JP2013010340A - Method of producing laminate, and method of producing film device utilizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film device excellent in heat resistance, and to provide a laminate of a heat resistant resin layer and an inorganic substance layer for producing the film device.SOLUTION: In methods of manufacturing the laminate configured by at least the inorganic layer and a resin film, and the film device utilizing the laminate, the method of manufacturing the laminate includes the processes (1)-(3), (1) the process of treating at least one surface of the inorganic layer with a coupling agent, (2) the process of providing parts of different peel strengths between the inorganic layer and the resin layer by irradiating at least the one surface of the inorganic layer treated with the coupling agent with UV according to a previously determined pattern, and (3) the process of drying and heat treating an applied solution layer obtained by applying a resin solution or a resin precursor solution on the patterned and coupling agent treated surface of the inorganic layer to form the resin layer. Production of the film device is implemented by peeling a part which is weak in adhesive peel strength to a substrate by the process of exposing it to UV according to a previously determined pattern from the inorganic substrate after producing the device using the laminate.

Description

The present invention is a method for producing a laminate comprising a resin layer and an inorganic layer, and more specifically, the laminate having a strongly bonded portion and a portion that can be easily peeled according to a predetermined pattern. It is a manufacturing method of a body. Laminate that consists of a thin film such as a semiconductor element or MEMS element, and the resin layer is temporarily or semi-permanently bonded to an inorganic layer that serves as a support for forming a device that requires fine processing on the surface of the resin layer. The present invention relates to a lamination method for obtaining a film device and a method for producing a film device using the laminate.
Furthermore, in the present invention, a thin resin layer excellent in heat resistance and insulation and a kind of inorganic layer selected from a glass plate, a ceramic plate, a silicon wafer, and a metal having substantially the same linear expansion coefficient are laminated. The present invention relates to a laminated body excellent in dimensional stability, heat resistance, and insulation, capable of mounting a fine circuit, and a method for producing a semiconductor-added film device using the semiconductor-added laminated body using the laminated body.

In recent years, for the purpose of reducing the weight and flexibility of devices such as fine circuit boards and sensor elements, technology development for forming these elements on polymer films has been actively conducted.
In forming devices such as sensor elements and MEMS elements on the surface of a resin film, it is ideal to process by a so-called roll-to-roll process using the flexibility that is a characteristic of the resin film. However, in the sensor industry and the MEMS industry, a process technology for a wafer-based or glass substrate-based rigid flat substrate has been established. As a practical choice, use existing infrastructure by attaching a resin film to a rigid support substrate made of an inorganic material such as a metal plate, wafer, glass substrate, etc., forming a desired element, and then peeling it from the support substrate Thus, a functional element formed on the resin film can be obtained.
In the bonding of a resin film and a support substrate made of an inorganic material, the level of surface smoothness, cleanliness, resistance to process temperature, and resistance to chemicals used for microfabrication are not problematic when forming such functional elements. Is required. In particular, when the formation temperature of the functional element is high, the heat resistance of the resin film as well as the bonding surface of the laminate must withstand the processing temperature.
Among the thin films, Si has a linear expansion coefficient of about 3 ppm / ° C. When this thin film is deposited on the substrate, if the difference in the linear expansion coefficient between the substrate and the thin film is large, stress is accumulated in the thin film. , Causing deterioration of performance, warping of the thin film, and peeling. In particular, when a high temperature is applied during the thin film formation process, stress due to a difference in linear expansion coefficient between the substrate and the thin film increases during the temperature change.
Conventionally, it has been widely performed to bond a resin film to an inorganic substrate using an adhesive or an adhesive. (Patent Document 1) However, when a process in a temperature range of about 200 to 500 ° C. is required, there is no known bonding method having sufficient resistance enough for practical use.

Conventionally, ceramic has been used as a base material for electronic components such as information communication equipment (broadcast equipment, mobile radio equipment, portable communication equipment, etc.), radar, high-speed information processing devices, and the like. A base material made of ceramic has heat resistance, and can cope with a recent increase in the frequency band of information communication equipment (reaching the GHz band). However, ceramics are not flexible and cannot be thinned, so the fields that can be used are limited.
Therefore, studies using resin films made of organic materials as base materials for electronic parts have been made, resin films made of polymers such as polyethylene naphthalate and polyethylene terephthalate, films made of polyimide, films made of polytetrafluoroethylene, glass fiber reinforced Epoxies have been proposed. A film made of polyimide is excellent in heat resistance and has an advantage that a resin film can be made thin because it is tough.
These polyimide layers generally have a large coefficient of linear expansion, have a significant dimensional change due to a temperature change, and are not suitable for the production of a circuit having fine wiring. Thus, a device using a polyimide layer having sufficient physical properties for a substrate having heat resistance, high mechanical properties, and flexibility has not yet been obtained.

  Attempts have been made to provide other structural reinforcements by providing an adhesive layer such as a thermoplastic resin on these polyimide films, but even if satisfactory in structural improvements, the heat resistance of these thermoplastic resins and the like The low value had a tendency to ruin the heat resistance of the folded polyimide film.

A step of forming a resin substrate on a fixed substrate through an amorphous silicon film serving as a release layer, a step of forming at least a TFT element on the resin substrate, and irradiating the amorphous silicon film with laser light In this way, a process of peeling the resin substrate from the fixed substrate in the amorphous silicon film is performed to manufacture a flexible display device using the resin substrate (Patent Document 2). However, laser irradiation and etching means are used for the adhesive layer at the time of peeling, which causes a complicated process and high cost. Adhesion of resin films by UV irradiation treatment has been disclosed (Patent Document 3), and it has been shown that it is effective to use a coupling agent at this time. That is, the adhesive peeling force control by the UV light irradiation of the coupling agent itself is not performed.

JP 2008-159935 A JP 2009-260387 A JP 2008-19348 A

  In the present invention, it is possible to carry out precise positioning at the time of circuit wiring creation and device formation in a state supported by a heat-resistant inorganic layer, and to perform multilayer thin film creation, circuit formation, etc. An object of the present invention is to provide a polyimide laminate used for a circuit-added laminate and a semiconductor-added laminate in which a semiconductor element is formed, which allows thin film deposition and the like without peeling. Moreover, since this resin film laminated body can be easily peeled off when only the easy peeling part of the pattern is peeled after the device is added, the produced semiconductor is not destroyed. And the resin film used for this circuit addition laminated body and the semiconductor addition laminated body in which the semiconductor element was formed is peeled, and the resin film with a fine circuit formed and the resin film with a device can be provided.

  As a result of intensive studies, the present inventors have found that a resin layer having a higher level of heat resistance and flexibility, a glass plate, a ceramic plate, a silicon wafer, and a metal having a linear expansion coefficient that is almost the same level. We found that a laminate with excellent heat resistance and insulation laminated with an inorganic layer is extremely significant when used in the production of fine circuit boards and devices, and we have developed an inorganic layer and an adhesive that can be used for it. A resin laminate that can be bonded without being used, has excellent adhesion, does not interfere with peeling from the support, has a low linear expansion coefficient in a specific range, and can form a precise circuit on a smooth surface. I found it.

That is, the present invention has the following configuration.
1. At least a method for producing a laminate comprising an inorganic layer and a resin layer,
The manufacturing method of the laminated body characterized by including the process of following (1)-(3).
(1) A step of treating the surface of at least one side of the inorganic layer with a coupling agent (2) By performing a patterning treatment on at least one side of the inorganic layer treated with the coupling agent according to a predetermined pattern, The process of providing the part from which the peeling strength between resin layers differs.
(3) A step of drying and heat-treating a coating solution layer obtained by coating a resin solution or a resin precursor solution on the patterned inorganic layer-treated surface of the coupling agent, and forming the resin layer;
2. The patterning process is performed after covering or shielding a predetermined portion, and includes at least a blast process, a vacuum plasma process, an atmospheric pressure plasma process, a corona process, an actinic radiation irradiation process, an active gas process, and a chemical solution process. The method for producing one laminate according to claim 1, wherein the method is one or more selected treatments.
3. The method for producing a laminate according to any one of claims 1 and 2, wherein the patterning treatment is a UV irradiation treatment.
4). The manufacturing method of the laminated body in any one of 1-3 in which this resin layer consists of a polyimide obtained by making aromatic diamines and aromatic tetracarboxylic acids react.
5. Manufacture of the laminated body in any one of 1-4 whose thickness of the said resin layer is 0.5 micrometer-50 micrometers, and whose linear expansion coefficient of the surface direction of the said resin layer is -2 ppm / degreeC-+35 ppm / degreeC. Method.
6). It is a laminate of an inorganic layer and a resin layer, and has a coupling agent layer between the inorganic layer and the resin layer, and a well-bonded portion and an easily peelable portion of the inorganic layer and the resin layer are predetermined. The 180 degree peel strength between the inorganic layer and the resin layer is 1 N / cm or more at the good adhesion portion, and the difference in peel strength between the good adhesion portion and the easy peel portion is a good adhesion portion. The method for producing a laminate according to any one of 1 to 5, which is 50% or more with respect to the peel strength.
7. The method for producing a laminate according to any one of 1 to 6, wherein the coupling agent layer has a thickness of 100 nm or less.
The laminate produced by the method for producing a laminate according to any one of 8.1 to 7, wherein the adhesive peel strength of the inorganic layer and the resin layer is different, and the good adhesion portion and the easy peel portion are separated according to the pattern. A laminate characterized by having
After forming a device on the resin layer surface of the easily peelable portion of the resin layer of the laminate using the laminate described in 9.8, the resin film in which the devices are laminated by cutting out and peeling off the easily peelable portion How to get.

In the laminate obtained by the production method of the present invention, one surface of a kind of inorganic layer selected from a glass plate, a ceramic plate, a silicon wafer, and a metal, and a resin layer are extremely thin in heat resistance instead of an adhesive layer. Layer, that is, a laminate bonded via a coupling agent layer, and the adhesive peel strength of the inorganic layer and the resin layer differs depending on the predetermined pattern, and the polyimide surface of the good adhesion part and easy peel part are separated according to the pattern And a resin layer having a linear expansion coefficient of −2 ppm / ° C. to +35 ppm / ° C., preferably 30 ° C. to 300 ° C., bonded via a coupling agent layer, The 180 degree peel strength of the good adhesion part between the layer and the inorganic layer is 1 N / cm or more, and the 180 degree peel strength of the easy peel part is 50% or less of the good adhesion part.
The resin film with a device obtained by the production method of the present invention is a resin film with a device obtained by using the laminate and easily peeling after cutting out the resin layer of the easily peelable portion. Then, after creating a device in the easily peelable portion, the resin film with the device is obtained by easily peeling off the resin layer in the easily peelable portion.
The laminated body of the present invention is excellent in dimensional stability even when an electronic device is formed by forming a circuit or the like on a thin resin layer having insulation, flexibility and heat resistance, and further mounting an electronic component. Accurate positioning is possible by laminating and fixing to an inorganic substrate, thin film formation and circuit formation can be performed in multiple layers, and it will not peel off even if heat is applied during the process. Even when the inorganic substrate is peeled off, the resin layer and the substrate can be smoothly peeled off, and the laminate has a peel strength that does not peel off during the process. Is possible.

UV irradiation process example 1 (1) Inorganic layer (2) Silane coupling agent coating and drying on inorganic layer to form silane coupling agent layer (3) UV irradiation treatment after mask installation to block UV light (4) UV irradiation After treatment, removal of mask for blocking UV light (5) Production of resin layer (6) Cutting of resin film around silane coupling agent layer UV irradiation treatment area and peeling from glass UV irradiation process example 2 (1) Inorganic layer (2) Silane coupling agent coating and drying on inorganic layer to form silane coupling agent layer (3) UV irradiation treatment after mask installation to block UV light (4) UV irradiation After treatment, removal of mask that blocks UV light (5) Production of resin layer and circuit wiring creation (6) Cutting of resin film around silane coupling agent layer UV irradiation treatment area and peeling from glass Pattern example Schematic conceptual diagram of a display device 1 Schematic conceptual diagram of a display device 2

As the resin layer in the present invention, polyethylene, polypropylene, polystyrene, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, acrylonitrile / butadiene / styrene copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene Terephthalate, polyphenylene sulfide, polysulfone, polyethersulfone, polymethylpentene, poly (meth) acrylate, polyamide, polycarbonate, polyvinyl alcohol, nitrocellulose, triacetylcellulose, polyvinyl chloride, polyencavinylidene, polyacetal, polyphenylene ether , Modified polyphenylene ether, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether Polymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene / ethylene copolymer, styrene / maleic acid copolymer resin Arton (trade name of JSR), ZONEX (trade name of Nippon Zeon), polyarylate, liquid crystal polymer, wholly aromatic polyester, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, diallyl phthalate, Silicone resin, polyurethane, polylactic acid, polycaprolactone, polybutyl succinate, polyethylene succinate, polybenzimidazole, polybenzothiazole, polybenzoxazole, polyetherimide, thermosetting Polyimide, polyimide, aromatic polyamideimide, aromatic polyether ether ketone, aromatic polyether ketone ketone, polyphenylene sulfide, the use of aromatic polyarylate.
The resin layer preferably used in the present invention has excellent heat resistance such as polyimide, aromatic polyamideimide, aromatic polyetheretherketone, aromatic polyetherketoneketone, polyphenylene sulfide, and aromatic polyarylate, and is tough. Certain resin materials can be applied, of which polyimide is particularly useful. Since heat resistance and dimensional stability are required, it is desirable to have —CONH—, —COO—, —CO—, —SO— or the like as a linking group having an aromatic ring and a large polarity. Furthermore, it is also preferable from the viewpoint of heat resistance and dimensional stability to introduce a double chain structure into the polymer main chain to have a rigid rod-like structure. Another way of thinking is to create a three-dimensional network structure as a means to improve heat resistance.

