of pre-polyimide resin layers are simultaneously coated on a conductor by a multilayer die.
2) After applying the pre-polyimide resin layer by an arbitrary method, another pre-polyimide resin layer is applied onto the undried application surface by a knife coating method, a die method, or the like.
3) A pre-polyimide resin layer is applied by an arbitrary method and dried, and then another pre-polyimide resin layer is applied to the dry coated surface by an arbitrary method.
The knife coating method described here is a method in which a resin solution is leveled and applied with a bar, squeegee, knife or the like.

As the drying and imidization (heat curing) treatment method, any method can be utilized. After the pre-polyimide resin layer is applied and formed, a laminate including a pre-dried uncured pre-polyimide resin layer, Heat treatment at a high temperature (200 ° C. or higher) by allowing it to stand for a certain period of time in a hot air drying furnace that can be set to a predetermined temperature, or by continuously moving within the drying furnace area range to ensure a predetermined drying and curing time ), A stacked body having one or more second layers can be formed.

In consideration of work efficiency and yield, the pre-polyimide resin layer is applied, and then the pre-dried uncured laminate is wound into a roll and then dried at a high temperature and heat-cured. Processing methods are also possible.

Further, in the drying and imidization (heat curing) treatment step, the solvent is removed from the pre-polyimide resin layer by heat treatment, and when the polyimide precursor resin solution is used, the imide ring is further closed. At this time, since a skin layer is formed on the resin surface when the heat treatment is suddenly performed at a high temperature and the solvent is difficult to evaporate or foams, it is desirable to perform the heat treatment while gradually raising the temperature from a low temperature to a high temperature. As a final heat treatment temperature for making an imidized (cured) polyimide resin layer and for volatilizing an adsorbed component derived from atmospheric components and moisture distributed on the surface of the first inorganic material. Is preferably 300 ° C. or higher. More preferably, it is 370 degreeC or more, More preferably, it is 430 degreeC or more.

Here, the heat treatment can be performed under any conditions in an inert gas such as nitrogen or argon and in the air. Moreover, it can carry out under any conditions of normal pressure, reduced pressure, increased pressure and vacuum. Among these, it is preferable to perform the heat treatment under the condition that the oxygen concentration is 10% or less because the adhesive force between the laminate and the inorganic substance including the resin-metal is increased. In nitrogen or argon, the oxygen concentration of 5% or less is more preferable because the adhesive strength between the laminate and the resin-metal-containing inorganic substance is further increased. The lower the oxygen concentration, the higher the adhesive strength between the laminate and the resin-metal-containing inorganic substance, and the oxygen concentration is more preferably 1% or less, and most preferably 0.5% or less.

Among these, it is preferable to perform the heat treatment in a control condition range where the oxygen concentration is 10% or less because it becomes possible to appropriately manage the adhesive force expression between the resin-metal-containing inorganic substance in the laminate. For example, when the inorganic layer of the laminate is copper, copper is a highly active metal species, so it is easy to form an oxide by reaction with oxygen, and the oxide suppresses or attenuates further reaction with oxygen. Because of its poor action (blocking action on dense oxide layer coating), further oxidation reaction proceeds, oxide formation develops to so-called corrosion and rusting, and adheres to dimensional change, conduction breakage and migration Since it causes various troubles such as a decrease, it is preferable that the oxygen in the surrounding atmosphere is small, that is, the oxygen concentration is close to 0%. As an example different from copper, when the inorganic layer of the laminate is stainless steel, the oxide film produced by reacting with oxygen in the surrounding atmosphere exerts an action of suppressing or attenuating further reaction with oxygen. Therefore, it is possible to prevent the occurrence of corrosion and rust. Therefore, the less oxygen in the surrounding atmosphere, that is, the closer it is to nothing, it is not preferable, and appropriate oxygen for preventing the oxide film from generating corrosion and rust. Concentration management, that is, a controlled aerobic atmosphere is preferred. In stainless steel, the appropriate relationship between oxide film formation and atmospheric oxygen has been studied in various processes such as manufacturing processes, forming processes such as rolling, and chemical conversion treatments such as surface treatment. By controlling the oxygen concentration during the treatment to 8% or less, the surface state can be improved so as not to generate cracks and patterns [see Patent Document 5], and the oxygen concentration during slab heating in rolling in the forming process is 2 By controlling the content within the range of ˜8%, it is possible to prevent surface flaws [see Patent Document 6]. In order for stainless steel to exhibit an appropriate state of the oxide film after the process, management of oxygen concentration requires management condition setting according to each process. Therefore, the metal material having an oxide film of a type that suppresses the oxidation reaction, such as stainless steel, is manufactured, processed, or processed through any process before the laminate is manufactured. Even if you do not know whether to maintain the oxide film of stainless steel metal at the time of laminate production in an appropriate state, or to lead to an appropriate state, oxygen concentration management is equal to or more than the management items other than oxygen It is important, and when the high temperature region is included in the laminate production conditions, it is based on the idea that it is even more important.

The resin solution concentration when using the precursor polyamic acid solution as the pre-polyimide resin layer is a polyimide precursor and depends on the degree of polymerization of the polyamic acid which is a polymer, but is usually 5 to 30% by weight, preferably Is 10 to 20% by weight. If the polymer concentration is higher than 5% by weight, a sufficient film thickness can be obtained by one application. If the polymer concentration is lower than 30% by weight, the viscosity of the resin solution does not become too high, and it is good in terms of uniformity and smoothness. It is because it can apply | coat to.

In addition to the method of applying a pre-polyimide resin layer on the second layer and heat-treating it as described above, a single polyimide layer is formed as the second layer on the surface. An inorganic material may be bonded.

For example, the following method can be used for thermocompression bonding when the polyimide layer and the inorganic material are bonded together. That is, a hydro press, a vacuum type hydro press, an autoclave pressurizing vacuum press, a continuous thermal laminator, or the like can be used. Among these, the vacuum hydropress is a preferable thermocompression bonding method because a sufficient pressing pressure can be obtained and oxidation of the conductor when a metal foil is used as the first layer can be prevented.

The hot press temperature at the time of thermocompression bonding is not particularly limited, but it is preferably higher than the glass transition temperature of the polyimide resin used. The hot press pressure is suitably 0.1 to 50 MPa (1 to 500 kg / cm 2), although it depends on the type of press equipment used. If the press temperature during thermocompression bonding becomes too high, there is a concern that problems such as deterioration of the inorganic layer and the polyimide resin layer may occur.

As described above, the example in which the polyimide is used as the second layer has been described. However, a resin other than polyimide can be applied under the same conditions.

In the laminate produced as described above, the resin layer has a thermal weight reduction at 545 ° C. of 1.0% or less, and the peel strength at the interface between the inorganic material and the resin layer is 100 N / m or more. Bond strength is very good. In other words, the compatibility with high heat resistance is achieved. For this reason, display members such as organic EL having TFT (Thin Film Transistor) semiconductors that require high temperature processing, inverter members equipped with power semiconductors characterized by high temperature operation, compound semiconductor solar cell substrates represented by chalcopyrite systems, etc. It can be suitably used for various materials that require heat resistance and flexibility. In particular, it can be suitably used for a flexible substrate for a compound semiconductor solar cell including a CIS-based chalcopyrite solar cell requiring heat resistance of about 500 ° C. The above-mentioned display member requires different heat resistance levels depending on the type of TFT material used. For example, when the material type is LTPS [Low Temperature Polysilicon], heat resistance of about 450 to 460 ° C. is required. IGZO [semiconductor oxide which is an oxide of indium (In), gallium (Ga) and zinc (Zn)] has a wide range of TFT formation conditions and has a heat resistance of about 300 to 400 ° C. The required laminated body of this embodiment can be used suitably as said display member.

As the solar cell substrate material, the following compound semiconductor solar cells can be produced. An embodiment of the flexible solar cell 20 of the present invention will be described with reference to FIG.
FIG. 3 is a cross-sectional view of an example of the flexible solar cell of the present embodiment, and is formed using the laminate 10 that is the polyimide layer-containing flexible substrate described with reference to FIG.
The solar cell 20 includes a lower electrode (back electrode) 6 on the second layer 2 which is a polyimide layer (insulating layer) of the laminate 10 which is a polyimide layer-containing flexible substrate, and a photoelectric conversion layer (light) on the lower electrode 6. The structure has a transparent electrode (upper electrode) 8, and a lower electrode 6 and a takeout electrode 9 connected to the transparent electrode 8 on the absorption layer 7 and the photoelectric conversion layer 7.