  The polyimide layer particularly useful in the present invention comprises a polyimide having the composition described below, and has a glass transition temperature in the region of 250 ° C. or higher, preferably 300 ° C. or higher, more preferably 350 ° C. or higher, or 500 ° C. or lower. Is preferably not observed. The glass transition temperature in the present invention is determined by differential thermal analysis (DSC).

The polyimide of the present invention is a polyimide obtained by a reaction between an aromatic diamine and an aromatic tetracarboxylic acid, and has a linear expansion coefficient in the plane direction of −2 ppm / ° C. to +35 ppm / ° C., and the aromatic diamine and aromatic The polyimide whose tetracarboxylic acids are the following combinations is preferable.
A. A combination of an aromatic tetracarboxylic acid having a pyromellitic acid residue and an aromatic diamine having a benzoxazole structure (skeleton).
B. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
C. A combination of an aromatic tetracarboxylic acid having a pyromellitic dianhydride skeleton and an aromatic diamine having a 4,4′-oxydianiline skeleton.
D. A combination of an aromatic tetracarboxylic acid having a pyromellitic dianhydride skeleton, an aromatic diamine having a phenylenediamine skeleton, and an aromatic diamine having a 4,4′-oxydianiline skeleton.
E. A combination of any of A to D that has been subjected to alkoxy group-containing silane modification treatment.
Specific examples of the aromatic diamines having a benzoxazole structure used in the present invention include the following, and these diamines may be used alone or in combination of two or more.

  The molecular structure of aromatic diamines having a benzoxazole structure is not particularly limited, and specific examples include the following.

  Among these, from the viewpoint of easy synthesis, each isomer of amino (aminophenyl) benzoxazole is preferable, and 5-amino-2- (p-aminophenyl) benzoxazole is more preferable. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.

  In the present invention, diamines exemplified below may be used alone or in combination of two or more. Examples of such diamines include 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, and bis [4- (3-aminophenoxy) phenyl]. Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-dia Nodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4 , 4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4, 4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-amino) Phenoxy) phenyl] ethane, 1,1-bis [4- 4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, , 4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl ] Butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-a Minophenoxy) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2- Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4 -Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-amino) Enoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1, 3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] Benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) ) Phenyl] propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) phenyl -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1 , 2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-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, bis [4- {4- (4-aminophenoxy) phenoxy} fe Sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethyl Benzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluoro) Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4 -Amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-dipheno Cibenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino- 4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4′-diamino-4 -Biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) Benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-bi) Phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- ( 4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile, 2,2′-bis (biphenyl) benzidine and water on the aromatic ring of the above aromatic diamine 1 or more carbon atoms in which some or all of the elementary atoms are substituted with halogen atoms, some or all of the hydrogen atoms of the alkyl group or alkoxyl group having 1 to 3 carbon atoms, cyano group, or alkyl group or alkoxyl group are substituted with halogen atoms And aromatic diamines substituted with ~ 3 halogenated alkyl groups or alkoxyl groups.

<Aromatic tetracarboxylic acid anhydrides>
Specific examples of the aromatic tetracarboxylic acid anhydrides used in the present invention include the following.

  These tetracarboxylic dianhydrides may be used alone or in combination of two or more. In addition, aromatic tetracarboxylic dianhydrides in which some or all of the hydrogen atoms on the aromatic ring of the aromatic tetracarboxylic dianhydride are substituted with a phenyl group, a biphenyl group, a naphthyl group, or the like are also included.

  In the present invention, an aromatic tetracarboxylic acid having a skeleton of pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, an aromatic diamine having a benzoxazole structure, and an aromatic having a 4,4′-diaminodiphenyl ether skeleton. It is particularly preferable to use a polyimide obtained by a combination of group diamines. This is because a polyimide film with small warpage can be obtained from the polyimide laminate when the combination of polyimides is used. When a device is produced in the easy peeling part of the polyimide layer of such a polyimide laminated body, destruction of the device produced on the polyimide film surface when peeled is not seen.

  The solvent used when the polyamic acid is obtained by reacting (polymerizing) the aromatic tetracarboxylic acid and the aromatic diamine is not particularly limited as long as it dissolves both the raw material monomer and the produced polyamic acid. Is preferably a polar organic solvent, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Examples include hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the weight of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by weight, The amount is preferably 10 to 30% by weight.

  Conventionally known conditions may be applied for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”). As a specific example, in a temperature range of 0 to 80 ° C., 10 Stirring and / or mixing continuously for minutes to 120 hours. If necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of adding both monomers is not particularly limited, but it is preferable to add aromatic tetracarboxylic acid anhydrides to the solution of aromatic diamines. The weight of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and the viscosity of the solution is measured with a Brookfield viscometer (20 ° C.). From the viewpoint of ease of handling, it is preferably 1 to 1000 Pa · s, more preferably 3 to 600 Pa · s.

  Vacuum defoaming during the polymerization reaction is effective for producing a good quality polyamic acid solution. Moreover, terminal blockers, such as a dicarboxylic acid anhydride, a tricarboxylic acid anhydride, and an aniline derivative, can be used for the molecular terminal blockage of the present invention. Preferably used in the present invention are phthalic anhydride, maleic anhydride, 4-ethynyl phthalic anhydride, 4-phenylethynyl phthalic anhydride, ethynylaniline, and the use of maleic anhydride is more preferred. The usage-amount of terminal blocker is 0.001-1.0 molar ratio per mol of monomer components.

In the present invention, an additive may be added to the polyamic acid solution for the purpose of improving the performance of the polyimide layer. These additives vary depending on the purpose and are not particularly limited. Further, the addition method and the addition time are not particularly limited. Examples of additives include cross-linking agents, alteration agents, dispersants, antifoaming agents, leveling agents, flame retardants and the like.

  In the present invention, a filler may be added to the polyamic acid solution for the purpose of improving the performance of the polyimide layer. The filler in the present invention is fine particles made of an inorganic substance having a volume average particle diameter of 0.001 to 10 μm, and is a metal, metal oxide, metal nitride, metal carbonide, metal acid salt, phosphate, carbonate, Particles composed of talc, mica, clay, other clay minerals, etc. can be used, preferably silicon oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass filler, etc. These metal oxides, phosphates, and carbonates can be used.

The average linear expansion coefficient between 30 and 300 ° C. of the polyimide layer in the present invention is preferably −2 ppm / ° C. to +12 ppm / ° C., more preferably +1 ppm / ° C. to +10 ppm / ° C., and most preferably. Is +3 ppm / ° C. to +8 ppm / ° C. If it is out of this range, the difference in the coefficient of linear expansion coefficient with the inorganic substrate becomes large, so that the polyimide layer and the inorganic layer are easily peeled off during the process of applying heat, making it difficult to use. Moreover, although the linear expansion coefficient of the polyimide layer in the present invention in question uses an average value between 30 and 300 ° C., the temperature range of interest varies depending on the application, and considering the process at a high temperature, When examining the range from 30 ° C. to 400 ° C., the range may be from 100 ° C. to 400 ° C. When considering the reflow process, when examining the range from 50 ° C. to 280 ° C., the operating temperature range is from −50 ° C. to 150 ° C. In some cases, the temperature range may be emphasized. In the present invention, the CTE may change within this temperature range, but the lower measurement limit may be replaced with 0 ° C, 30 ° C, 50 ° C, and the upper measurement limit is replaced with 200 ° C, 300 ° C, 400 ° C. Is also possible.

  The thickness of the resin layer in the present invention is not particularly limited, but is preferably 0.5 μm to 50 μm, more preferably 1 μm to 40 μm, still more preferably 5 μm to 30 μm, and most preferably 7 ~ 15 μm. The thickness unevenness of these resin layers is also preferably 20% or less. When the thickness is 0.5 μm or less, it is difficult to control the thickness, and it is difficult to peel off the inorganic layer. When the thickness is 50 μm or more, it is difficult to form a polyimide layer, and the resin layer is likely to be bent when peeled off.

In the present invention, it is preferable to use a transparent polyimide layer as a resin layer, preferably a polyimide layer.
Here, the transparent polyimide layer is a resin layer made of a polyimide resin capable of forming a transparent polyimide film having a light transmittance of 50% or more at a wavelength of 500 nm. In the transparent polyimide layer in the present invention, the diamine is t-CHDA (a kind selected from isomers of transdiaminocyclohexane such as trans 1,4-diaminocyclohexane), methylene bis such as MBCA (4,4′-methylenebis (cyclohexylamine), etc. (A kind selected from isomers of (cyclohexylamine)), and a transparent polyimide layer mainly comprising at least one kind selected from DDS (one kind selected from isomers of diaminodiphenylsulfone such as 3,3′-diaminodiphenylsulfone) is preferred. At least one diamine selected from these is preferably used in an amount of 70 mol% or more, more preferably 85 mol% or more of the total diamine.

In the present invention, the resin layer has a glass transition temperature of 150 ° C. or higher, a logarithmic viscosity of 0.5 dl / g or higher, a light transmittance of 80% or higher in the wavelength region 400 to 550 nm, and a color difference b value of less than 1. It is preferable to use a polyamide-imide layer using a polyamide-imide resin that is characterized.
Preferred as the structure of the main component polymer constituting the polyamideimide layer used in the present invention is, for example, a polyamide whose main acid component is trimellitic acid-based aromatic acid and acid anhydride compound and cyclohexanedicarboxylic acid-based alicyclic acid It is an imide. More preferred is a polyamideimide having a cyclohexanedicarboxylic acid content of 15 mol% or more. Moreover, the polyamideimide whose amine residue is 4,4'-dicyclohexylmethane and / or isophorone is preferable.

The polyamideimide used in the present invention can be obtained by a conventional method such as an isocyanate method obtained by a reaction of an acid component and an isocyanate, an amine method obtained by a reaction of an acid component and an amine component, or an acid chloride method. It is synthesized in a high boiling polar solvent such as an amide solvent.

Examples of the acid component used in the synthesis of the polyamideimide of the present invention include polyvalent carboxylic acids, acid chlorides, and acid anhydrides. Examples of acid anhydrides include, for example, trimellitic anhydride, ethylene glycol bisanhydride trimellitate, propylene glycol bisanhydride trimellitate, 1,4-butanediol bisanhydride trimellitate, hexamethylene glycol Alkylene glycol bisanhydride trimellitate such as bisanhydride trimellitate, polyethylene glycol bisanhydride trimellitate, polypropylene glycol bisanhydride trimellitate, pyromellitic anhydride, benzophenone tetracarboxylic anhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic anhydride, 4,4′-oxydiphthalic anhydride, etc. It is done.

Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, 4,4′-biphenyl dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 4,4′-biphenyl sulfone dicarboxylic acid, 4,4 '-Benzophenone dicarboxylic acid, pyromellitic acid, trimellitic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, stilbene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid Examples of the acid chloride include acid chlorides of the polyvalent carboxylic acids.

Examples of the isocyanate component include dicyclohexylmethane 4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and diphenylmethane. 4,4'-diisocyanate, 3,3'-dichlorodiphenyl 4,4'-diisocyanate, 3,3'-dimethylbiphenyl 4,4'-diisocyanate, hexamethylene diisocyanate, isophorone Examples thereof include diisocyanate, p-phenylene diisocyanate, and m-phenylene diisocyanate.