The lower electrode 6 is not particularly limited as long as it is a conductive material. Preferably, for example, a metal or semiconductor having a volume resistivity of 6 × 10 6 Ω · cm or less can be used. Specifically, for example, molybdenum (Mo) can be used. The thickness of the lower electrode 6 is preferably 0.1 to 1 μm from the viewpoint of flexibility.

In order to obtain high power generation efficiency, the photoelectric conversion layer 7 preferably has a good light absorption, that is, a large light absorption coefficient. As the photoelectric conversion layer for the flexible solar cell of the present invention, a compound semiconductor is preferable, and a chalcopyrite-based I-III-VI group compound composed of Cu, In, Ga, Al, Se, S or the like is used. For example, CdS / CdTe, CIS [CuInS ₂ ], CIGS [Cu (In, Ga) Se ₂ ], CIGSS [Cu (In, Ga) (Se, S) ₂ ], SiGe, CdSe, GaAs, GaN, and InP Etc. The thickness of the photoelectric conversion layer 7 is preferably 0.1 to 4 μm from the viewpoint of achieving both power generation efficiency and flexibility.

Since the transparent electrode 8 is an electrode on the light incident side, a material having high transparency is used so that the light can be efficiently collected. For example, aluminum-doped zinc oxide (ZnO) or indium tin oxide (ITO) is used. The thickness of the transparent electrode 8 is 0.1 to 0.3 μm from the viewpoint of flexibility. In order to prevent loss of incident light due to reflection or the like, an antireflection film may be formed in contact with the transparent electrode 8.

As the extraction electrode 9, for example, metals and alloys such as Ni, Al, Ag, Au, and NiCr can be used as materials.

Further, between the photoelectric conversion layer 7 and the transparent electrode 8, a Cd-based material such as CdS, ZnS, ZnO, ZnO _1-X S _X , Zn (S, O, OH) _X , Zn _1-X Mg _X O, etc. An In-based buffer layer (not shown) such as Zn-based, InS, In (S, OH) _X may be provided.

It continues and demonstrates the schematic manufacturing method of the flexible solar cell which concerns on this embodiment with reference to FIG.
FIG. 4 is a flowchart showing a method for manufacturing the flexible solar cell of the present embodiment.
First, an electrode material, for example, molybdenum is laminated on the second layer 2 that is a polyimide layer of the laminate 10 that is a polyimide layer-containing flexible substrate to form the lower electrode 6 (S11). Specifically, for example, molybdenum is stacked on the second layer 2 by sputtering or vapor deposition.

After the formation of the lower electrode 6, one of the above compound semiconductors is laminated thereon to form the photoelectric conversion layer 7 (S12). Specifically, for example, the compound semiconductor material is laminated on the lower electrode 6 by any method such as sintering, chemical precipitation, sputtering, proximity sublimation, multi-source deposition, and selenization.

When a CdS / CdTe film is formed as the photoelectric conversion layer 7, a method of forming a thin film by sequentially applying a CdS paste and a CdTe paste and sintering at 600 ° C. or lower can be exemplified. Further, instead of this method, a method of forming a CdTe film by proximity sublimation after forming a CdS film by chemical precipitation or sputtering can be employed.

When a CIS [CuInS ₂ ] film, a CIGS [Cu (In, Ga) Se ₂ ] film, or a CIGSS [Cu (In, Ga) (Se, S) ₂ ] film is formed as the photoelectric conversion layer 7, these compounds The paste is applied on the second layer 2 and sintered at 350 to 550 ° C. to form the compound semiconductor-based photoelectric conversion layer 7.