Examples of the diamine component include 4,4′-diaminodicyclohexylmethane, 1,3-cyclohexanebis (methylamine), orthochloroparaphenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4 ′. -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,4 ' -Diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,2'-bis (aminophenyl) propane, 2,4-tolylenediamine, 2,6-tri Rangeamine, p-xylenediamine, isophoronediamine, hexamethylenediamine, p-phenylenediamine Min, and moths m- phenylenediamine and the like.

These acid component and isocyanate (amine) component can be used as one kind or a mixture of two or more kinds, respectively. As the acid component, a mixture of trimellitic acid and cyclohexanedicarboxylic acid is preferable. The content is particularly preferably 15 mol% or more. When the mol% of cyclohexanedicarboxylic acid is 15 or less, the coloring becomes large, and the use is limited such that it may not be used for optical applications.

Further, as the isocyanate component, dicyclohexylmethane 4,4'-diisocyanate and isophorone diisocyanate alone or in mixture are preferable from the viewpoint of light transmittance, heat resistance, and productivity. As the amine component, dicyclohexylmethane 4,4'-diamine and isophoronediamine are used alone or as a mixture from the viewpoint of light transmittance, heat resistance, and productivity.

Solvents used in synthesizing the polyamideimide of the present invention are dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylurea, dimethylsulfoxide, γ-butyrolactone, dimethylimidazolyl dinone, and other high boiling polar solvents, either alone or in combination. Although a solvent can be used, it is not limited to these.

The polyamideimide of the present invention is synthesized by stirring in the above solvent at 50 to 250 ° C., preferably 80 to 230 ° C., but in order to accelerate the reaction, an amine such as triethylamine, lutidine, picoline, triethylenediamine, etc. , Lithium methylate, sodium methylate, lithium ethylate, sodium ethylate, magnesium ethylate, potassium butoxide, potassium fluoride, sodium fluoride, and other alkali metals, alkaline earth metal compounds, or cobalt, titanium, The reaction may be performed in the presence of a catalyst such as a metal such as tin or zinc, or a metalloid compound.

The polyamideimide thus obtained has a logarithmic viscosity (25 ° C. in N-methylpyrrolidone, polymer concentration 0.5 g / 100 ml) of 0.5 dl / g or more, but in terms of film moldability, It is preferably 0.6 dl / g or more. As a means for obtaining these resins having logarithmic viscosity, a method of controlling the equivalent ratio of reaction components, the order of addition, reaction time, reaction temperature and the like can be used, but is not limited thereto.

  In the treatment with the coupling agent in the present invention, the coupling agent preferably used for laminating the inorganic layer is not particularly limited, but those having an amino group or an epoxy group are preferred. Specific examples of the coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl). ) -3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane vinyltrichlorosilane, vinyltri Methoxysilane, vinyltriethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltri Methoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 -Merka Topropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate, chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, 1-mercapto-2-propanol, methyl 3-mercaptopropionate, 3-mercapto-2-butanol, butyl 3-mercaptopropionate, 3- (dimethoxymethylsilyl) -1-propanethiol, 4- (6-mercaptohexa Royl) benzyl alcohol, 11-amino-1-undecenethiol, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecyltrifluoroacetic acid, 2,2 ′-(ethylenedioxy) diethanethiol 11-mercaptoundecyl tri (ethylene glycol), (1-mercaptoundec-11-yl) tetra (ethylene glycol), 1- (methylcarboxy) undec-11-yl) hexa (ethylene glycol), hydroxyundecyl disulfide , Carboxyundecyl disulfide, hydroxyhexadodecyl disulfide, carboxyhexadecyl disulfide, tetrakis (2-ethylhexyloxy) titanium, titanium dioctyloxybis (octylene glycolate), zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetate Nate bis (ethyl acetoacetate), zirconium tributoxy monostearate, acetoalkoxyaluminum diisopropylate, etc. I can get lost.

Among these, preferred are N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, aminophenyltrimethoxysilane, amino Phenethyltrimethoxysilane, aminophenylamino Such as methyl phenethyltrimethoxysilane the like. In the case where heat resistance is required in the process, it is desirable to use an aromatic group between Si and an amino group.

  As a processing method performed by the coupling agent treatment in this invention, the method of apply | coating and drying the solution of a coupling agent to an inorganic layer, and heat-processing can be illustrated. In addition, it is known that the pH during the treatment greatly affects the performance, and the pH may be adjusted as appropriate.

  As the inorganic layer when laminating the resin layer on the inorganic layer in the present invention, a glass plate, a ceramic plate, a silicon wafer, a material mainly composed of metal, and a composite of these glass plate, ceramic plate, silicon wafer, metal And the like, those obtained by laminating these, those in which these are dispersed, and those containing these fibers.

The linear expansion coefficient of the inorganic layer in the present invention is calculated as an average value measured between 30 to 300 ° C. as CTE. In general, the linear expansion coefficient of metals and ceramics does not change greatly in this temperature range.

  As the glass plate as the inorganic layer when laminating the resin layer in the present invention on the inorganic layer, quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate Glass (Pyrex (registered trademark)), borosilicate glass (non-alkali), borosilicate glass (microsheet), and aluminosilicate glass are included. Among them, those having a linear expansion coefficient of 5 ppm / ° C. or lower are desirable, and liquid crystal glass Corning 7059, 1737, EAGLE, Asahi Glass AN100, Nippon Electric Glass OA10, SCHOTT AF32, etc. are desirable.

As the ceramic plate as the inorganic layer when laminating the resin layer in the present invention to the inorganic layer, Al2O3, Mullite, AlN, SiC, Si3N4, BN, crystallized glass, Cordierite, Spodumene, Pb-BSG + CaZrO3 + Al2O3, Crystallized glass + AL2O3, Crystallized Ca-BSG, BSG + Quartz, BSG + Quartz, BSG + AL2O3, Pb + BSG + AL2O3, Glass-ceramic, Zerodur, etc. Substrate ceramics, TiO2, strontium titanate, calcium titanate, titanic acid magnesium. Capacitor materials such as alumina, MgO, steatite, BaTi4O9, BaTiO3, BaTi4 + CaZrO3, BaSrCaZrTio3, Ba (TiZr) O3, PMN-PT PFN-PFW, PbNb2O6, Pb0.5Be0.5Nb2O6, PbTiO3, BaTiO3, PZ. This includes piezoelectric materials such as 95PT-0.5BT, 0.873PZT-0.97PT-0.3BT, PLZT.

  The silicon wafer as the inorganic layer when laminating the resin layer on the inorganic layer in the present invention includes all n-type or p-type doped silicon wafers and intrinsic silicon wafers, and the surface of the silicon wafer. In addition to silicon wafers including silicon oxide layers and silicon wafers with various thin films deposited, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony are often used. Yes. General-purpose semiconductor wafers such as InP (indium phosphorus), InGaAs, GaInNAs, LT, LN, ZnO (zinc oxide), CdTe (cadmium tellurium), and ZnSe (zinc selenide) are included.

  The metal as the inorganic layer when laminating the resin layer on the inorganic layer in the present invention is a single element metal such as W, Mo, Pt, Fe, Ni, Au, Inconel, Monel, Nimonic, carbon copper, Fe-Ni. Alloys such as invar alloys and super invar alloys are included. Moreover, the multilayer metal plate which added the other metal layer and the ceramic layer to said metal is also contained. In this case, if the total CTE with the additional layer is low, Cu, Al or the like is also used for the main metal layer. The metal used as the additional metal layer is limited as long as it has strong properties such as adhesion to the polyimide layer, no diffusion, and good chemical resistance and heat resistance. However, chromium, nickel, TiN, and Mo-containing Cu can be cited as preferable examples.

The patterning treatment in the present invention refers to a treatment for intentionally creating a portion where the peel strength between the inorganic layer and the polyimide layer is strong and a portion where the peel strength is weak. More specifically, the process of increasing or decreasing the action of the coupling agent is performed in a state where a predetermined portion is covered or shielded by some means. In general, the method of weakening the action of the coupling agent is easier to select,
A method of physically removing the coupling agent layer,
A method of physically masking the coupling agent layer microscopically A method of chemically modifying the coupling agent layer can be exemplified.
Specifically, the treatment for enhancing or weakening the action of the coupling agent includes blast treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, corona treatment, actinic radiation treatment, active gas treatment, chemical solution treatment and laser light treatment. One or more selected processes can be used.

The blast treatment in the present invention refers to a treatment in which particles having an average particle diameter of 0.1 to 1000 μm are sprayed on an object together with gas or liquid. In the present invention, it is preferable to use blasting using particles having a small average particle diameter as much as possible.
The vacuum plasma treatment in the present invention refers to a treatment in which an object is exposed to plasma generated by discharge in a decompressed gas, or ions generated by the discharge collide with the object. As the gas, neon, argon, nitrogen, oxygen, carbon fluoride, carbon dioxide, hydrogen or the like alone or a mixed gas can be used.
The atmospheric pressure plasma treatment in the present invention means that an object is exposed to plasma generated by a discharge generated in a gas that is generally in an atmospheric pressure atmosphere, or ions generated by the discharge are applied to the object. This is the collision process. As the gas, neon, argon, nitrogen, oxygen, carbon dioxide, hydrogen or the like alone or a mixed gas can be used.
The corona treatment in the present invention refers to a treatment in which an object is exposed to a corona discharge atmosphere generated in a gas that is generally in an atmospheric pressure atmosphere, or ions generated by the discharge collide with the object. .
The actinic radiation irradiation treatment in the present invention refers to treatment for irradiating radiation such as electron beam, alpha ray, X-ray, beta ray, infrared ray, visible ray, ultraviolet ray.
The active gas treatment in the present invention is a gas having an activity that causes a chemical or physical change in the coupling agent treatment layer, for example, halogen gas, hydrogen halide gas, ozone, high concentration oxygen gas, ammonia. This refers to a treatment in which an object is exposed to a gas such as an organic alkali or an organic acid.
The chemical treatment in the present invention is a liquid having an activity that causes a chemical or physical change in the coupling agent treatment layer, for example, a liquid such as an alkaline solution, an acid solution, a reducing agent solution, an oxidizing agent solution, It also refers to the treatment of exposing an object to a solution.

These processes can be performed by a direct drawing method if possible. That is, it is possible to perform patterning by concentrating these processes directly on the part where the adhesive force is desired to be strengthened or the part where the adhesive force is desired to be weakened.
When performing laser light irradiation processing as a kind of actinic radiation irradiation processing, it is particularly easy to perform processing by a direct drawing method. In this case, even a visible light laser has much larger energy than general visible light, and therefore can be treated as a kind of actinic radiation in the present invention.
In addition, these treatments may be performed by covering or shielding a predetermined portion of the inorganic layer and then performing the treatment on the entire surface, and removing the coating or shielding material after the treatment. As a covering or shielding material, a material generally used as a resist, a photomask, a metal mask, etc. may be appropriately selected according to the processing method and used. A method combining actinic radiation and a mask, or a method combining an atmospheric pressure plasma treatment and a mask can be preferably used from the viewpoint of productivity. The actinic radiation treatment that can be preferably used is an ultraviolet irradiation treatment, that is, a UV irradiation treatment from the viewpoint of economy and safety.
In addition, as one of the unique forms of the present invention, when the inorganic layer has UV transparency, direct drawing or masking is performed from the surface opposite to the surface of the inorganic layer which has been treated with the coupling agent. UV irradiation can also be performed.

The UV irradiation treatment in the present invention is a treatment in which an inorganic layer is placed in an apparatus that generates UV light (ultraviolet rays) having a wavelength of 400 nm or less, and the UV light wavelength is desirably 260 nm or less. More desirably, it includes a wavelength of 200 nm or less. However, since UV light is significantly absorbed by oxygen at a wavelength of 170 nm or less, it is necessary to consider the fact that UV light reaches the inorganic layer. However, when irradiation is performed in a completely oxygen-free atmosphere, the surface modification effect due to active oxygen or ozone does not appear, and therefore, it is necessary to devise so that active oxygen and ozone can reach while UV light passes. A pattern is formed by intentionally creating a portion that is irradiated with light and a portion that is not irradiated. As a method of forming, a pattern can be formed by making a portion that shields UV light and a portion that does not shield UV light, or by scanning UV light. In order to clarify the end of the pattern, it is effective to block the UV light and cover the inorganic layer with a shield. It is also effective to scan with a parallel beam of a UV laser. The intensity of UV light is preferably 5 mW / cm 2 or more. 200 mW / cm 2 or less is desirable for preventing the glass from being deteriorated. The irradiation time is preferably from 0.1 minute to 30 minutes, more preferably from 1 to 10 minutes, and more preferably from 2 minutes to 5 minutes.
Examples of light sources that can be used for UV irradiation include excimer lamps, low-pressure mercury lamps, high-pressure mercury lamps, Xe lamps, Xe excimer lasers, ArF excimer lasers, KrF excimer lasers, XeCl excimer lasers, XeF excimer lasers, Ar lasers, and D2 lamps. Can be mentioned. Among these, excimer lamps, low-pressure mercury lamps, Xe excimer lasers, ArF excimer lasers, KrF excimer lasers, and the like are preferable.

  The well-bonded portion in the present invention refers to a portion where the peel strength between the inorganic layer and the resin layer is strong by changing the surface properties depending on the presence or absence of UV light irradiation. And the easy peeling part in this invention points out the part with weak peeling strength of an inorganic layer and a resin layer by changing the property of the surface by the presence or absence of UV light irradiation.

  A non-polyimide portion may be provided by providing a polyimide layer in the polyimide laminate as an application example in the present invention or a hole portion penetrating in the film thickness direction of the laminate. The part is not particularly limited, but is preferably filled with a metal whose main component is a metal such as Cu, Al, Ag, Au, or formed by a mechanical drill or laser drilling. Examples of the formed holes and the wall surfaces of the holes include a metal film formed by sputtering, electroless plating seed layer formation, or the like.

  The resin laminate of the present invention is applied to the substrate surface of the inorganic layer treated with the coupling agent by melt extrusion when the resin is thermoplastic, or by applying a resin solution when the resin is solvent-soluble. Or in the case of an insoluble and infusible resin such as a non-thermoplastic type polyimide resin, it is applied in the intermediate state of the raw material or precursor of the resin, and on the substrate surface of the inorganic layer. A method of forming a resin layer by a chemical reaction or the like can be used.

  The polyimide laminate of the present invention can be obtained by applying a polyamic acid solution to the substrate surface of an inorganic layer treated with a coupling agent and imidizing it by heating or chemical treatment after drying to form a polyimide layer. Alternatively, in the case of a solvent-soluble polyimide resin, it can also be obtained by applying a polyimide resin solution to the substrate surface of the inorganic layer treated with the coupling agent and drying it to form a polyimide layer. In addition, it is possible to form a polyimide layer using an intermediate raw material, such as drying and partial imidization from a mixed state of a polyamide acid solution and a solvent-soluble polyimide resin partially imidized.

In the present invention, the method of applying the polyamic acid solution or the polyimide resin solution to the inorganic layer on the base material is, for example, spin coating, doctor blade, applicator, comma coater, screen printing method, casting from a slit base, Extrusion by an extruder, slit coating, reverse coating, dip coating, and the like are included, but not limited to these, conventionally known solution application means can be appropriately used.
These means can also be applied to all resin materials other than polyamic acid.

In this invention, 50 to 120 degreeC is preferable and the heating temperature at the time of drying a polyamic acid has more preferable 80 to 100 degreeC. The treatment time is preferably 5 minutes to 3 hours, more preferably 15 minutes to 2 hours. The residual solvent amount after drying is preferably 25% to 50%, more preferably 35% to 45%.

In this invention, 150-500 degreeC is preferable and the heating temperature at the time of heating a polyamic acid and producing a polyimide layer has more preferable 300-450 degreeC. The heating time is preferably 0.05 to 10 hours. The heat treatment is usually performed while raising the temperature stepwise or continuously. The heating rate is preferably 20 ° C./min or less, more preferably 10 ° C./min or less, and most preferably 5 ° C./min or less. Further, the rate of temperature rise is preferably 0.5 ° C./min or more.

About the continuous temperature increase conditions in imidation by heating in the present invention, the temperature is increased from 100 ° C. to a maximum temperature of 150 ° C. to 500 ° C. at a temperature increase rate of 0.5 ° C. to 20 ° C./min. Is preferably held for 0.1 minute to 120 minutes, and more preferably, the rate of temperature rise is 1 ° C. to 10 ° C./minute, the maximum temperature reached is 300 ° C. to 480 ° C., and the time of retention at the maximum temperature reached is 1 to 60 minutes. Most preferably, the rate of temperature rise is 2 ° C. to 5 ° C./min, the maximum temperature reached is 400 ° C. to 450 ° C., and the holding time at the maximum temperature reached is 5 to 30 minutes.

About the temperature rising conditions in drying by heating and imidization in the present invention, after drying at 80 ° C. for 30 minutes and then at 100 ° C. for 90 minutes, the temperature is increased to 400 ° C. at a temperature rising rate of 5 ° C./minute, It is particularly preferable to hold at 400 ° C. for 5 minutes.

In the present invention, a ring-closing catalyst may be used in the production of the polyimide layer on the inorganic layer. Specific examples of the ring-closing catalyst used in the present invention include aromatic carboxylic acids such as benzoic acid, aliphatic tertiary amines such as trimethylamine and triethylamine, and heterocyclic tertiary amines such as isoquinoline, pyridine and betapicoline. However, it is preferable to use at least one amine selected from heterocyclic tertiary amines. The content of the ring-closing catalyst is preferably in a range in which the content (mol) of the ring-closing catalyst (mol) / the content (mol) of the precursor polyamic acid is 0.01 to 10.00.

In the present invention, a dehydrating agent may be used when the polyimide layer is formed on the inorganic layer. Examples thereof include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. It is not limited. The content of the dehydrating agent is preferably in a range where the content of dehydrating agent (mole) / polyamic acid content (mole) is 0.01 to 10.00.

The resin film in the present invention is a resin film obtained by easily peeling off a resin layer at an easily peelable portion of a resin laminate. A resin film with a device can be obtained by creating a device at an easily peelable portion of the laminate, and then peeling off the resin layer at the easily peelable portion, followed by peeling.
The polyimide film in the present invention is a polyimide film obtained by easily peeling off a polyimide layer at an easily peelable portion of a polyimide laminate. A device-prepared polyimide film can be obtained by creating a device at an easily peelable portion of the laminate, and then peeling off the polyimide layer at the easily peelable portion and then peeling off.

In the present invention, as a method of cutting out the resin film of the easily peelable portion after creating a device in the easily peelable portion of the laminate for obtaining a resin film with a device, a method of cutting out the film with a blade, a laser and the A method of cutting out a film by relatively scanning the laminate, a method of cutting out a film by relatively scanning the water jet and the laminate, and cutting out the film while cutting slightly to the glass layer by a semiconductor chip dicing apparatus. There are methods, but the apparatus is not particularly limited.
Moreover, when attaching a reinforcement member by making the resin film with a device into a final product, it can cut out, after fixing a reinforcement member to this laminated body which attached a device previously. Examples of the reinforcing member include a method of separately bonding or sticking a polymer film. In this case, since the polymer film used separately is after passing through a process that already requires a high temperature, there are less restrictions on heat resistance than the resin film, and various polymer films can be selected.
Further, regarding the position to be cut out, an error occurs when the pattern is accurately followed on the resin surface of the good adhesion portion and the easily peelable portion. Therefore, cutting slightly to the easily peelable portion side from the pattern increases the productivity. There can also be a production system that prevents the film from peeling off by itself until it is peeled off by cutting into a slightly difficult-to-bond part from the pattern. Furthermore, by setting the width of the difficult-to-adhere part narrow, eliminating the resin film remaining on the good adhesion part at the time of peeling increases the use efficiency of the film and improves the device area with respect to the laminate area. It becomes one form of this invention which raises the property. Furthermore, a system in which the outer peripheral portion of the laminate itself is used as a cut-out position regardless of the number of devices and is peeled off without actually carrying out a cut-out process can be an extreme form of the present invention.

In the present invention, as a method of easily peeling from the substrate made of the inorganic material after cutting the film of the easily peelable part after creating a device in the easily peelable part of the laminate for obtaining a resin film with a device, Although it can be rolled from the end with tweezers, etc., one side of the cutout portion of the film with the device is fixed with an adhesive tape and then the side of the cutout portion of the film with the device is vacuum-adsorbed. There can also be a way to hit that part later. In these cases, if the cutout portion of the film with the device is bent with a small curvature, stress is applied to the device at that portion and the device may be destroyed. Therefore, it is desirable to peel off the device with a large curvature as much as possible. . For this reason, it is desirable to roll while winding on a roll having a large curvature or to roll using a machine having a configuration in which a roll having a large curvature comes to the peeling portion.
In addition, when the reinforcing member is fixed to the laminate with the device attached thereto and then cut out, and when the reinforcing member is separately attached to the cutout portion of the film with the device and then peeled off, the film and the polymer film Considering the elastic modulus and the film thickness, it is desirable because it is possible to make the device part less susceptible to stress.
Examples of the reinforcing member include a polymer film, ultrathin glass, and SUS when a reinforcing member is separately attached to the cutout portion of the resin film with the device. By using a polymer film, there is an advantage that the lightness of the device is maintained, and there are advantages such as transparency, various workability, and resistance to cracking. Using ultra-thin glass has the advantage of providing gas barrier properties, chemical stability, and transparency. Using SUS is advantageous in that it can be shielded electrically and is difficult to break.

  In the resin laminate of the present invention, an adhesive layer is not interposed between the inorganic layer and the resin layer, and only the one containing 10 wt% or more of Si derived from the coupling agent is present. Since the intermediate layer can be made thin by using the coupling agent layer, there are few degassing components during heating, and it is difficult to elute even in the wet process. However, the layer derived from the coupling agent has many heat-resistant silicon oxide components and has heat resistance at a temperature of about 400 ° C., and the layer derived from this coupling agent is used in a range of 100 nm or less, preferably , 50 nm or less, more preferably 20 nm or less. In processes where it is desired to have as few coupling agents as possible, even a thickness of 5 nm or less can be used. If the thickness is 1 nm or less, the peel strength may be reduced, or a portion that is not partially attached may appear.

  The planar portion of the inorganic layer may not be flat. This is because even if there is a certain degree of roughness, a resin layer having a smooth surface can be obtained by applying and curing the resin. Regarding the resin layer, it is desirable that the resin layer be sufficiently smooth in consideration of forming a device on the surface. The PV value of the surface roughness is 50 nm or less, more desirably 20 nm or less, and more desirably 5 nm or less. The same applies to the case where polyimide is used as the resin, and the planar portion of the inorganic layer may not be flat. This is because even if there is a certain degree of roughness, a polyimide layer having a smooth surface can be obtained by applying and curing the polyamic acid solution. Regarding the polyimide layer, it is desirable that the polyimide layer be sufficiently smooth in view of forming a device on the surface. The PV value of the surface roughness is 50 nm or less, more desirably 20 nm or less, and more desirably 5 nm or less.

  Examples of the device of the present invention include an active device, a passive device, a MEMS, a semiconductor device, a sensor device, a photoelectric conversion device, etc., which are manufactured by combining thin film technology or thick film technology, photolithography process, printing process, etc. Devices include strain gauges, load cells, semiconductor pressure sensors, optical sensors, photoelectric elements, photodiodes, magnetic sensors, contact temperature sensors, thermistor temperature sensors, resistance thermometer temperature sensors, thermocouple temperature sensors, Non-contact temperature sensor, radiation thermometer, microphone, ion concentration sensor, gas concentration sensor, displacement sensor, potentiometer, differential transformer displacement sensor, rotation angle sensor, linear encoder, tachometer, rotary encoder, optical position Sensor (PSD), Ultrasonic Distance Meter, Capacitance Displacement Meter, Laser Doppler Vibrometer, Laser Doppler Velocimeter, Gyro Sensor, Accelerometer, Earthquake Sensor, One-dimensional Image, Linear Image Sensor, Two-dimensional Image, CCD Image Sensor, CMOS image sensor, liquid, leak sensor (leak sensor), liquid sensor (level sensor), hardness sensor, electric field sensor, current sensor, voltage sensor, power sensor, infrared sensor, radiation sensor, humidity sensor, odor sensor , Flow sensors, tilt sensors, vibration sensors, time sensors, composite sensors that combine these sensors, sensors that output other physical quantities or sensitivity values based on some formula from the values detected by these sensors, etc. Including.