When forming the compound semiconductor-based photoelectric conversion layer 7 as described above, zinc (Zn) may be mixed into the compound semiconductor film. By mixing zinc, the photoelectric conversion efficiency can be improved.
As the mixing method, for example, a method of applying an aqueous solution such as zinc sulfate, zinc chloride, or zinc iodide to the compound semiconductor film can be used. Or you may immerse the laminated body which formed even the photoelectric converting layer 7 in these aqueous solution.

After the photoelectric conversion layer 7 is formed, a transparent electrode 8 of zinc oxide (ZnO) or indium tin oxide (ITO) doped with aluminum is laminated thereon by a sputtering method or the like (S13). Then, it connects with each of the lower electrode 6 and the transparent electrode 8, and each taking-out electrode 9 is formed (S14). Aluminum or nickel can be used as the material for the extraction electrode.

Note that an alkali metal supply layer may be formed between the second layer 2 and the lower electrode 6. The effect of improving the photoelectric conversion efficiency can be expected when a part of the alkali metal permeates and diffuses into the photoelectric conversion layer 7 from the alkali metal supply layer.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. Further, the superiority of the present embodiment will be clarified by showing a comparative example.

1. As the inorganic material for the first layer, the thickness of the stainless steel foil manufactured by Nippon Steel & Sumikin Materials Co., Ltd. is 30 μm, the coefficient of thermal expansion is 11 ppm / K, and the surface roughness on the side in contact with the first layer (Ra ) Was 0.08 μm ferritic stainless steel foil.

2. Various physical property measurement and performance test methods

[Measurement of linear thermal expansion coefficient]
With respect to the laminate and the inorganic layer before lamination, a test piece for measurement cut out to a size of 3 mm × 20 mm was applied with a constant heating rate while applying a load of 5 g with a Bruker thermomechanical analysis (TMA) apparatus (4000SA). A tensile test is performed at a temperature range of 30 ° C. to 260 ° C. at 20 ° C./min, and then cooled to 30 ° C. at a constant rate of temperature decrease (5 ° C./min). ) Was measured.

[Measurement of thermal weight loss rate]
About a laminated body, an inorganic substance layer is made into a polyimide resin film by wet etching, 20 mg is put into an aluminum cup, and using a thermogravimetric measuring device (TG / DTA6200) manufactured by SII Nanotechnology, under nitrogen (200 ml / min) or The temperature was increased from 30 ° C. to 550 ° C. at a rate of 10 ° C./min in the air, and the weight loss rate between 200 ° C. and 545 ° C. was measured.

[Measurement of adhesive strength (peel strength)]
The adhesive force between the inorganic layer and the polyimide resin layer is such that the laminate is subjected to a pattern etching process with a line width of 1 mm, and the resin layer is applied using a tensile tester (Strograph-M1) manufactured by Toyo Seiki Co., Ltd. The peel strength was measured by peeling off in the 180 ° direction. In addition, the thing with the strong adhesion | attachment between a process fine wire and a resin interface and being difficult to peel was made impossible to peel. In addition, it was determined that measurement was impossible when the polyimide resin layer was agglomerated.

[Measurement of surface roughness]
The surface roughness of the stainless steel layer was measured using a laser microscope (VK-8710) manufactured by Keyence Corporation on a stainless steel foil cut to 2 cm × 2 cm.
The surface roughness (Ra) on the side in contact with the first layer of the stainless steel foil manufactured by Nippon Steel & Sumikin Materials Co., Ltd. used as the first layer was 0.08 μm.

3. Synthesis of polyamic acid (polyimide precursor) solution
Reference Examples The raw materials, aromatic diamino compounds, aromatic tetracarboxylic acid anhydride compounds and solvents used in the synthesis of the polyamic acid (polyimide precursor) solutions handled in the following synthesis examples, examples and comparative examples are as follows: Show.
[Aromatic diamino compounds]
・ 1,4-Phenylenediamine (PPD, manufactured by Daishin Kogyo Co., Ltd.)
・ 4,4'-diaminodiphenyl ether (DAPE, manufactured by Seika Corporation)
・ 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl (TFMB, manufactured by Seika Corporation)
・ 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB, manufactured by Seika Corporation)
・ 1,3-Bis (4-aminophenoxy) benzene (TPER, manufactured by Seika Corporation)
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP, Seika Corporation)
[Anhydrous compound of aromatic tetracarboxylic acid]
・ Pyromellitic anhydride (PMDA, manufactured by Daicel Chemical Industries)
・ 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride (BPDA, manufactured by Mitsubishi Chemical Corporation)
・ 2,3,6,7-Naphthalenetetracarboxylic dianhydride (NTCDA, manufactured by JFE Chemical Co., Ltd.)
〔solvent〕
・ N, N-dimethylacetamide (DMAc, manufactured by Kanto Chemical Co., Inc.)