  In the present invention, the 180-degree peel strength of the good adhesion portion between the resin layer and the inorganic layer of the laminate is preferably 1 N / cm or more, and more preferably 2 N / cm or more. Further, the 180 degree peel strength of the easy peelable portion is 50% or less of the good adhesive portion (that is, the difference in peel strength between the good adhesive portion and the easy peelable portion is 50% or more with respect to the peel strength of the good adhesive portion). Preferably, it is more preferably 30% or less (that is, the difference in peel strength between the good adhesion portion and the easy peel portion is 70% or more with respect to the peel strength of the good adhesion portion). Further, the 180 degree peel strength value of the easily peelable portion is 1 N / cm or less, preferably 0.5 N / cm, more preferably 0.05 N / cm or less, but may be 0.01 N / cm or more. preferable. If the adhesive strength is too weak, it tends to cause film floating.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in the following examples is as follows.
1. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube. (When the solvent used for preparing the polyamic acid solution was N, N-dimethylacetamide, the polymer was dissolved using N, N-dimethylacetamide and measured.)
2. The thickness of the resin film or the like was measured using a micrometer (Finereuf, Millitron 1245D).
3. Measurement of Resin Film Warpage A polyimide film to be measured was cut into 20 mm × 20 mm and placed on an aluminum foil to remove static electricity. Thereafter, the film was placed on a flat glass plate, the distance from the glass plates at the four ends was measured with a ruler, and the average of these was taken to determine the warp of the film.
4. 180 degree peel strength
According to the 180 degree peeling method of JIS C6471, the peeling strength of the sample was determined by performing a 180 degree peeling test under the following conditions. The sample for measuring peel strength was measured by attaching a resin layer to the inorganic layer before patterning in the same manner as in Example 1. Specifically, after attaching a resin layer, Nikkan Kogyo adhesive sheet SAFW and further, a large commercially available polyimide film 25 μm thick is roll laminated at 100 ° C., and then pressed at 160 ° C. for 1 hour, After cooling at room temperature, N = 5 was measured with the commercially available polyimide film on both sides sandwiching the SAFW and the inorganic layer resin layer laminate on the side where the commercially available polyimide film was bent 180 degrees, and the average value was taken as the measured value.
Device name: Autograph AG-IS, manufactured by Shimadzu Corporation
Measurement temperature; Room temperature peeling speed; 50mm / min
Atmosphere: Air measurement sample width: 1cm
Since the interfacial peeling between the commercially available polyimide layer and the SAFW or the SAFW material destruction occurs near 8 N / cm, the peeling strength between the inorganic layer and the polyimide layer can only be estimated to be higher.
5. Linear expansion coefficient (CTE)
Measurements of the stretch rate of the resin layer peeled off from the inorganic substrate under the following conditions, and the stretch rate / temperature at intervals of 30 ° C. to 45 ° C., 45 ° C. to 60 ° C.,. Then, this measurement was performed up to 300 ° C., and the average value of all measured values was calculated as CTE.
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon Initial load: 34.5 g / mm2
8). Measuring Method of Coupling Agent Layer Thickness Coupling layer thickness was a film thickness prepared on a silicon wafer.
The film thickness was measured by ellipsometry, and the measuring instrument used was FE-5000 manufactured by Hottal.
The hardware specifications of this measuring instrument are as follows.
Reflection angle range 45 to 80 °, wavelength range 250 to 800 nm, wavelength resolution 1.25 nm, spot diameter 1 mm, tan Ψ measurement accuracy ± 0.01, cosΔ measurement accuracy ± 0.01, system rotation analyzer method. Measurement was performed at a deflector angle of 45 ° and an incident angle of 70 °, and the analyzer measured from 0 to 360 ° and 250 to 800 nm in increments of 11.25 °.
The film thickness was obtained by fitting by a non-linear least square method. At this time, the model is Air / thin film / Si model,
n = C3 / λ4 + C2 / λ2 + C1
k = C6 / λ4 + C5 / λ2 + C4
The wavelength dependence C1 to C6 was obtained by the following formula.

[Synthesis Example 1]
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 574 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO), N-methyl-2-pyrrolidone After 9900 parts by mass of (NMP) is introduced and completely dissolved, 501 parts by mass of pyromellitic dianhydride (PMDA) and 50 parts by mass of maleic anhydride (MA) as an end-capping agent are obtained. And stirred at a reaction temperature of 25 ° C. for 96 hours, a yellow and viscous polyamic acid solution A was obtained. The properties of the polyamic acid solution are shown in Table 1.
[Synthesis Example 2]
According to the same procedure as in Synthesis Example 1, 493 parts by mass of 4-4 ′ oxydianiline (ODA), 9000 parts by mass of NMP, 483 parts by mass of PMDA, and 48 parts by mass of MA were introduced and stirred for 120 hours. A yellow and viscous polyamic acid solution B was obtained.
[Synthesis Example 3]
According to the same procedure as in Synthesis Example 1, 268 parts by mass of paraphenylenediamine (PDA), 8550 parts by mass of NMP, 659 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) , 48.6 parts by mass of MA were introduced and stirred for 120 hours to obtain a yellow and viscous polyamide acid solution C. The properties of the polyamic acid solution are shown in Table 1.
[Synthesis Example 4]
According to the same procedure as in Synthesis Example 1, 133 parts by mass of paraphenylenediamine (PDA), 246 parts by mass of 4-4′oxydianiline (ODA), 8550 parts by mass of NMP, 483 parts by mass of PMDA, and 48 of MA By introducing part by mass and stirring for 120 hours, a yellow and viscous polyamic acid solution D was obtained.
[Synthesis Example 5]
(Production of epoxy group-containing alkoxysilane partial condensate)
In a reactor equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 200 parts by mass of glycidol and a partial condensate of tetramethoxysilane (manufactured by Tama Chemical Co., Ltd., methyl silicate 51, Si average number 4) 1280 masses Then, the mixture was heated to 90 ° C. with stirring in a nitrogen stream, and then 0.3 parts by mass of dibutyltin dilaurate was added as a catalyst for reaction. During the reaction, when 90 g of methanol produced using a water separator was distilled off, the reaction was cooled. Subsequently, about 10 g of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes to obtain an epoxy group-containing alkoxysilane partial condensate.
(Production of silane-modified polyamic acid resin composition)
900 parts by mass of the polyamic acid of Synthesis Example 4 was heated to 80 ° C., 26 parts by mass of the epoxy group-containing alkoxysilane partial condensate and 0.15 parts by mass of 2-methylimidazole were added as a catalyst, and the reaction was performed at 80 ° C. for 4 hours. did. After cooling to room temperature, a silane-modified polyamic acid solution E was obtained. (Equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate (2)) / (Equivalent of carboxylic acid group of tetracarboxylic acid used for polyamic acid) = 0.07 at the time of preparation.

[Synthesis Example 6]
In a dry nitrogen atmosphere, 333 parts by mass of 3,6-diphenyl-pyromellitic anhydride (DPPMDA) and 489 parts by mass of 2,2′-bis (biphenyl) benzidine (BPBz), maleic anhydride as a terminal blocking agent 10 parts by mass of (MA) was dissolved in m-cresol to obtain a 4% by mass solution. After stirring this at room temperature for 2 hours, isoquinoline was added as a catalyst and stirred at 200 ° C. for 30 minutes under a nitrogen stream to obtain a polyimide solution. The polyimide solution was reprecipitated in 2-propanol to obtain a yellow powdery polymer. The obtained polymer was washed with 2-propanol, dried, and then dissolved in N-methyl-2-pyrrolidone by heating to obtain 10% by mass of polyimide solution F.
[Synthesis Example 7]
After purging the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring bar with nitrogen, 8 mL of a 50:50 volume ratio mixed solution of N-methyl-2-pyrrolidone (NMP) and γ-butyllactone was introduced, After completely dissolving 0.888 g (2.55 mmol) of bis) 4-aminophenyl) terephthalate (BAPT), 0.500 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) (2. 55 mmol) was mixed and stirred, and the viscosity increased vigorously in several minutes. Therefore, the mixture was diluted with 4 ml of the mixed solvent and further stirred for 1 hour to obtain a clear, yellow and viscous polyamide acid solution G. The resin concentration was 10 wt%, the solution viscosity was 57 Pa · s, and the reduced viscosity was 1.8 dL / g.
[Synthesis Example 8]
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 2,2′-bis (trifluoromethyl) benzidine 5 mmol (1.6012 g) was sufficiently dehydrated with molecular sieves 4A, N, After dissolving in 15 mL of N-dimethylacetamide, 5 mmol (1.1208 g) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride powder was gradually added. The mixture was stirred at room temperature for 48 hours to obtain a clear, pale yellow, viscous polyamic acid solution H. The resin concentration was 15 wt%, the solution viscosity was 52 Pa · s, and the reduced viscosity was 1.73 dL / g.
[Synthesis Example 9]
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 411 parts by mass of 2,2′-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), N-methyl- 750 parts by mass of 2-pyrrolidone and 5.08 parts by mass of triethylamine were added and stirred to obtain a solution.
To this, 202 parts by mass of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), 21.8 parts by mass of pyromellitic dianhydride and 204 parts by mass of NMP were added, and then up to 200 ° C. with a mantle heater. The mixture was heated for 30 minutes and kept at 200 ° C. for 5 hours while removing distillate.
After adding 1440 parts by mass of N, N-dimethylacetamide, the mixture was stirred at 130 ° C. for 30 minutes to obtain a homogeneous solution and then air-cooled to 100 ° C. to obtain polyimide solution I. The resin concentration of this solution was 20 wt%, the solution viscosity was 200 Pa · s, and the reduced viscosity was 1.11 dL / g.

(Polyamide acid solution)

(Polyamide acid solution)

[Inorganic layer treatment example 1]
After replacing the inside of the glove box with nitrogen, the coupling agent (3-aminopropyltrimethoxysilane; 3-APS) was diluted to 0.5 wt% with isopropyl alcohol in the glove box flowing N2. After preparing the liquid, an inorganic 8-inch silicon wafer (diameter 20 cm, 0.725 mm thickness) was subjected to ultrasonic cleaning 5 minutes with pure water, ultrasonic cleaning 5 minutes with ethanol, and ultrasonic cleaning 5 minutes with pure water. Set on a spin coater, sprinkle and dry the liquid at 1000 rpm with isopropyl alcohol, and then drop this coupling agent dilution on the center of rotation and rotate to 3000 rpm over 15 seconds, then 15 seconds Rotate at 3000 rpm and stop rotating for 15 seconds Between, and a dry state after wetting the entire surface. This was placed on a hot plate heated to 100 ° C. placed in a clean bench for 1 minute and reacted with the inorganic layer to obtain a treated inorganic layer 1. Table 3 shows the treatment of the inorganic layer. The film thickness of the coupling agent layer was calculated by an ellipsometer by the above method. This time it was 11 nm.
[Inorganic layer treatment example 2]
A treated inorganic layer 2 was obtained in exactly the same manner as in Treatment Example 1, except that the coupling agent was 3-APS and the inorganic layer was glass (Corning EAGLE XG 100 mm × 100 mm 0.7 mm thickness). Table 3 shows the treatment of the inorganic layer.
[Inorganic layer treatment example 3]
Treated inorganic layer 3 was treated in the same manner as in Treatment Example 1, except that the coupling agent was n-propyltrimethoxysilane (n-PS) and the inorganic layer was glass (Corning EAGLE XG 100 mm × 100 mm 0.7 mm thickness). Obtained. Table 3 shows the treatment of the inorganic layer.
[Inorganic layer treatment example 4]
A treated inorganic layer 4 was obtained in the same manner as in Treatment Example 1 except that the coupling agent was not used and the inorganic layer was an 8-inch silicon wafer (diameter 200 mm, 0.725 mm thickness). Table 3 shows the treatment of the inorganic layer.

[Inorganic layer treatment example 5]
A treated inorganic layer 5 was obtained in exactly the same manner as in Treatment Example 1 except that the coupling agent was not used and the inorganic layer was glass (Corning EAGLE XG 100 mm × 100 mm 0.7 mm thickness). Table 3 shows the treatment of the inorganic layer.
[Inorganic layer treatment example 6]
After replacing the inside of the glove box with nitrogen, the coupling agent (3-aminopropyltrimethoxysilane; 3-APS) was diluted to 0.5 wt% with isopropyl alcohol in the glove box flowing N2. After preparing the liquid, an inorganic 8-inch silicon wafer (diameter 20 cm, 0.725 mm thickness) was subjected to ultrasonic cleaning 5 minutes with pure water, ultrasonic cleaning 5 minutes with ethanol, and ultrasonic cleaning 5 minutes with pure water. Then, it was set on a spin coater, and isopropyl alcohol was applied thereto, and the liquid was shaken off and dried at 1000 rpm.
After immersing this coupling agent diluted solution in a sachet with silicone rubber in the part surrounded by a square with an inner side of 80 mm and an outer side with a square of 120 mm, the glass substrate After pressing so that the diluted solution of silane coupling agent is attached to the outer periphery of the surface, rotate to 3000 rpm over 15 seconds, then rotate at 3000 rpm for 15 seconds, and stop rotating for 15 seconds to wet the entire surface. And then dried. This was placed on a hot plate heated to 100 ° C. placed in a clean bench for 1 minute and reacted with the inorganic layer to obtain a treated inorganic layer 1. Table 3 shows the treatment of the inorganic layer. The film thickness of the coupling agent layer was calculated by an ellipsometer by the above method. This time it was 13 nm.
[Inorganic layer treatment example 7]
In the inorganic layer treatment example 6, a square-shaped shape was used, but the outer circumference was 120 mm and the square was the same, but the central portion of this 120 mm square was shaped like a rice field with a 10 mm wide silicone rubber. A treated inorganic layer 5 was obtained in the same manner except that it was pressed after pressing against another glass plate before pressing the coupling agent diluent onto the glass using a stamp (the shape of FIG. 3 (2)). Similarly, when a silicon wafer is treated with a silane coupling agent and then measured by an ellipsometer, the portion where the solder is present has a film thickness of 10 to 13 nm, whereas there is no solder. In the portion, the film thickness was 1 nm or less, and it was spread over the portion of the solder.

(Inorganic layer treatment)

(Example 1)
A SUS plate in which a square with a side of 70 mm is cut out is placed as a mask so as to be in contact with the silicon wafer of the treated inorganic layer 1, and UV irradiation treatment is performed for 2 minutes so that only the central portion of the silicon wafer is exposed to UV light. . Thereafter, the polyamic acid solution A was applied with an applicator. The gap was adjusted so that the film thickness of the polyimide layer was 25 μm. Put in a muffle furnace where N2 is flowing, heat at 80 ° C. for 30 minutes, then heat up to 100 ° C. at 2 ° C./minute, hold at 100 ° C. for 90 minutes to dry and heat up at 5 ° C./minute The temperature was raised from 100 ° C. to 400 ° C., and the temperature was maintained at 400 ° C. for 5 minutes to imidize the polyamic acid solution to obtain a laminate 1. Moreover, by cutting out a rough □ 60 mm of a □ 70 mm portion subjected to UV irradiation in the polyimide layer of the laminate 1 with a cutter and peeling it off with tweezers, the polyimide film 1 was obtained. Thereafter, when the film thickness of the polyimide film was examined, it was actually 24 μm thick. Table 4 shows the evaluation results of the obtained laminate. The film thickness of the coupling agent layer after the UV irradiation treatment was calculated by an ellipsometer by the above method after the UV irradiation treatment for 2 minutes. This time it was impossible to measure.
(Example 2)
A laminate 2 and a polyimide film 2 were obtained in exactly the same manner as in Example 1 except that the inorganic layer was the treated inorganic layer 2 and the gap of the applicator was adjusted so that the film thickness of the polyimide layer was 10 μm. Table 4 shows the evaluation results of the obtained laminate.

(Example 3)
The inorganic layer is the treated inorganic layer 3, the gap of the applicator is adjusted so that the film thickness of the polyimide layer is 30 μm, the central part □ 70 mm of the silicon wafer is masked, and the other part is UV irradiated for 1 minute Except for the above, the laminate 3 and the polyimide film 3 were obtained in the same manner as in Example 1. Table 4 shows the evaluation results of the obtained laminate.
(Example 4)
Lamination was performed in exactly the same manner as in Example 1 except that the inorganic layer was treated inorganic layer 2, the gap of the applicator was adjusted so that the film thickness of the polyimide layer was 25 μm, and the polyamic acid solution was polyamic acid solution B. The body 4 and the polyimide film 4 were obtained. Table 4 shows the evaluation results of the obtained laminate.
(Example 5)
Lamination was performed in exactly the same way as in Example 1 except that the inorganic layer was treated inorganic layer 2, the gap of the applicator was adjusted so that the film thickness of the polyimide layer was 25 μm, and the polyamic acid solution was polyamic acid solution C. The body 5 and the polyimide film 5 were obtained. Table 4 shows the evaluation results of the obtained laminate.

(Example 6)
Lamination was performed in exactly the same way as in Example 1 except that the inorganic layer was treated inorganic layer 2, the gap of the applicator was adjusted so that the film thickness of the polyimide layer was 25 μm, and the polyamic acid solution was polyamic acid solution D. The body 6 and the polyimide film 6 were obtained. Table 5 shows the evaluation results of the obtained laminate.
(Example 7)
A laminate 7 and a polyimide film 7 were obtained in the same manner as in Example 1 except that the inorganic layer was treated inorganic layer 2 and the polyamic acid solution was polyamic acid solution E. Table 5 shows the evaluation results of the obtained laminate.
(Example 8)
The inorganic layer is treated inorganic layer 2, the polyamic acid solution is polyimide solution F, and the inorganic layer coated with the solution is placed in a muffle furnace in which N2 is flowing, and then at 80 ° C. for 30 minutes and then at 2 ° C./minute up to 120 ° C. Raise the temperature, hold at 120 ° C. for 15 minutes, raise the temperature from 120 ° C. to 350 ° C. at a rate of 5 ° C./min, and maintain the temperature at 350 ° C. for 1 hour to dry the laminate. Except for the above, a laminate 7 and a polyimide film 7 were obtained in the same manner as in Example 1. Table 5 shows the evaluation results of the obtained laminate.

(Example 9)
A muffle furnace in which the inorganic layer is treated inorganic layer 2, the polyamic acid solution is polyimide solution G, the gap of the applicator is adjusted so that the thickness of the polyimide layer is 25 μm, and the inorganic layer coated with the solution is flowing N2. Then, the temperature was raised from 80 ° C. to 300 ° C. at a rate of 3 ° C./min at 80 ° C. for 50 minutes, and the laminate was obtained by maintaining the temperature at 300 ° C. for 1 hour and drying. Except for the above, a laminate 8 and a polyimide film 8 were obtained in the same manner as in Example 1. Table 5 shows the evaluation results of the obtained laminate.
(Example 10)
A muffle furnace in which the inorganic layer is treated inorganic layer 2, the polyamic acid solution is polyimide solution H, the gap of the applicator is adjusted so that the thickness of the polyimide layer is 15 μm, and the inorganic layer coated with the solution is flowing N2. The laminate was heated at 60 ° C. for 120 minutes, then heated from 60 ° C. to 330 ° C. at a rate of 3 ° C./min, and maintained at 300 ° C. for 2.5 hours to dry the laminate. Except having obtained, the laminated body 9 and the polyimide film 9 were obtained like Example 1 completely. Table 5 shows the evaluation results of the obtained laminate.
Example 11
The inorganic layer is treated inorganic layer 2, the polyamic acid solution is polyimide solution I, and the inorganic layer coated with the solution is placed in a muffle furnace flowing N2, and heated at 100 ° C. for 60 minutes and then at a rate of 5 ° C./min. The laminate 11 and the polyimide film 11 were completely the same as in Example 1 except that the laminate was obtained by raising the temperature from 100 ° C. to 200 ° C. and maintaining the temperature at 200 ° C. for 300 minutes and drying. Obtained. Table 6 shows the evaluation results of the obtained laminate.

[Synthesis Example 10]
A polycarbonate having a molecular weight of 38,000 obtained by condensation of phosgene and bisphenol A was dissolved in methylene chloride to obtain a 20% solution.
[Synthesis Example 11]
Bisphenol A and bisphenol having a perhydroisophorone skeleton were copolymerized using a phosgene method to obtain an aromatic polycarbonate resin having an average molecular weight of 35,000. The copolymerization ratio was 15 mol% of bisphenol having a perhydroisophorone skeleton with respect to the bisphenol A component, and the glass transition temperature was 172 ° C. The polymer was dissolved in methylene chloride to give a 20% by weight solution.
[Synthesis Example 12]
Bisphenol A and bisphenol having a fluorene skeleton were copolymerized using a phosgene method to obtain an aromatic polycarbonate resin having an average molecular weight of 36000. The copolymerization ratio was 16 mol% of bisphenol having a fluorene skeleton with respect to the bisphenol A component, and the glass transition temperature was 175 ° C. The polymer was dissolved in 1,3-dioxolane to give a 20% by weight solution.
[Synthesis Example 13]
(Polyamide acid polymerization)
In a reaction vessel, 1140 parts by mass of trans 1,4-diaminocyclohexane was dissolved in 34,000 parts by mass of N, N-dimethylacetamide, and then stirred with 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. 2646 parts by mass of the product powder and 218 parts by mass of pyromellitic dianhydride were gradually added. When the formed salt solution was heated in an oil bath at 150 ° C. with vigorous stirring for 5 minutes, a part of the salt began to dissolve, so the reaction vessel was removed from the oil bath and stirred at room temperature for several hours. A clear and viscous polyamic acid solution was obtained.

[Synthesis Example 14]
(Polyamide acid polymerization)
Into a reaction vessel, 2,100 parts by mass of 4,4′-methylenebis (cyclohexylamine) was dissolved in 28600 parts by mass of N-methyl-2-pyrrolidone, and then pyromellitic dianhydride powder 2180 with stirring in a nitrogen stream. Mass parts were gradually added and reacted at 35 ° C. for 8 hours to obtain a transparent and viscous polyamic acid solution.
[Synthesis Example 15]
(Polyamide acid polymerization)
After putting 4966 parts by mass of 3,3′DDS (3,3′-diaminodiphenylsulfone) in a reaction vessel and dissolving in 32551 parts by mass of N-methyl-2-pyrrolidone (NMP), the vessel was cooled with water and stirred. Then, 5,843 parts by mass of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride powder was gradually added. By continuing stirring for 8 hours while cooling with water, a transparent and viscous polyamic acid solution was obtained.
[Synthesis Example 16]
(Polyamideimide)
Trimellitic anhydride; 15 mol, cyclohexanedicarboxylic acid; 15 mol, isophorone diisocyanate; 29.85 mol, potassium fluoride; 0.1 mol, γ-butyrolactone; 9.48 kg are added to the reaction vessel and stirred. The mixture was reacted at 120 ° C for 1.5 hours and further at 190 ° C for 5 hours, and then cooled to room temperature while adding N-methylpyrrolidone to dilute the polymer concentration to 20% by weight. The polymer was gradually added while stirring in water, and the polymer was precipitated while washing, then further stirred and washed at 50 ° C. in ion-exchanged water, filtered, and dried under reduced pressure at 60 ° C. for 10 hours. The logarithmic viscosity of the obtained polyamideimide was 0.70 dl / g. The obtained polyamideimide; 9 kg of toluene; 13.5 kg, ethanol; 13.5 kg of a mixed solvent was stirred and dissolved at 25 ° C. for 10 minutes, and then left to stand for 24 hours for defoaming. 25 wt% polyamide An imide solution was obtained.
[Synthesis Example 17]
(Polyamideimide)
Trimellitic anhydride; 6 mol, cyclohexanedicarboxylic acid; 24 mol, isophorone diisocyanate; 29.85 mol, sodium methoxide; 0.1 mol, γ-butyrolactone; In the same manner as in Example 1, polymerization and dilution were performed to obtain a polyamideimide solution. As a result of reprecipitation and drying of a part of the solution, the polyamidoimide had a logarithmic viscosity of 0.73 dl / g.