Synthesis example 1
Under a nitrogen stream, PPD (8.002 g, 0.074 mol) was added to 170 g of the solvent DMAc while stirring in a 300 ml separable flask, and dissolved at 50 ° C. BPDA (22.000 g, 0.075 mol) was then added. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a viscous polyamic acid a. In addition, the polyimide a is obtained by heating this polyamic acid a.

Synthesis example 2
Under a nitrogen stream, PPD (7.4077 g, 0.06850 mol) and TFMB (1.1545 g, 0.00361 mol) were added to 170 g of solvent DMAc with stirring in a 300 ml separable flask and heated at 50 ° C. Dissolved. BPDA (21.4378 g, 0.07286 mol) was then added. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain viscous polyamic acid b. In addition, the polyimide b is obtained by heating this polyamic acid b.

Synthesis example 3
Under a nitrogen stream, PPD (7.4077 g, 0.06850 mol) and TFMB (1.1545 g, 0.00361 mol) were added to 170 g of solvent DMAc with stirring in a 300 ml separable flask and heated at 50 ° C. Dissolved. BPDA (20.9050 g, 0.07105 mol) was then added. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a viscous polyamic acid c. In addition, the polyimide c is obtained by heating this polyamic acid c.

Synthesis example 4
Under a nitrogen stream, PPD (8.272 g, 0.076 mol) was added to 170 g of solvent DMAc while stirring in a 300 ml separable flask, and dissolved at 50 ° C. BPDA (11.372 g, 0.039 mol) and NTCDA (10.356 g, 0.039 mol) were then added. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a pale yellow viscous polyamic acid d. In addition, the polyimide d is obtained by heating this polyamic acid d.

Synthesis example 5
Under nitrogen flow, PPD (7.0611 g, 0.06530 mol) and TFMB (2.3233 g, 0.00726 mol) were added to 170 g of solvent DMAc with stirring in a 300 ml separable flask and heated at 50 ° C. Dissolved. BPDA (10.7851 g, 0.03666 mol) and NTCDA (9.8305 g, 0.03666 mol) were then added. Thereafter, the solution was continuously stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a pale yellow viscous polyamic acid e. In addition, the polyimide e is obtained by heating this polyamic acid e.

Synthesis Example 6
Under a nitrogen stream, m-TB (2.381 g, 0.011 mol) and TPE-R (13.113 g, 0.045 mol) were added and dissolved in 170 g of solvent DMAc with stirring in a 300 ml separable flask. . PMDA (6.176 g, 0.028 mol) and BPDA (8.331 g, 0.028 mol) were then added. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a pale yellow viscous polyamic acid f. In addition, the polyimide f is obtained by heating this polyamic acid f.

Synthesis example 7
Under a nitrogen stream, m-TB (14.337 g, 0.068 mol) was dissolved in 170 g of solvent DMAc with stirring in a 300 ml separable flask. PMDA (11.714 g, 0.054 mol) and BPDA (3.950 g, 0.013 mol) were then added. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a pale yellow viscous polyamic acid g. In addition, the polyimide g is obtained by heating this polyamic acid g.

Synthesis example 8
Under a nitrogen stream, BAPP (19.618 g, 0.048 mol) was dissolved in 170 g of solvent DMAc with stirring in a 300 ml separable flask. PMDA (10.382 g, 0.048 mol) was then added. Thereafter, the solution was stirred at room temperature for 3 hours to carry out a polymerization reaction to obtain a pale yellow viscous polyamic acid h. In addition, the polyimide h is obtained by heating this polyamic acid h.