(Example 12)
A glass plate (Corning EAGLE XG 650 mm × 830 mm 0.7 mm thickness) as an inorganic layer was submerged in a container filled with a 0.2 wt% isopropyl alcohol solution of n-propyltrimethoxysilane, and the speed was 10 mm per second in a space purged with nitrogen. At the same time, dry nitrogen gas was blown with an air knife to drain the liquid. Then, the glass plate was placed in a 120 ° C. dry oven with nitrogen substituted for 15 minutes, and the process up to this point was treated with a silane coupling agent. The thickness of the silane coupling agent layer measured by ellipsometry when the silicon wafer was processed under the same coating conditions was 40 nm.
A stainless steel metal mask in which rectangular openings of 68 mm × 110 mm are arranged in an array via a 5 mm-width shielding portion is stacked on the obtained glass plate treated with a coupling agent, and a gap is formed between the metal mask and the glass plate. It was confirmed that there was no atmospheric pressure plasma treatment as a patterning treatment in an atmospheric pressure plasma treatment apparatus using a mixed gas of nitrogen 95 / oxygen 5 at a flow rate ratio. The atmospheric pressure plasma processing apparatus has a mechanism of a type in which a slit-like long head automatically moves on a workpiece, and the glass plate is exposed to the plasma for about 45 seconds.
Next, the polycarbonate solution obtained in Synthesis Example 10 was applied using a die coater, dried at 80 ° C. for 30 minutes and 100 ° C. for 90 minutes in a dry oven in which dry nitrogen gas was passed, and then transferred to an inert heat treatment furnace purged with nitrogen. The temperature was raised from 100 ° C. to 200 ° C. at a rate of temperature increase of 5 ° C./minute, held for 1 minute, and then cooled to room temperature at 20 ° C./minute to obtain a laminate. The thickness of the resin layer of the laminate was 40 μm.
The 180-degree peel strength of the resin layer at the mask portion of the obtained laminate was 3.5 N / cm. On the other hand, the 180 degree peel strength at the non-mask portion was 0.46 N / cm.
As a simulation process of thin film transistor array fabrication using amorphous silicon, a silicon oxide layer, a source and a drain electrode are formed on the obtained laminated plate by a reactive sputtering method as a planarization layer and gas barrier layer using a predetermined test pattern. A tantalum layer, a barrier metal layer, and an amorphous silicon layer as a semiconductor layer were stacked by a sputtering method and a CVD method, respectively, and then a SiN layer as a gate insulating layer and aluminum as a gate electrode layer. Each layer is patterned by masking or photolithography according to a predetermined test pattern to form a simulated device: thin film transistor array. The device portion is formed in the opening portion of the metal mask during the patterning process. During the above process, it was exposed to a vacuum atmosphere, a resist solution, a developing solution, an etching solution, and a stripping solution used in the photolithographic method, but the resin layer did not peel from the glass layer, and the process suitability was good. It was.
Subsequently, according to the pattern of the metal mask used at the time of the patterning process, the resin layer was cut at the boundary between the mask shielding part and the opening part, and the part where the device was formed was peeled off. Peeling could be easily performed by slightly raising the end with a blade. Although it tried to peel similarly about the 5 mm width part which was shielded, it was difficult to peel so that a resin layer might not be destroyed.

(Example 13)
The silane coupling agent treatment in Example 12 was changed to the spin coating method, the solution was changed to the solution obtained in Synthesis Example 11, and the atmospheric pressure plasma treatment was performed in the same manner except that the blast treatment was performed. A simulation process experiment of thin film transistor array fabrication using amorphous silicon was conducted.
The silane coupling agent treatment by the spin coater was performed according to the following procedure. A glass plate (Corning EAGLE XG 300 mm × 300 mm 0.7 mm thickness) is mounted on a spin coater manufactured by Japan Create, and n-propyltrimethoxysilane is used as a silane coupling agent, and a 0.1 wt% isopropyl alcohol solution is used. The glass plate was used for coating, and then the glass plate was dried and heat-treated for 10 minutes in a dry oven at 100 ° C. in which the nitrogen plate was replaced with dry nitrogen. The thickness of the silane coupling agent layer measured by ellipsometry when the silicon wafer was processed under the same coating conditions was 40 nm.
A small wet blasting machine manufactured by Macau Corporation was used for the blasting, water was used as the medium, and # 2000 silica particles were used as the abrasive. Blasting was carried out through a mask, and after blasting, the glass plate was rinsed with ultrapure water, dried with dry air, and proceeded to a polyamic acid solution coating step with a die coater as the next step.
As a result, the 180-degree peel strength of the resin layer at the mask portion of the obtained laminate was 4.7 N / cm. On the other hand, the 180 degree peel strength at the non-mask portion was 1.03 N / cm. There was no problem in process passability, and the peelability of the weakly bonded part was also good.

(Example 14)
The silane coupling agent treatment in Example 12 is changed to the spin coating method of Example 13, the solution is changed to the solution obtained in Synthesis Example 12, and the atmospheric pressure plasma treatment is replaced with the blast treatment of Example 13. Except for the above, the same process was carried out, and a simulation process experiment for fabricating a thin film transistor array using amorphous silicon was conducted.
As a result, the 180-degree peel strength of the resin layer at the mask portion of the obtained laminate was 4.1 N / cm. On the other hand, the 180 degree peel strength at the non-mask portion was 0.34 N / cm. There was no problem in process passability, and the peelability of the weakly bonded part was also good.

(Example 15)
The silane coupling agent treatment in Example 12 was changed to the spin coating method shown in Example 13, the solution was changed to the polyamic acid solution obtained in Synthesis Example 13, and the atmospheric pressure plasma treatment was changed to vacuum plasma treatment. Other than that, the same processing was carried out, and the patterning process was advanced. Vacuum plasma processing was performed using a single-wafer glass device, and a metal mask was placed on the glass silane coupling agent-treated surface, which was then set in the device. The chamber is evacuated to 1 × 10 −3 Pa or less, argon gas is introduced into the vacuum chamber, and the argon gas plasma treatment is performed on the glass plate surface for 20 seconds under the conditions of a discharge power of 100 W and a frequency of 15 kHz. It was. Thereafter, the process proceeds to a polyamic acid solution coating step using a die coater, which is the next step, and the polyamic acid solution obtained in Synthesis Example 13 is coated and dried at 80 ° C. for 30 minutes and 100 ° C. 90 ° C. in a dry oven in which dry nitrogen gas is passed. Then, it is transferred to an inert heat treatment furnace which is purged with nitrogen, heated from 100 ° C. to 280 ° C. at a heating rate of 5 ° C./min, held for 5 minutes, cooled to room temperature at 20 ° C./min, and laminated. Got the body. The thickness of the resin layer of the laminate was 35 μm. Thereafter, a simulation process experiment for manufacturing a thin film transistor array using amorphous silicon was conducted in the same manner. Through the prescribed process. As a result, the 180 ° peel strength of the polyimide layer at the mask portion of the obtained laminate was 5.4 N / cm. On the other hand, the 180 degree peel strength at the non-mask portion was 0.35 N / cm. There was no problem in process passability, and the peelability of the weakly bonded part was also good.

(Example 16)
A vacuum plasma treatment in Example 15 was replaced with a corona treatment, and the treatment was performed in the same manner except that the solution was changed to the polyamic acid solution obtained in Synthesis Example 14, and a simulation process experiment for fabricating a thin film transistor array using amorphous silicon was conducted. It was.
Using a corona treatment device manufactured by Kasuga Denki, electric power with a discharge amount of 1000 W was applied and treatment was performed at 10 W / m ² / min. In this experiment, an acrylic plate having a thickness of 0.5 mm processed in the same shape as the metal mask was used instead of the metal mask. Thereafter, the process proceeded to a polyamic acid solution coating step using a die coater, which was the next step, and passed through a predetermined process. As a result, the 180 degree peel strength of the polyimide layer at the mask portion of the obtained laminate was 4.6 N / cm. On the other hand, the 180 degree peel strength at the non-mask portion was 1.8 N / cm. There was no problem in process passability, and the peelability of the weakly bonded part was also good.
(Example 17)
The silane coupling agent in Example 15 was changed to 3-aminopropyltrimethoxysilane, the polyamic acid solution was changed to the polyamic acid solution obtained in Synthesis Example 15, and atmospheric pressure plasma treatment was performed using active gas treatment (chlorine gas). Except for the above, the same process was performed, and a simulation process experiment for fabricating a thin film transistor array using amorphous silicon was conducted.
The active gas treatment using chlorine gas was performed according to the following procedure. First, set a glass that has been treated with a silane coupling agent on a glass that can be depressurized with a metal mask overlaid, depressurize the chamber, and then introduce a mixed gas of 95% nitrogen gas and 5% chlorine gas into the chamber. Introduced and held for 30 seconds after reaching the state where the chamber was filled with a mixed gas of 1 atm for flow rate calculation, stopped supplying chlorine gas, continued supplying nitrogen gas for 60 seconds, and then supplied nitrogen gas Then, the inside of the chamber was depressurized again, once returned to normal pressure with dry air, once again depressurized again and returned to normal pressure, and the glass plate was taken out from the chamber.
Thereafter, the process proceeded to a polyamic acid solution coating step using a die coater, which was the next step, and passed through a predetermined process. As a result, the 180 degree peel strength of the polyimide layer at the mask portion of the obtained laminate was 4.2 N / cm. On the other hand, the 180 degree peel strength at the non-mask portion was 0.75 N / cm. There was no problem in process passability, and the peelability of the weakly bonded part was also good.

(Example 18)
The solution in Example 15 was changed to the polyamideimide solution obtained in Synthesis Example 16, and the same treatment was performed except that the vacuum plasma treatment was replaced with an active gas treatment (ozone gas), and a thin film transistor array using amorphous silicon was manufactured. A simulated process experiment was conducted.
The active gas treatment with ozone was performed as follows. First, set a glass that has been treated with a silane coupling agent in a evacuable chamber with a metal mask overlaid, depressurize the chamber, and then generate an ozone generator (PSA Ozonizer SGA-01-PSA2, Sumitomo Precision Industries, Ltd.) The ozone gas was introduced into the chamber from the product), and after maintaining for 60 seconds after the chamber reached a state filled with one atmosphere of ozone for flow rate calculation, the supply of ozone gas was stopped, the inside of the chamber was depressurized and dried again The glass plate was taken out from the chamber after returning to normal pressure once with air, reducing pressure again, and returning to normal pressure again.
Thereafter, the process proceeded to a polyamic acid solution coating step using a die coater, which was the next step, and passed through a predetermined process. As a result, the 180 ° peel strength of the polyamideimide layer at the mask portion of the obtained laminate was 5.2 N / cm. On the other hand, the 180-degree peel strength at the non-mask portion was 0.7 N / cm. There was no problem in process passability, and the peelability of the weakly bonded part was also good.

(Example 19)
A thin film transistor array using amorphous polysilicon was manufactured in the same manner as in Example 15 except that the vacuum plasma treatment was changed to direct drawing with laser light and the solution was changed to the polyamideimide solution obtained in Synthesis Example 17. A simulated process experiment was conducted.
A YAG laser marking device was used as a direct writing device using laser light, and a patterning process was performed by scanning a portion corresponding to the opening of the metal mask with YAG laser light. The output of the YAG laser light was 1/10 of the power that allows marking on the glass.
Thereafter, the process proceeded to a polyamic acid solution coating step using a die coater, which was the next step, and passed through a predetermined process. As a result, the 180 ° peel strength of the polyamideimide layer at the mask portion of the obtained laminate was 3.8 N / cm. On the other hand, the 180 degree peel strength at the non-mask portion was 0.52 N / cm. There was no problem in process passability, and the peelability of the weakly bonded part was also good.

(Comparative Example 1)
Except having changed the inorganic layer into the processed inorganic layer 4, the laminated body 11 and the polyimide film 11 were obtained like Example 1 completely. Table 7 shows the evaluation results of the obtained laminate.
(Comparative Example 2)
Except having changed the inorganic layer into the processed inorganic layer 5, the laminated body 12 and the polyimide film 12 were obtained like Example 1 completely. Table 7 shows the evaluation results of the obtained laminate.
(Comparative Example 3)
A laminate 13 was obtained in the same manner as in Example 1 except that the inorganic layer was not subjected to UV irradiation treatment. Table 7 shows the evaluation results of the obtained laminate.
(Comparative Example 4)
A laminate 14 was obtained in the same manner as in Example 1 except that the inorganic layer was treated inorganic layer 2 and UV irradiation treatment was not performed on the inorganic layer. Table 7 shows the evaluation results of the obtained laminate.

(Comparative Example 5)
A laminate 15 was obtained in the same manner as in Example 5 except that the inorganic layer was not subjected to UV irradiation treatment. Table 8 shows the evaluation results of the obtained laminate.
(Comparative Example 6)
A laminate 16 was obtained in exactly the same manner as in Example 6 except that the inorganic layer was not subjected to UV irradiation treatment. Table 8 shows the evaluation results of the obtained laminate.

(Measurement examples 1 to 5)
Use 5 pieces of silicon wafer cut to □ 50 mm as the substrate, and after performing ultrasonic cleaning with pure water for 5 min, ultrasonic cleaning with ethanol for 5 min, and ultrasonic cleaning with pure water for 5 min, set them on the spin coater. Then, the solution was shaken off and dried at 1000 rpm by applying isopropyl alcohol, and subsequently, the same coating agent application and reaction with the inorganic layer as in the inorganic layer treatment example 1 were performed. Thereafter, samples were prepared by irradiating the silicon wafer coated with the coupling agent with UV irradiation times of 0 sec, 10 sec, 30 sec, 120 sec, and 1800 sec, respectively. The surface composition ratios at this time are summarized in Table 9.

When 3-aminopropyltrimethoxysilane having a functional group is applied to a silicon wafer, a portion not subjected to UV irradiation treatment becomes a good adhesion portion, and a UV irradiation treatment portion becomes an easy peeling portion (Example 1). It is known that ozone and active oxygen are generated when the UV irradiation treatment is performed. From measurement examples 1 to 5, when the UV irradiation treatment is performed, the atomic percentage of the nitrogen (N) element is lowered, and then carbon ( The decrease in C) suggests the decomposition of the aminopropyl group. By performing a coupling agent treatment having a functional group, the adhesive strength is increased and a good adhesion portion is obtained. However, by performing UV irradiation treatment, reaction by ozone or active oxygen atoms proceeds, the aminopropyl group is decomposed, and the inorganic layer It is considered that the adhesive strength between the polyimide layer and the polyimide layer was lowered, and easy peelability was observed.
On the other hand, when an inorganic layer such as n-propyltrimethoxysilane is applied to the inorganic layer, the part that has not been subjected to UV irradiation treatment becomes an easily peelable part, and the part that has undergone UV irradiation treatment has good adhesion (Example 3). From Measurement Examples 1 to 5, oxygen (O) is increased by UV irradiation treatment, suggesting oxidation of the propyl group portion. The adhesive strength of the polyimide layer to the alkyl group such as propyl group is low and it becomes an easily peelable part, but the UV irradiation treatment generated functional groups such as aldehyde group, carboxyl group, or carboxylic acid group from the alkyl group, so UV irradiation It is thought that the part became a good adhesion part.

[Application Example 1]
The laminates obtained in Example 5 and Comparative Example 2 were covered with a stainless steel frame having an opening and fixed to a substrate holder in the sputtering apparatus. The substrate holder and the inorganic layer are fixed so as to be in close contact with each other. For this reason, the temperature of the film can be set by flowing a coolant through the substrate holder. The substrate temperature was set at 2 ° C. Next, plasma treatment of the polyimide layer surface was performed. The plasma treatment conditions were argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 × 10 −3 Torr, treatment temperature 2 ° C., treatment time 2 minutes. Next, using a target of a frequency of 13.56 MHz, an output of 450 W, a gas pressure of 3 × 10 −3 Torr, a nickel-chromium (chromium 10 mass%) alloy target, a DC magnetron sputtering method in an argon atmosphere was performed at 1 nm / second. A nickel-chromium alloy film (underlayer) having a thickness of 7 nm is formed at a rate, and then a coolant whose temperature is controlled to 2 ° C. on the back side of the sputter surface of the substrate is flown into the substrate so that the substrate temperature is set to 2 ° C. Sputtering was performed in contact with the SUS plate of the substrate holder. Copper was deposited at a rate of 10 nm / second to form a copper thin film having a thickness of 0.25 μm. The base metal thin film formation laminated body from each film was obtained. The thickness of the copper and NiCr layers was confirmed by the fluorescent X-ray method.
Then, the base metal thin film formation laminated body from each laminated body was fixed to the frame made from Cu, and the thick copper layer was formed using the copper sulfate plating bath. The electrolytic plating conditions were immersed in an electrolytic plating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, a small amount of brightener), and electricity was passed through 1.5 Adm2. As a result, a thick copper plating layer (thickening layer) having a thickness of 4 μm was formed, followed by heat treatment and drying at 120 ° C. for 10 minutes to obtain a metallized laminate.
Using the obtained metallized laminate, photoresist: FR-200, manufactured by Shipley Co., Ltd. was applied and dried, and then contact-exposed with a glass photomask, and further developed with a 1.2 mass% KOH aqueous solution. Next, etching is performed with a cupric chloride etching line containing HCl and hydrogen peroxide at 40 ° C. and a spray pressure of 2 kgf / cm 2, and a line string of lines / spaces = 20 μm / 20 μm is formed as a test pattern. Electroless tin plating was performed to a thickness of 5 μm. Thereafter, annealing was performed at 125 ° C. for 1 hour. The pattern from the resin layer was evaluated by observing drool, pattern residue, pattern peeling, etc. with an optical microscope.

From the resin film laminate of Example 5, a good pattern with no pattern residue and pattern peeling was obtained. In addition, even if the film was heated to 400 ° C. at a rate of temperature increase of 10 ° C./min in a muffle furnace substituted with nitrogen, the film was kept at 400 ° C. for 1 hour, and then naturally cooled, so that no blistering or peeling occurred. .
After that, even when peeling from the inorganic layer, pattern peeling or the like did not occur. As a result, a resin film with a wiring pattern was obtained.
From the resin film laminate of Comparative Example 2, film peeling, dripping, pattern residue, and pattern peeling were observed, and a good pattern was not obtained.

[Application 2]

As an example of creating a display panel, a structure as shown in FIG. 4 is used.
On the insulating substrate, Al is formed by sputtering at 200 nm and patterned to form a gate wiring bus line, a gate electrode, and a gate wiring. At this time, each gate wiring is connected to the gate wiring bus line. This gate wiring bus line is used as a power supply line during anodization. Thereafter, 3 μm of photoresist is applied and the resists in the regions A and B are removed by a photoetching process. Region A is the TFT portion. Bha wiring intersection. In this state, the substrate is immersed in a chemical conversion solution, and a voltage of +72 V is applied to the bus line of the gate wiring for 30 minutes, so that 70 nm of Al in the regions A and B becomes Al2O3, and an Al2O3 film of about 100 nm is obtained. It is done. As a chemical conversion solution, a 3% tartaric acid solution was diluted with ethylene glycol, and ammonia water was added to adjust the pH to 7.0. After removing the resist, heating is performed in the atmosphere at 200 ° C. for 1 hour. This is intended to reduce the leakage current of the Al2O3 film.
On top of this, 300 nm of silicon nitride is formed by plasma CVD, and 100 nm of hydrogenated amorphous silicon (a-Si) and 200 nm of second silicon nitride are formed. The substrate temperature at this time was 380 ° C. After this, the second silicon nitride was patterned so that only the wiring intersections were on the TFT channel.
An amorphous silicon n layer doped with about 2% phosphorous is deposited to a thickness of 50 nm and patterned, leaving only the source and drain portions of the TFT. At this time, a-Si is also removed at the same time. Cr is deposited to 100 nm and Al 500 nm is deposited by sputtering and patterned to form signal lines, TFT drains, source wires, and the like. The gate wiring bus lines previously formed in this Al conversion work are removed to separate each gate wiring.
Next, ITO as a transparent electrode is formed by 100 nm sputtering to form pixel electrodes, terminals, and the like. Finally, about 1 μm of silicon nitride is deposited by plasma CVD,
The silicon nitride in the terminal portion is removed by a photoetching process to complete the TFT substrate.
A light emitting layer is formed on the pixel electrode. Here, an organic layer containing poly (para-phenylene vinylene) which is not doped as a light-emitting substance was formed by a screen printing method. The drying temperature of the membrane is a maximum of 180 ° C. Finally, ITO was sputtered on the light emitting layer as a second electrode, and a fluororesin coating was performed to form a protective film, thereby producing a display device using an organic EL element. At this time, the substrate temperature is heated to 350 ° C. (Fig. 5)
When an alternating voltage of 1000 Hz having a peak-to-peak of 60 V was applied to the organic EL element-use display device using the obtained laminate of Example 1, light emitted bright green. Similarly, a self-luminous display device is manufactured using other films, and good light emission is obtained in the display device of the example, but sufficient light emission is not obtained in the display device of the comparative example. . This is presumed to be because the conductive layer, particularly the transparent conductive layer, was damaged due to inferior flatness maintenance at a high temperature of the film used by increasing and decreasing the temperature during the process.

The laminate obtained by the production method of the present invention is obtained by reaction of one surface of a kind of inorganic layer selected from a glass plate, a ceramic plate, a silicon wafer, and a metal, and an aromatic tetracarboxylic acid and an aromatic diamine. , A polyimide layer and a laminated body bonded without an adhesive layer,
The polyimide film with a device obtained by the production method of the present invention can be made by easily peeling off a polyimide layer at an easily peelable portion obtained by using the laminate, and then peeling off the polyimide layer with a device.
The laminate of the present invention can be effectively used in the process of manufacturing a fine circuit board on ultra-thin polyimide film, a device structure, etc., and has a heat-resistant laminate that can withstand the temperature rising process such as metallization. In the subsequent pattern creation, since the dimensional change is small, a circuit pattern with a small error can be obtained. Furthermore, if necessary, this inorganic substrate can be peeled off smoothly, and circuits and devices can be accurately formed on a very thin polyimide film with excellent insulation, heat resistance, and dimensional stability. It is effective for manufacturing devices such as plates and sensors.

(Figure 1)
1: Glass substrate 2: Silane coupling agent layer 3: UV light blocking mask 4: Silane coupling agent layer UV irradiation untreated portion 5: Silane coupling agent layer UV irradiation treatment portion 6: Resin layer 7: Silane coupling agent Resin film on layer UV irradiation treatment part (Fig. 2)
1: Glass substrate 2: Silane coupling agent layer 3: UV light blocking mask 4: Silane coupling agent layer UV light non-irradiated part 5: Silane coupling agent layer UV light irradiated part 6: Resin layer 7: Silane coupling agent Resin film 8 on layer UV light irradiation part: circuit (FIG. 3)
1: Silane coupling agent layer UV irradiation untreated portion 2: Silane coupling agent layer UV irradiation treatment portion (FIG. 4)

1. Substrate (support)
2. Al
3. Anodized film (Al2O3)
4). Silicon nitride (1)
5. 5. Hydrogenated amorphous silicon Silicon nitride (2)
7. Amorphous silicon n layer 8. Cr
9. Gate wiring 10. Signal line 11. Gate wiring bus line 12. Transparent electrode A TFT part B Wiring intersection (Figure 5)
1. Substrate (support)
2. First electrode Light emitting layer 4. Second electrode 5. Bulkhead 6. Protective film

Claims (9)

At least a method for producing a laminate comprising an inorganic layer and a resin layer,
The manufacturing method of the laminated body characterized by including the process of following (1)-(3).
(1) A step of treating the surface of at least one side of the inorganic layer with a coupling agent (2) By performing a patterning treatment on at least one side of the inorganic layer treated with the coupling agent according to a predetermined pattern, The process of providing the part from which the peeling strength between resin layers differs.
(3) A step of drying and heat-treating a coating solution layer obtained by coating a resin solution or a resin precursor solution on the patterned inorganic layer-treated surface of the coupling agent, and forming the resin layer;   The patterning process is performed after covering or shielding a predetermined portion, and includes at least a blast process, a vacuum plasma process, an atmospheric pressure plasma process, a corona process, an actinic radiation irradiation process, an active gas process, and a chemical solution process. The method for producing a laminate according to claim 1, wherein the process is one or more selected.   The method for producing a laminate according to claim 1, wherein the patterning process is a UV irradiation process. The manufacturing method of the laminated body in any one of Claims 1-3 which this resin layer consists of a polyimide obtained by making aromatic diamines and aromatic tetracarboxylic acids react. The laminate according to any one of claims 1 to 4, wherein the resin layer has a thickness of 0.5 µm to 50 µm, and a linear expansion coefficient in the surface direction of the resin layer is -2 ppm / ° C to +35 ppm / ° C. Manufacturing method. It is a laminate of an inorganic layer and a resin layer, and has a coupling agent layer between the inorganic layer and the resin layer, and a well-bonded portion and an easily peelable portion of the inorganic layer and the resin layer are predetermined. The 180 degree peel strength between the inorganic layer and the resin layer is 1 N / cm or more at the good adhesion portion, and the difference in peel strength between the good adhesion portion and the easy peel portion is a good adhesion portion. It is 50% or more with respect to the peeling strength of this, The manufacturing method of the laminated body in any one of Claims 1-5 characterized by the above-mentioned. The thickness of this coupling agent layer is 100 nm or less, The manufacturing method of the laminated body in any one of Claims 1-6 characterized by the above-mentioned.   The laminate produced by the method for producing a laminate according to any one of claims 1 to 7, wherein the adhesive peel strength of the inorganic layer and the resin layer is different, and divided into a good adhesion portion and an easy peel portion according to a pattern. A laminate characterized by having After forming a device on the resin layer surface of the easily peelable portion of the resin layer of the laminate using the laminate according to claim 8, the resin film in which the devices are laminated by cutting out and peeling off the easily peelable portion How to get.