4). Performance evaluation
Example 1
Prepare the ferritic stainless steel foil having a thickness of 30 μm described above, and apply the polyamic acid a solution prepared in advance in Synthesis Example 1 and heat at a temperature of 100 to 140 ° C. for 5 minutes, In a nitrogen atmosphere (controlled oxygen concentration of 1% or less), the temperature was raised to 370 ° C. at 4 ° C./min, then raised to 500 ° C. at 20 ° C./min and held for 40 minutes, 50-60 ° C. After cooling, a laminate having a polyimide layer a having a film thickness of about 8 μm was obtained.

Example 2
Prepare the 30 μm-thick ferritic stainless steel foil described above, and apply the polyamic acid b solution prepared in advance in Synthesis Example 2 and heat at a temperature of 100 to 140 ° C. for 5 minutes, In a nitrogen atmosphere (controlled oxygen concentration of 1% or less), the temperature was raised to 370 ° C. at 4 ° C./min, then raised to 500 ° C. at 20 ° C./min and held for 40 minutes, 50-60 ° C. After cooling, a laminate comprising a polyimide layer b having a film thickness of about 8 μm was obtained.

Example 3
Prepare the 30 μm-thick ferritic stainless steel foil described above, and apply the polyamic acid c solution prepared in advance in Synthesis Example 2 and heat at a temperature of 100 to 140 ° C. for 5 minutes, In a nitrogen atmosphere (controlled oxygen concentration of 1% or less), the temperature was raised to 370 ° C. at 4 ° C./min, then raised to 500 ° C. at 20 ° C./min and held for 40 minutes, 50-60 ° C. After cooling, a laminate having a polyimide layer c having a film thickness of about 8 μm was obtained.

Example 4
A laminate including the polyimide layer d was obtained in the same manner as in Example 1 except that the polyamic acid d solution prepared in advance in Synthesis Example 4 was used.

Example 5
Prepare the ferritic stainless steel foil having a thickness of 30 μm described above, and apply the polyamic acid e solution prepared in advance in Synthesis Example 5 and heat at a temperature of 100 to 140 ° C. for 5 minutes, In a nitrogen atmosphere (controlled oxygen concentration of 1% or less), the temperature was raised to 370 ° C. at 4 ° C./min, then raised to 500 ° C. at 20 ° C./min and held for 40 minutes, 50-60 ° C. A laminated body having a polyimide layer e having a film thickness of about 8 μm after curing was obtained.

Comparative Example 1
A laminate including the polyimide layer f was obtained in the same manner as in Example 1 except that the polyamic acid f solution prepared in advance in Synthesis Example 6 was used.

Comparative Example 2
A laminate including the polyimide layer g was obtained in the same manner as in Example 1 except that the polyamic acid g solution prepared in advance in Synthesis Example 7 was used.

Comparative Example 3
A laminate including the polyimide layer h was obtained in the same manner as in Example 1 except that the polyamic acid h solution prepared in advance in Synthesis Example 8 was used.

Comparative Example 4
A laminate was obtained in the same manner as in Example 1 except that the heating condition was changed from the nitrogen atmosphere to the atmosphere.

[Table 1]

The thermal weight reduction shown in Table 1 is a case where the resin layer thickness is about 8 μm. By reducing the layer thickness by adjusting the application, etc., for example, by reducing the layer thickness such as 3 μm, the thermal weight reduction is further reduced. Reduce and improve.

As shown in Table 1, in Examples 1 to 5, the thermal weight loss at 545 ° C. is 1.0% or less, and the peel strength at the interface between the second layer and the first layer is 100 N / m. Strong adhesion was exhibited, and in the measurement of peel strength, it was a strong adhesion state that could not be peeled off. Further, as shown in Table 1 above, in Examples 1, 3 and 4, the thermal weight loss at 545 ° C. is 0.7% or less, and the peel strength at the interface between the second layer and the first layer is Strong adhesion was developed exceeding 100 N / m, and in the measurement of peel strength, it was in a strong adhesion state that could not be peeled off.
Comparative Example 1 has a thermal weight reduction of 10.1%, and Comparative Examples 2 and 3 also have a thermal weight reduction greatly exceeding 1.0%, which is insufficient in heat resistance. Further, the resin layer was broken during the peel strength measurement, and the peel strength at the interface could not be measured.
Comparative Example 4 has a peel strength of 10 N / m, less than 100 N / m, and is inferior in adhesion performance with peeling.
As shown in the examples, it is possible to use for various applications by obtaining a laminate having both barrier properties by the inorganic layer and electrical insulation by the resin layer, high heat resistance and good adhesion, and preferable properties of the resin By making use of the above, enabling handling and processing in a high temperature range that has not been possible in the past, it becomes possible to provide products, parts, and members with higher performance than before. As shown in the examples, it is a laminate produced by heat treatment up to a temperature of 500 ° C., but the interface between the inorganic layer and the resin layer is good, so it can be used in many applications that require high-temperature processes. Can be applied.
In addition, the peel strength of each laminate produced in Example 1 with the heating condition set to an oxygen concentration of 10% or less, 5% or less, and 1% or less in a nitrogen atmosphere is not peeled off as in Example 1, and is 100 N / m or more.

Applications include display substrate materials such as liquid crystal and organic EL that involve TFT fabrication, SiC power device substrate materials that are subject to high-temperature use, organic EL lighting substrate materials that continue for long periods of time, and compounds that require high-temperature conditions in the manufacturing process Examples include products, parts, members, and the like, such as semiconductor-based solar cell substrate materials.

Claims

A laminate in which a second layer made of a resin and a first layer made of an inorganic material are laminated, the thermal weight loss of the resin at 545 ° C. being 1.0% or less, and the second layer and A laminate having a peel strength at an interface of the first layer of 100 N / m or more.
The laminate according to claim 1, wherein a decrease in thermal weight of the resin at 545 ° C is 0.7% or less.
The laminate according to claim 1 or 2, wherein the linear thermal expansion coefficient in the plane direction of the first layer is 15 ppm / K or less.
The laminate according to any one of claims 1 to 3, wherein the second layer is formed of one or more resin materials selected from the group consisting of polyimide and derivatives thereof. .
The second layer includes a polyimide synthesized from a biphenyltetracarboxylic acid compound and a phenylenediamine compound and derivatives thereof, a biphenyltetracarboxylic acid compound, a phenylenediamine compound, and 4,4′-diamino-2,2′-bis ( Polyimide and its derivatives synthesized from trifluoromethyl) biphenyl, polyimide and its derivatives synthesized from biphenyltetracarboxylic acid compounds, naphthalenetetracarboxylic acid compounds and phenylenediamine compounds, or biphenyltetracarboxylic acid compounds and naphthalenetetracarboxylic A polyimide synthesized from an acid compound, a phenylenediamine compound and 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, or a derivative thereof, or two or more of these Polyimide and laminate according to any one of claims 1 to 4, characterized by being formed by a derivative thereof.
The laminate according to any one of claims 1 to 5, wherein the first layer is formed of one or more metal materials selected from the group consisting of metals.
The laminate according to any one of claims 1 to 6, wherein the first layer is formed of one or more metal materials selected from the group consisting of ferritic stainless steel and titanium. body.
The laminate according to any one of claims 1 to 7, wherein the laminate is obtained by applying the resin or a precursor thereof to the surface of the first layer and then performing a heat treatment at 300 ° C or higher. .
The laminate according to claim 8, wherein the laminate is obtained by performing a heat treatment at an oxygen concentration of 10% or less as the heat treatment.
A compound semiconductor solar cell member comprising the laminate according to any one of claims 1 to 9.
A compound semiconductor solar cell comprising the laminate according to any one of claims 1 to 9.
A member for a display device comprising the laminate according to any one of claims 1 to 9.
A display device comprising the laminate according to any one of claims 1 to 9.
The method for producing a laminate according to any one of claims 1 to 9, wherein a step of continuously applying a resin or a precursor thereof to the surface of the first layer made of an inorganic material, and a heat treatment at 300 ° C or higher And a step of forming a second layer made of the resin on the surface of the first layer by a roll-to-roll method.
The method for manufacturing a laminate according to claim 14, wherein the heat treatment is performed at an oxygen concentration of 10% or less.